U.S. patent application number 15/174421 was filed with the patent office on 2016-09-29 for catalyst for olefin polymerization, method for producing olefin polymer, method for producing propylene-based copolymer, propylene polymer, propylene-based polymer composition, and use of those.
This patent application is currently assigned to MITSUI CHEMICALS, INC.. The applicant listed for this patent is MITSUI CHEMICALS, INC.. Invention is credited to Shigenobu IKENAGA, Hiromasa MARUBAYASHI, Ryoji MORI, Kouji NAGAHASHI, Takashi NAKAGAWA, Masahiko OKAMOTO, Shiro OTSUZUKI, Yasushi TOHI.
Application Number | 20160280819 15/174421 |
Document ID | / |
Family ID | 37431331 |
Filed Date | 2016-09-29 |
United States Patent
Application |
20160280819 |
Kind Code |
A1 |
TOHI; Yasushi ; et
al. |
September 29, 2016 |
CATALYST FOR OLEFIN POLYMERIZATION, METHOD FOR PRODUCING OLEFIN
POLYMER, METHOD FOR PRODUCING PROPYLENE-BASED COPOLYMER, PROPYLENE
POLYMER, PROPYLENE-BASED POLYMER COMPOSITION, AND USE OF THOSE
Abstract
A catalyst for olefin polymerization, comprising: (A-1) a
bridged metallocene compound represented by the following Formula
[1-1], and (b) at least one compound selected from: (b-1) an
organoaluminum oxy compound, (b-2) a compound which forms an ion
pair, and (b-3) an organoaluminum compound: ##STR00001## wherein in
Formula [1-1], R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.8, R.sup.9, and R.sup.12 are each selected from a hydrogen, a
hydrocarbon group and a silicon-containing group; the four groups
of R.sup.6, R.sup.7, R.sup.10, and R.sup.11 are not hydrogen atoms,
and are each selected from a hydrocarbon group or a
silicon-containing group; R.sup.13 and R.sup.14 are each a
hydrocarbon group or the like, excluding a hydrogen atom and a
methyl group; M is Ti, Zr or the like; Y is carbon or the like; Q
is a halogen or the like; and j is an integer from 1 to 4.
Inventors: |
TOHI; Yasushi;
(Ichihara-shi, JP) ; OKAMOTO; Masahiko;
(Chiba-shi, JP) ; MORI; Ryoji; (Ichihara-shi,
JP) ; NAKAGAWA; Takashi; (Ichihara-shi, JP) ;
IKENAGA; Shigenobu; (Ichihara-shi, JP) ; MARUBAYASHI;
Hiromasa; (Chigasaki-shi, JP) ; NAGAHASHI; Kouji;
(Kuga-gun, JP) ; OTSUZUKI; Shiro;
(Hatsukaichi-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
MITSUI CHEMICALS, INC. |
Tokyo |
|
JP |
|
|
Assignee: |
MITSUI CHEMICALS, INC.
Tokyo
JP
|
Family ID: |
37431331 |
Appl. No.: |
15/174421 |
Filed: |
June 6, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11984440 |
Nov 16, 2007 |
9382356 |
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15174421 |
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PCT/JP2006/309972 |
May 18, 2006 |
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11984440 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08F 4/65912 20130101;
C08L 23/142 20130101; C08F 210/06 20130101; C08F 2500/17 20130101;
C08L 2203/00 20130101; C08F 2800/10 20130101; C08F 4/65908
20130101; C08F 210/06 20130101; C08F 2500/03 20130101; C08L 23/14
20130101; C08J 2323/10 20130101; C08L 23/14 20130101; C08F 210/06
20130101; C08L 2314/06 20130101; C08F 10/00 20130101; C08L 2207/04
20130101; C08F 2500/01 20130101; C08F 2500/16 20130101; C08F 210/06
20130101; C08F 2420/00 20130101; C08J 5/18 20130101; C08L 2205/03
20130101; C08F 2500/11 20130101; Y10T 428/1397 20150115; C08L 23/14
20130101; C08L 2207/12 20130101; C08F 4/65916 20130101; C08L
2203/16 20130101; C08L 2205/025 20130101; C08F 2500/03 20130101;
C08F 2500/26 20130101; C08F 2500/11 20130101; C08F 2500/16
20130101; C08F 210/16 20130101; C08F 2500/12 20130101; C08F 2500/03
20130101; C08F 2500/20 20130101; C08F 2500/16 20130101; C08L
23/0815 20130101; C08F 2500/26 20130101; C08F 210/08 20130101; C08F
4/65927 20130101; C08F 2500/03 20130101; C08F 2500/16 20130101;
C08F 2500/20 20130101; C08F 2500/12 20130101; C08L 23/142 20130101;
C08F 210/16 20130101; C08F 210/08 20130101; C08F 2500/11 20130101;
C08F 2500/12 20130101; C08F 2500/20 20130101; C08F 2500/11
20130101; C08L 23/142 20130101; C08F 10/00 20130101; C08F 2500/26
20130101 |
International
Class: |
C08F 210/06 20060101
C08F210/06; C08L 23/14 20060101 C08L023/14 |
Foreign Application Data
Date |
Code |
Application Number |
May 18, 2005 |
JP |
2005-144873 |
Jul 25, 2005 |
JP |
2005-214685 |
Nov 9, 2005 |
JP |
2005-324814 |
Jan 20, 2006 |
JP |
2006-012494 |
Jan 20, 2006 |
JP |
2006-012970 |
Jan 20, 2006 |
JP |
2006-012971 |
Feb 24, 2006 |
JP |
2006-047857 |
Apr 13, 2006 |
JP |
2006-111398 |
Apr 13, 2006 |
JP |
2006-111399 |
Apr 20, 2006 |
JP |
2006-116963 |
May 1, 2006 |
JP |
2006-127890 |
May 1, 2006 |
JP |
2006-127891 |
Nov 17, 2006 |
JP |
2006-312233 |
Nov 22, 2006 |
JP |
2006-316026 |
Claims
1. A propylene-based polymer composition (X1) comprising: 10 to 95
parts by weight of a syndiotactic propylene polymer (AA) and 90 to
5 parts by weight of a propylene..alpha.-olefin copolymer (B2)
(provided that the sum of amounts of (AA) and (B2) is 100 parts by
weight), wherein the polymer (AA) satisfies the following
requirement (a), and the copolymer (B2) satisfies the following
requirement (b): (a) the syndiotactic pentad fraction (rrrr
fraction) as measured by .sup.13C-NMR is 85% or greater, the
melting point (Tm) as determined by DSC is 145.degree. C. or
higher, and constituent units derived from propylene is contained
in an amount of more than 90 mol % (provided that the total amount
of the constituent units in the polymer (AA) is 100 mol %); (b)
constituent units derived from propylene is contained in an amount
of 55 to 90 mol %, constituent units derived from at least one
olefin selected from .alpha.-olefins having 2 to 20 carbon atoms
(excluding propylene) is contained in an amount of 10 to 45 mol %
(provided that the sum of amounts of the constituent units derived
from propylene and the constituent units derived from the
.alpha.-olefin having 2 to 20 carbon atoms (excluding propylene) is
100 mol %), the MFR measured according to JIS K-6721 at 230.degree.
C. under a load of 2.16 kg is in the range of 0.01 to 100 g/10 min,
and at least one of the following requirements (b-1) and (b-2) is
satisfied; (b-1) the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater; and (b-2) the intrinsic
viscosity [.eta.] (dL/g) as measured in decalin at 135.degree. C.
and the MFR (g/10 min, 230.degree. C., under a load of 2.16 kg)
satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.2-
0).
2. The propylene-based polymer composition (X1) according to claim
1, which comprises: 50 parts by weight or more and 95 parts by
weight or less of the syndiotactic propylene polymer (AA), and 5
parts by weight or more and 50 parts by weight or less of the
propylene..alpha.-olefin copolymer (B2) (the sum of amounts of (AA)
and (B2) is 100 parts by weight).
3. The propylene-based polymer composition (X1) according to claim
1, which comprises: 10 parts by weight or more and less than 50
parts by weight of the syndiotactic propylene polymer (AA), and
more than 50 parts by weight and 90 parts by weight or less of the
propylene..alpha.-olefin copolymer (B2) (the sum of amounts of (AA)
and (B2) is 100 parts by weight).
4. The propylene-based polymer composition (X1) according to claim
1, which has (1) a half-crystallization time (t.sub.1/2) during
isothermal crystallization at 110.degree. C. as determined by
differential scanning calorimetry in the range of 1,000 sec or
less.
5. The propylene-based polymer composition (X1) according to claim
1, which has (2) a needle penetration temperature of 145.degree. C.
or higher.
6. The propylene-based polymer composition (X1) according to claim
2, which has: (2) a needle penetration temperature of 145.degree.
C. or higher, (3) an Izod impact strength at 0.degree. C. of 50 J/m
or larger, (4) a tensile modulus in the range of 100 MPa to 2,000
MPa, and (5) an internal haze value of a press sheet having a
thickness of 1 mm of 50% or less.
7. The propylene-based polymer composition (X1) according to claim
3, which has: (2) a needle penetration temperature of 145.degree.
C. or higher, (4) a tensile modulus in the range of 1 MPa to 400
MPa, and (5) an internal haze value of a press sheet having a
thickness of 1 mm of 30% or less.
8. The propylene-based polymer composition (X1) according to claim
1, wherein the syndiotactic propylene polymer (AA) has an intrinsic
viscosity [.eta.] measured in decalin at 135.degree. C. in the
range of 0.1 to 10 dL/g, and a heat of fusion (.DELTA.H) determined
by differential scanning calorimetry (DSC) of 40 mJ/mg or
greater.
9. The propylene-based polymer composition (X1) according to claim
1, wherein the propylene..alpha.-olefin polymer (B2) has a
molecular weight distribution (Mw/Mn, Mn: number average molecular
weight, Mw: weight average molecular weight) as determined by GPC,
of 3.5 or less.
10. Pellets comprising a propylene-based polymer composition (W),
said composition (W) comprising: 1 to 65 parts by weight of a
syndiotactic propylene polymer (AA1), and 99 to 35 parts by weight
of a propylene..alpha.-olefin copolymer (B21) (provided that the
sum of amounts of (AA1) and (B21) is 100 parts by weight), wherein
the polymer (AA1) satisfies the following requirement (a1), and the
copolymer (B21) satisfies the following requirement (b1): (a1) the
syndiotactic pentad fraction (rrrr fraction) as measured by
.sup.13C-NMR is 85% or greater, the melting point (Tm) as
determined by DSC is 145.degree. C. or higher, and constituent
units derived from propylene are contained in an amount of more
than 90 mol % (provided that the total amount of the constituent
units in the polymer (AA1) is 100 mol %), (b1) constituent units
derived from propylene are contained in an amount of 55 to 90 mol
%, constituent units derived from at least one olefin selected from
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene)
are contained in an amount of 10 to 45 mol % (provided that the sum
of amounts of the constituent units derived from propylene and the
constituent units derived from the .alpha.-olefin having 2 to 20
carbon atoms (excluding propylene) is 100 mol %), the MFR measured
according to JIS K-6721 at 230.degree. C. under a load of 2.16 kg
is in the range of 0.01 to 100 g/10 min, and at least one of the
following requirements (b1-1) and (b1-2) is satisfied: (b1-1) the
syndiotactic triad fraction (rr fraction) as measured by
.sup.13C-NMR is 60% or greater. (b1-2) the intrinsic viscosity
[.eta.] (dL/g) as measured in decalin at 135.degree. C. and the MFR
(g/10 min, 230.degree. C., under a load of 2.16 kg) satisfy the
following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.2-
0).
11. A propylene-based polymer composition (X2) comprising: 100 to
25 parts by weight of a syndiotactic propylene polymer (AA), 0 to
75 parts by weight of a propylene..alpha.-olefin copolymer (B2)
(provided that the sum of amounts of (AA) and (B2) is 100 parts by
weight), and 1 to 100 parts by weight of an ethylene..alpha.-olefin
copolymer (C0) based on 100 parts by weight of the sum of amounts
of (AA) and (B2), wherein the polymer (AA) satisfies the following
requirement (a), the polymer (B2) satisfies the following
requirement (b), and the copolymer (C0) satisfies the following
requirement (c): (a) the syndiotactic pentad fraction (rrrr
fraction) as measured by .sup.13C-NMR is 85% or greater, the
melting point (Tm) as measured by DSC is 145.degree. C. or higher,
and constituent units derived from propylene is contained in an
amount of more than 90 mol % (provided that the total amount of the
constituent units in the polymer (AA) is 100 mol %), (b)
constituent units derived from propylene are contained in an amount
of 55 to 90 mol %, constituent units derived from at least one
olefin selected from .alpha.-olefins having 2 to 20 carbon atoms
(excluding propylene) are contained in an amount of 10 to 45 mol %
(provided that the sum of amounts of the constituent units derived
from propylene and the constituent units derived from the
.alpha.-olefin having 2 to 20 carbon atoms (excluding propylene) is
100 mol %), the MFR measured according to JIS K-6721 at 230.degree.
C. under a load of 2.16 kg is in the range of 0.01 to 100 g/10 min,
and at least one of the following requirements (b-1) and (b-2) is
satisfied: (b-1) the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater, and (b-2) the intrinsic
viscosity [.eta.] (dL/g) as measured in decalin at 135.degree. C.
and the MFR (g/10 min, 230.degree. C., under a load of 2.16 kg)
satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.2-
0), (c) constituent units derived from ethylene are contained in an
amount of 50 to 99 mol %, and constituent units derived from an
.alpha.-olefin having 3 to 20 carbon atoms other than ethylene are
contained in an amount of 1 to 50 mol % (provided that the sum of
amounts of the constituent units derived from ethylene and the
constituent units derived from the .alpha.-olefin having 3 to
carbon atoms is 100 mol %).
12. The propylene-based polymer composition (X2) according to claim
11, which comprises: 98 to 40 parts by weight of the syndiotactic
propylene polymer (AA); 2 to 60 parts by weight of the
propylene..alpha.-olefin copolymer (B2) (provided that the sum of
amounts of (AA) and (B2) is 100 parts by weight); and 1 to 100
parts by weight of the ethylene..alpha.-olefin copolymer (C0) based
on 100 parts by weight of the sum of amounts of (AA) and (B2),
wherein the polymer (AA) satisfies the following requirement (a),
the copolymer (B2) satisfies the following requirement (b'), and
the copolymer (C0) satisfies the following requirement (c'): (a)
the syndiotactic pentad fraction (rrrr fraction) as measured by
.sup.13C-NMR is 85% or greater, the melting point (Tm) as
determined by DSC is 145.degree. C. or higher, and constituent
units derived from propylene is contained in an amount of more than
90 mol % (provided that the total amount of the constituent units
in the polymer (AA) is 100 mol %), (b') constituent units derived
from propylene are contained in an amount of 65 to 90 mol %,
constituent units derived from at least one olefin selected from
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene)
are contained in an amount of 10 to 35 mol % (provided that the sum
of amounts of the constituent units derived from propylene and the
constituent units derived from the .alpha.-olefin having 2 to 20
carbon atoms (excluding propylene) is 100 mol %), the MFR as
measured according to JIS K-6721 at 230.degree. C. under a load of
2.16 kg is in the range of 0.01 to 100 g/10 min, and at least one
of the following requirements (b-1) and (b-2) is satisfied: (b-1)
the syndiotactic triad fraction (rr fraction) as measured by
.sup.13C-NMR is 60% or greater, and (b-2) the intrinsic viscosity
[.eta.] (dL/g) as measured in decalin at 135.degree. C. and the MFR
(g/10 min, 230.degree. C., under a load of 2.16 kg) satisfy the
following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.2-
0), (c') constituent units derived from ethylene are contained in
an amount of 60 to 95 mol %, and constituent units derived from the
.alpha.-olefin having 3 to 20 carbon atoms other than ethylene are
contained in an amount of 5 to 40 mol % (provided that the sum of
amounts of the constituent units derived from ethylene and the
constituent units derived from the .alpha.-olefin having 3 to 20
carbon atoms is 100 mol %).
13. The propylene-based polymer composition (X2) according to claim
11, which comprises: 100 parts by weight of the syndiotactic
propylene polymer (AA); and 1 to 100 parts by weight of the
ethylene..alpha.-olefin copolymer (C0), wherein the polymer (AA)
satisfies the following requirement (a), and the copolymer (C0)
satisfies the following requirement (c'): (a) the syndiotactic
pentad fraction (rrrr fraction) as measured by .sup.13C-NMR is 85%
or greater, the melting point (Tm) as determined by DSC is
145.degree. C. or higher, and constituent units derived from
propylene are contained in an amount of more than 90 mol %
(provided that the total amount of the constituent units in the
polymer (AA) is 100 mol %), and (c') constituent units derived from
ethylene are contained in an amount of 60 to 95 mol %, and
constituent units derived from the .alpha.-olefin having 3 to 20
carbon atoms other than ethylene are contained in an amount of 5 to
40 mol % (provided that the sum of amounts of the constituent units
derived from ethylene and the constituent units derived from the
.alpha.-olefin having 3 to 20 carbon atoms is 100 mol %).
14. The propylene-based polymer composition (X2) according to claim
11, which has (1) a half-crystallization time (t.sub.1/2) during
isothermal crystallization at 110.degree. C. as determined by
differential scanning calorimetry in the range of 1,000 sec or
less.
15. The propylene-based polymer composition (X2) according to claim
11, which has (2) a needle penetration temperature of 145.degree.
C. or higher.
16. The propylene-based polymer composition (X2) according to claim
11, wherein the syndiotactic propylene polymer (AA) has an
intrinsic viscosity [.eta.] as measured in decalin at 135.degree.
C. in the range of 0.1 to 10 dL/g, and a heat of fusion (.DELTA.H)
of 40 mJ/mg or greater.
17. The propylene-based polymer composition (X2) according to claim
11, wherein the propylene..alpha.-olefin polymer (B2) has a
molecular weight distribution (Mw/Mn, Mn: number average molecular
weight, Mw: weight average molecular weight), as measured by GPC,
of 3.5 or less.
18. The propylene-based polymer composition (X2) according to claim
11, wherein the ethylene..alpha.-olefin copolymer (C0) has an MFR
in the range of 0.01 to 100 g/10 min, as measured according to JIS
K-6721 at 190.degree. C. under a load of 2.16 kg, and a density of
0.910 to 0.850 (g/cm.sup.3).
19. A propylene-based polymer composition (X3), comprising: 10 to
95 parts by weight of a syndiotactic propylene polymer (AA), and 90
to 5 parts by weight of a propylene..alpha.-olefin copolymer (B3)
(provided that the sum of amounts of (AA) and (B3) is 100 parts by
weight), wherein the polymer (AA) satisfies the following
requirement (a) and the copolymer (B3) satisfies the following
requirement (b): (a) the syndiotactic pentad fraction (rrrr
fraction) as measured by .sup.13C-NMR is 85% or greater, the
melting point (Tm) as determined by DSC is 145.degree. C. or
higher, and constituent units derived from propylene are contained
in an amount of more than 90 mol % (provided that the total amount
of the constituent unit in the polymer (AA) is 100 mol %), and (b)
constituent units derived from propylene are contained in an amount
of 30 to 90 mol %, constituent units derived from at least one
olefin selected from .alpha.-olefins having 2 to 20 carbon atoms
(excluding propylene) are contained in an amount of 10 to 70 mol %
(provided that the sum of amounts of the constituent units derived
from propylene and the constituent units derived from the
.alpha.-olefin having 2 to 20 carbon atoms (excluding propylene) is
100 mol %), the MFR measured according to JIS K-6721 at 230.degree.
C. under a load of 2.16 kg is in the range of 0.01 to 100 g/10 min,
and at least one of the following requirements (b-1) and (b-2) is
satisfied: (b-1) the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater, and (b-2) the intrinsic
viscosity [.eta.] (dL/g) as measured in decalin at 135.degree. C.
and the MFR (g/10 min, 230.degree. C., under a load of 2.16 kg)
satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.2-
0).
20. The propylene-based polymer composition (X3) according to claim
19, wherein the propylene..alpha.-olefin copolymer (B3) comprises
constituent units derived from propylene in an amount of 30 to 90
mol %, and constituent units derived from ethylene and constituents
unit derived from an .alpha.-olefin having 4 to 20 carbon atoms in
a total amount of 10 to 70 mol % (the sum of amounts of the
constituent units derived from propylene, the constituent units
derived from ethylene and constituent units derived from the
.alpha.-olefin having 4 to 20 carbon atoms is 100 mol %), and
satisfies P.sub.EP.sub.HAO when the proportion of the constituent
units derived from ethylene is designated as P.sub.E (mol %), and
the proportion of the constituent units derived from the
.alpha.-olefin having 4 to 20 carbon atoms is designated as
P.sub.HAO (mol %).
21. The propylene-based polymer composition (X3) according to claim
19, further comprising 0.1 to 100 parts by weight of one or more
resins (C1) selected from the group consisting of rosin-based
resins, terpene-based resins and petroleum resins, based on 100
parts by weight of the sum of amounts of the syndiotactic propylene
polymer (AA) and the propylene..alpha.-olefin copolymer (B3).
22. The propylene-based polymer composition (X3) according to claim
19, further comprising 0.1 to 500 parts by weight of a
non-crosslinked or partially crosslinked olefin-based thermoplastic
elastomer (C2) based on 100 parts by weight of the sum of amounts
of the syndiotactic propylene polymer (AA) and the
propylene..alpha.-olefin copolymer (B3).
23. A molded product formed using the propylene-based polymer
composition according to claim 1.
24. A sheet obtained from the propylene-based polymer composition
(X1) according to claim 1.
25. An unstretched or stretched film obtained from the
propylene-based polymer composition (X1) according to claim 1.
26. A laminate comprising the film according to claim 25.
27. A non-woven fabric obtained from the propylene-based polymer
composition (X1) according to claim 1.
28. A molded product formed using the pellets according to claim
10.
29. A sheet obtained from the pellets according to claim 10.
30. An unstretched or stretched film obtained from the pellets
according to claim 10.
31. A laminate comprising the film according to claim 30.
32. A non-woven fabric obtained from pellets according to claim
10.
33. A molded product formed using the propylene-based polymer
composition (X2) according to claim 11.
34. A sheet obtained from the propylene-based polymer composition
(X2) according to claim 11.
35. An unstretched or stretched film obtained from the
propylene-based polymer composition (X2) according to claim 11.
36. A laminate comprising the film according to claim 35.
37. A non-woven fabric obtained from the propylene-based polymer
composition (X2) according to claim 11.
38. A molded product formed using the propylene-based polymer
composition (X3) according to claim 19.
39. A sheet obtained from the propylene-based polymer composition
(X3) according to claim 19.
40. An unstretched or stretched film obtained from the
propylene-based polymer composition (X3) according to claim 19.
41. A laminate comprising the film according to claim 40.
42. A non-woven fabric obtained from the propylene-based polymer
composition (X3) according to claim 19.
Description
TECHNICAL FIELD
[0001] The present invention (1) relates to a catalyst for olefin
polymerization which contains a bridged metallocene compound having
a specific structure, and a method for producing an olefin polymer
using the catalyst for olefin polymerization.
[0002] The present invention (2) relates to a method for producing
a propylene-based copolymer.
[0003] The present invention (3) relates to a propylene polymer,
and molded products obtained from the polymer, and more
particularly, to a syndiotactic propylene polymer, and molded
products obtained from the polymer.
[0004] The present invention (4) relates to a propylene-based
polymer composition, molded products formed from the composition,
pellets formed from the propylene-based polymer composition, a
modifier for thermoplastic polymer comprising the pellets, and a
method for producing a thermoplastic resin composition.
[0005] The present invention (5) relates to a propylene-based
polymer composition, and molded products formed from the
composition.
[0006] The present invention (6) relates to a propylene-based
polymer composition, and molded products using the composition.
BACKGROUND ART
[0007] So-called "metallocene compounds" are well known as
homogeneous catalysts for olefin polymerization. Methods for
polymerizing olefins using the metallocene compounds, particularly
those methods for stereoregularly polymerizing .alpha.-olefins,
have been the subject of numerous researches for amelioration,
since the reports made by W. Kaminsky, et al. on isotactic
polymerization, from the viewpoints of further enhancement of
polymerization activity and improvement in stereoregularity
(Non-Patent Document 1).
[0008] In an exemplary research, J. A. Ewen has reported that when
propylene is polymerized in the presence of a catalyst comprising
aluminoxane and a metallocene compound, which is a transition metal
catalyst having a ligand of
isopropylidene(cyclopentadienyl)(9-fluorene) synthesized from a
ligand comprising cyclopentadienyl and fluorenyl bridged by
isopropylidene, a polypropylene having a high tacticity with a
syndiotactic pentad fraction of greater than 0.7 can be obtained
(Non-Patent Document 2).
[0009] To improve this metallocene compound, it has been attempted
to enhance the stereoregularity by replacing the fluorenyl with a
2,7-di-tert-butylfluorenyl group (Patent Document 1).
[0010] In addition to that, an attempt to enhance stereoregularity
by replacing the fluorenyl with a 3,6-di-tert-butylfluorenyl group
(Patent Document 2), or attempts to convert the bridging moiety
which joins the cyclopentadienyl and fluorenyl (Patent Documents 3
and 4), have also been reported. Furthermore,
dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(fluorenyl)zircon-
ium dichloride having a methyl group introduced at the 5-position
of the cyclopentadienyl ring, rather than
dimethylmethylene(3-tert-butylcyclopentadienyl)(fluorenyl)zirconium
dichloride, gives high molecular weight isotactic polypropylene
(Patent Document 5).
[0011] However, the polymerization performance of these metallocene
compounds is not sufficient. Moreover, with the catalysts of
related art, it was not impossible to obtain .alpha.-olefin
polymers having fairly high melting point, which is an index for
stereoregularity, but polymers having high molecular weights could
not be obtained. Thus, there has been a demand for production of a
polymer having a fairly high melting point and a high molecular
weight. Also, there has been a demand for a polymer having a higher
melting point compared to the polymers of related art. Moreover, in
order to enable industrialization, it is demanded to produce an
.alpha.-olefin polymer having the above-described features at
normal temperature or above, preferably at a high temperature
exceeding normal temperature, but a catalyst which is capable of
such production has not been reported heretofore.
[0012] Furthermore, even if an existing catalyst has improved
polymerization performance for a specific .alpha.-olefin, the same
catalyst cannot be said to be necessarily suitable for the
polymerization of other .alpha.-olefins, for example, ethylene, and
the catalyst had to be changed whenever the type of the polymer to
be produced was varied, thus giving much inconvenience during the
production.
[0013] Considering such circumstances, the inventors of the present
invention have devotedly conducted research. As a result, the
inventors have found that when an .alpha.-olefin such as, for
example, propylene, is polymerized using a catalyst for olefin
polymerization containing a specific transition metal catalyst, an
.alpha.-olefin polymer having a high melting point can be obtained
in a polymerization process at normal temperature, as well as in a
polymerization process at a high temperature which is capable of
industrialization, and also have found that even in the case of
polymerizing .alpha.-olefins including ethylene as the main
component under high temperature polymerization conditions, an
ethylene-based polymer having a high molecular weight can be
obtained with high polymerization activity, that is, the catalyst
exhibits high performance in a wide range of polymerization
processes, thus completing the present invention (1).
[0014] Meanwhile, a propylene-based copolymer is used in a variety
of uses as a thermoplastic resin material or as a modifier for
thermoplastic resin. As the polymerization catalyst used in the
production of propylene-based copolymers, titanium-based catalysts
and metallocene-based catalysts are known. However, in the case of
using a titanium-based catalyst, there are problems such as that
the composition of propylene that can be produced is limited, and
the compatibility is not uniform because of wide molecular weight
distribution. Furthermore, a metallocene-based catalyst shows
excellent properties for copolymerization with .alpha.-olefins and
enables polymerization of products with a wide range of
composition, but on the other hand, there are problems such as that
the molecular weight is not increased when polymerization is
performed at high temperatures, and that the polymerization
activity is so low that cost reduction cannot be achieved.
[0015] On the other hand, J. A. Ewen et al. found that when a
catalyst comprising aluminoxane and a transition metal catalyst
having a ligand of isopropylidene(cyclopentadienyl)(9-fluorene), in
which cyclopentadiene and fluorene are bridged by isopropylidene,
is used, a polypropylene having a high tacticity with a
syndiotactic pentad fraction of greater than 0.7 can be obtained
(Non-Patent Document 2).
[0016] It is also reported that a copolymer of propylene and
ethylene with a high molecular weight can be obtained using a
catalyst similar to the transition metal catalyst exhibiting
syndiotactic polypropylene activity (Patent Document 6). However,
this transition metal catalyst has low polymerization performance
at high temperatures, and in particular, needs further improvement
in the molecular weight.
[0017] The present inventors report that a propylene-based
copolymer having a high molecular weight can be obtained using a
specific transition metal catalyst (Patent Document 7). However,
there still is a demand for enabling production of high molecular
weight polymers under higher temperature conditions.
[0018] Therefore, the present inventors have devotedly conducted
research under such circumstances, and as a result, have found that
a propylene-based copolymer obtained using a specific transition
metal catalyst has a high molecular weight and can be produced by
polymerization at high temperatures, thus completing the present
invention (2).
[0019] Meanwhile, polypropylene includes isotactic polypropylene,
syndiotactic polypropylene and the like, and among these, isotactic
polypropylene is used in various uses because of its low cost, and
excellent rigidity, heat resistance and surface gloss.
[0020] In contrast to this, it is known that syndiotactic
polypropylene can be obtained by low temperature polymerization in
the presence of a catalyst comprising a vanadium compound, ether
and an organoaluminum compound. The polymer obtained by this method
has low syndiotacticity, so that the polymer is not considered to
properly show the original syndiotactic properties.
[0021] Recently, since J. A. Ewen et al. first discovered that
polypropylene having high tacticity with a syndiotactic pentad
fraction larger than 0.7 can be obtained by a catalyst comprising
aluminoxane and a transition metal catalyst having an asymmetric
ligand (J. Am. Chem. Soc., 1988, 110, 6255-6256 (Non-Patent
Document 2)), numerous successful results concerning syndiotactic
polypropylene have been disclosed. For example, JP-A No. 8-67713
(Patent Document 8) discloses a method for producing syndiotactic
polypropylene using a catalyst comprising
rac-2,2-dimethylpropylidene
(1-.eta..sup.5-cyclopentadienyl)(1-.eta..sup.5-fluorenyl)dichlorometalloc-
ene of titanium, zirconium, hafnium and vanadium, and a
co-catalyst. Also, the Applicant of the present invention disclosed
that a syndiotactic polypropylene satisfying particular properties
is produced using a polymerization catalyst comprising
1,4-cyclohexanediylidenebis[(cyclopentadienyl-9-fluorenyl)zirconium
dichloride](JP-A No. 4-802147 (Patent Document 9)).
[0022] Syndiotactic polypropylene has very high transparency, very
high surface gloss and excellent flexibility compared to
conventional isotactic polypropylene. Thus, in addition to the
applications known for conventional isotactic polypropylene, such
as films, sheets, fibers, injection molded products and blow molded
products, new applications that so far could not be applied to
isotactic polypropylene are expected. However, the syndiotactic
polypropylene that can be obtained by the method described in the
unexamined patent application publications described above, is slow
in the rate of crystallization and has low crystallization
temperature, thus having a problem of poor molding processability.
For example, it is difficult for syndiotactic polypropylene to be
crystallized even in the pelletization step during a continuous
operation, and moreover the crystallization temperature is low, so
that the time required in cooling an injection molded product or an
extrusion processed film or sheet is much longer than that required
by isotactic polypropylene. This property impedes the production
rate of molded products, and consequently leads to an increase in
the energy cost. There is also a need for further improvement in
the moldability as well as in the balance between the heat
resistance, transparency, rigidity and strength exhibited by molded
products.
[0023] Materials prepared with plastics have been used in many
industrial fields where needs cannot be met by using existing
propylene-based resins only. Of the industrial fields, films for
food containers and medical containers are required to be excellent
in the balance between high heat resistance, flexibility, low
temperature impact resistance, and transparency.
[0024] Recently, a demand for retort foods has been rapidly
increased at home as well as in business fields, and thus the
advent of packaging materials (retort pouches) which can pack a
mass of foods at once has been desired. Retort foods are usually
used for storage at room temperature or in a fridge or freezer over
a long period of time, and thus a film for use in the packaging
material is required to have a high heat sealing strength and a
good low temperature impact resistance such that a content therein
does not break out of the heat sealed part of the package. In
addition, since the retort sterilization treatment is carried out
at high temperature of about 100 to 140.degree. C./through
autoclave after the retort pouches are filled with foods and
sealed, it is necessary for the heat sealed part to maintain its
heat resistance and heat sealing strength during the treatment in
view of ensuring the food quality. Meanwhile, since the
sterilization at higher temperature for a shorter period of time
leads to enhanced working efficiency as well as improvements in
retaining the quality and function of the content, further improved
heat resistance of a propylene-based resin for use in a sealant
layer of retort pouches or the like has been demanded (JP-A No.
09-216640 (Patent Document 910)).
[0025] For medical containers, containers made from relatively
flexible and soft vinyl chloride resins and ethylene/vinyl acetate
copolymer resins have been generally used. These medical bags are
advantageous in that contamination from outside will not happen
because they have a closed system that requires no vent needle in
infusion. However, since containers made from a soft vinyl chloride
resin contain additives such as a plasticizer and a stabilizer, it
has been necessary to prevent the dissolution thereof. In addition,
since medical bags made from an ethylene/vinyl acetate copolymer
resin have poor heat resistance, the resin has to be crosslinked
(JP-A Nos. 2005-053131 and 2004-244044 (Patent Documents 11 and
12)).
[0026] The Applicant of the present invention has offered the
following proposals before.
[0027] JP-A No. 3-12439 (Patent Document 10) proposes a
syndiotactic polypropylene resin composition comprising a
substantial homopolymer of propylene in which the peak intensity of
syndiotactic pentad bonding of a methyl group in the spectrum
determined by .sup.13C-NMR is greater than or equal to 0.7 of the
peak intensity of methyl groups in total, and a copolymer of
ethylene and propylene. The composition has high syndiotacticity,
and has excellent impact resistance and transparency.
[0028] JP-A No. 7-247387 (Patent Document 11) proposes a
syndiotactic polypropylene resin composition comprising 50 to 99.9
parts by weight of a resin component which is composed of 50 to 99
parts by weight of syndiotactic polypropylene and 1 to 50 parts by
weight of isotactic polypropylene, and 0.1 to 50 parts by weight of
a plasticizer. The composition has excellent molding processability
and can result in molded products having excellent transparency and
flexibility. The composition also has a rapid crystallization rate
and excellent molding processability.
[0029] Furthermore, JP-A No. 8-59916 (Patent Document 12) proposes
a syndiotactic polypropylene resin composition comprising 97 to
99.99% by weight of a syndiotactic polypropylene of which
syndiotactic pentad fraction as measured by .sup.13C-NMR is 0.7 or
more, and 0.01 to 3% by weight of polyethylene. The composition has
a rapid crystallization rate and excellent molding
processability.
[0030] JP-A No. 2000-191852 (Patent Document 13) proposes a
flexible transparent syndiotactic polypropylene composition
comprising syndiotactic polypropylene and an amorphous
propylene..alpha.-olefin copolymer. The composition has excellent
transparent, flexibility, scratch resistance and heat
resistance.
[0031] JP-A No. 2000-191858 (Patent Document 14) proposes a
flexible transparent syndiotactic polypropylene composition
comprising syndiotactic polypropylene and a propylene.ethylene
copolymer which has a substantial syndiotactic structure. The
composition is described to have excellent transparency,
flexibility, scratch resistance and heat resistance.
[0032] However, all of these compositions described in the
publications described above are still in need of further
improvement in the balance between moldability, heat resistance,
transparency, impact resistance, flexibility and scratch
resistance.
[0033] Furthermore, all of these compositions described in the
publications described above are still in need of further
improvement in the balance between moldability, heat resistance,
transparency, low temperature impact resistance and
flexibility.
[0034] Also, all of these compositions described in the
publications described above are still in need of further
improvement in the balance between moldability, heat resistance,
flexibility, scratch resistance, abrasion resistance and damping
properties. [0035] [Patent Document 1] JP-A No. H4-69394 [0036]
[Patent Document 2] JP-A No. 2000-212194 [0037] [Patent Document 3]
JP-A No. 2004-189666 [0038] [Patent Document 4] JP-A No.
2004-189667 [0039] [Patent Document 5] JP-W No. 2001-526730 [0040]
[Patent Document 6] JP-A No. H2-274703 [0041] [Patent Document 7]
JP-A No. 2004-161957 [0042] [Patent Document 8] JP-A No. 1996-67713
[0043] [Patent Document 9] JP-A No. 1992-802147 [0044] [Patent
Document 10] JP-A No. 09-216640 [0045] [Patent Document 11] JP-A
No. 2005-053131 [0046] [Patent Document 12] JP-A No. 2004-244044
[0047] [Patent Document 13] JP-A No. H3-12439 [0048] [Patent
Document 14] JP-A No. H7-247387 [0049] [Patent Document 15] JP-A
No. H8-59916 [0050] [Patent Document 16] JP-A No. 2000-191852
[0051] [Patent Document 17] JP-A No. 2000-191858 [0052] [Non-Patent
Document 1] Angew. Chem. Int. Ed. Engl., 24, 507 (1985) [0053]
[Non-Patent Document 2]J. Am. Chem. Soc., 110, 6255-6256 (1988)
DISCLOSURE OF THE INVENTION
[0054] The problem to be solved by the present invention (1) is to
provide a catalyst for olefin polymerization which, in the case of
polymerizing an .alpha.-olefin such as propylene or the like, can
give an .alpha.-olefin polymer having a high melting point and a
sufficient molecular weight under high temperature conditions as
well as normal temperature conditions, and also, in the case of
polymerizing .alpha.-olefins including ethylene as the main
component under high temperature conditions, can give with good
activity an ethylene polymer having high molecular weight, that is,
a catalyst showing high performance in the production of a wide
range of olefin polymers. Also, the present invention is to provide
a method for producing an olefin polymer using such catalyst for
olefin polymerization.
[0055] The problem to be solved by the present invention (2) is to
provide a method for producing a propylene copolymer, wherein the
method yields a propylene copolymer a high molecular weight, and
enables excellent polymerization activity and polymerization at
high temperatures.
[0056] The problem to be solved by the present invention (3) is to
provide a syndiotactic propylene copolymer having improved
properties with respect to the problems described above, and molded
products obtainable from the copolymer. More particularly, the
present invention (3) is to provide a syndiotactic propylene
polymer having excellent moldability which has been acquired by
improving the crystallization rate and crystallization temperature,
and to provide a molded product having excellent heat resistance,
transparency, rigidity and breaking tensile strength.
[0057] The problem to be solved by the present invention (3) is
also to provide a propylene-based polymer composition having
excellent moldability and heat resistance.
[0058] The problem to be solved by the present invention (4) is to
address the problems described above, and to provide a composition
having excellent flexibility, transparency and scratch resistance
as well as excellent moldability and heat resistance, and a molded
product comprising the composition. Furthermore, the problem to be
solved by the present invention (4) is to provide pellets
comprising a propylene-based polymer composition, which pellets can
yield a thermoplastic polymer composition having excellent
flexibility, transparency and scratch resistance as well as
excellent moldability and heat resistance, a modifier for
thermoplastic polymer comprising the pellets, and a method for
producing a thermoplastic resin composition, using the
above-described composition.
[0059] The problem to be solved by the present invention (5) is to
address the problems described above, and to provide a composition
having excellent flexibility, transparency and low temperature
impact resistance as well as excellent moldability and heat
resistance, and a molded product comprising the composition.
[0060] The problem to be solved by the present invention (6) is to
address the problems described above, and to provide a
propylene-based polymer composition having excellent moldability
and heat resistance; to provide a propylene-based polymer
composition having excellent moldability, heat resistance, scratch
resistance, abrasion resistance and damping properties; to provide
a propylene-based polymer composition having excellent flexibility,
in addition to moldability, heat resistance, scratch resistance,
abrasion resistance and damping properties; and to provide a
propylene-based polymer composition having excellent scratch
resistance, abrasion resistance, flexibility and low temperature
impact resistance, in addition to moldability and heat
resistance.
[0061] Objects of the present invention (7) are to solve the
problems described above, and to provide monolayer and multilayer
polypropylene-based resin films excellent in all of heat
resistance, transparency, flexibility, and impact resistance.
[0062] The catalyst (1) for olefin polymerization of the present
invention (1) comprises:
[0063] (a-1) a bridged metallocene compound represented by the
following formula [1-1]; and
[0064] (b) at least one compound selected from:
[0065] (b-1) an organoalumium oxy compound,
[0066] (b-2) a compound which reacts with the bridged metallocene
compound (a-1) to form an ion pair, and
[0067] (b-3) an organoaluminum compound;
##STR00002##
wherein in Formula [1-1], R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.8, R.sup.9 and R.sup.12, which may be identical to
or different from each other, are each selected from hydrogen, a
hydrocarbon group and a silicon-containing group;
[0068] the four groups of R.sup.6, R.sup.7, R.sup.10 and R.sup.11,
which may be identical to or different from each other, are not
hydrogen atoms, and are each selected from a hydrocarbon group and
a silicon-containing group;
[0069] R.sup.2 and R.sup.3 may be linked to each other to form a
ring;
[0070] in one or more combinations of adjacent groups selected from
R.sup.5 and R.sup.6, R.sup.7 and Re, Re and R.sup.9, R.sup.9 and
R.sup.10, and R.sup.11 and R.sup.12, the adjacent groups may be
linked to each other to form a ring;
[0071] R.sup.13 and R.sup.14, which may be identical to or
different from each other, are each an atom or a substituent
selected from the group consisting of a hydrogen atom, a
hydrocarbon group excluding a methyl group, and a silicon
atom-containing group, and the substituents may be linked to each
other to form a ring;
[0072] M is Ti, Zr or Hf;
[0073] Y is carbon or silicon;
[0074] Q, which may be identical to or different from each other,
is selected from a halogen, a hydrocarbon group, an anion ligand
and a neutral ligand capable of coordination with a lone electron
pair; and
[0075] j is an integer from 1 to 4.
[0076] Furthermore, it is preferable that R.sup.1, R.sup.2, R.sup.3
and R.sup.4 in the Formula [1-1] are each a hydrogen. The catalyst
(1) for olefin polymerization of the present invention (1)
preferably further contains a support (c).
[0077] The method for producing an olefin polymer of the present
invention (1) comprises polymerizing at least one monomer selected
from .alpha.-olefins having 2 or more carbon atoms in the presence
of the catalyst (1) for olefin polymerization.
[0078] The present invention (2) is a method for producing a
propylene-based copolymer (B1), said method comprising polymerizing
propylene, and at least one monomer selected from .alpha.-olefins
excluding propylene and polyenes, in the presence of a catalyst (2)
for olefin polymerization comprising:
[0079] (a-2) a bridged metallocene compound represented by the
following Formula [1-2],
[0080] (b) at least one compound selected from:
[0081] (b-1) an organoaluminum oxy compound,
[0082] (b-2) a compound which reacts with the bridged metallocene
compound (a-2) to form an ion pair, and
[0083] (b-3) an organoaluminum compound.
Hereinafter, with regard to the present invention (2), unless
otherwise noted, this .alpha.-olefin does not include
propylene.
##STR00003##
wherein in Formula [1-2], R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.8, R.sup.9 and R.sup.12, which may be identical to
or different from each other, are each an atom or a group selected
from a hydrogen atom, a hydrocarbon group and a silicon-containing
group;
[0084] R.sup.6 and R.sup.11 are the same atoms or same groups
selected from a hydrogen atom, a hydrocarbon group and a
silicon-containing group;
[0085] R.sup.7 and R.sup.10 are the same atoms or same groups
selected from a hydrogen atom, a hydrocarbon group and a
silicon-containing group;
[0086] all of R.sup.6, R.sup.7, R.sup.10 and R.sup.11 cannot be
simultaneously hydrogen atoms;
[0087] R.sup.2 and R.sup.3 may be linked to each other to form a
ring;
[0088] among R.sup.5 to R.sup.12, adjacent groups may be linked to
each other to form a ring;
[0089] R.sup.13 and R.sup.14, which may be identical to and
different from each other, are each selected from an aryl group
having 6 to 18 carbon atoms, an alkyl group having 1 to 40 carbon
atoms, an alkylaryl group having 6 to 40 carbon atoms, a fluoroaryl
group having 6 to 20 carbon atoms, a fluoroalkylaryl group having 7
to 40 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms,
a chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl
group having 6 to 20 carbon atoms, a bromoalkylaryl group having 7
to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms,
and an iodoalkylaryl group having 7 to 40 carbon atoms;
[0090] at least one of R.sup.13 and R.sup.14 is selected from an
aryl group having 7 to 18 carbon atoms, a chloroaryl group having 6
to 20 carbon atoms, a chloroalkylaryl group having 7 to 40 carbon
atoms, a bromoaryl group having 6 to 20 carbon atoms, a
bromoalkylaryl group having 7 to 40 carbon atoms, an iodoaryl group
having 6 to 20 carbon atoms, an iodoalkylaryl group having 7 to 40
carbon atoms, and a fluoroalkylaryl group having 7 to carbon
atoms;
[0091] M is Ti, Zr or Hf;
[0092] Y is carbon or silicon;
[0093] Q is selected from halogen, a hydrocarbon group, a neutral,
conjugated or non-conjugated diene having 10 or fewer carbon atoms,
an anion ligand, and a neutral ligand capable of coordination with
a lone electron pair, in identical or different combinations;
and
[0094] j is an integer from 1 to 4.
[0095] In a preferred embodiment of the present invention (2), in
the Formula [1-2], R.sup.13 and R.sup.14 are each selected from an
aryl group having 11 to 18 carbon atoms, a chloroaryl group having
6 to 20 carbon atoms, a chloroalkylaryl group having 7 to 40 carbon
atoms, a bromoaryl group having 6 to 20 carbon atoms, a
bromoalkylaryl group having 7 to 40 carbon atoms, an iodoaryl group
having 6 to 20 carbon atoms, an iodoalkylaryl group having 7 to 40
carbon atoms, and a fluoroalkylaryl group having 7 to carbon atoms,
and may be identical to or different from each other.
[0096] In a preferred embodiment of the present invention (2), in
the Formula [1-2], R.sup.6 and R.sup.11 are the same groups
selected from a hydrocarbon group and a silicon-containing group,
and R.sup.7 and R.sup.10 are the same groups selected from a
hydrocarbon group and a silicon-containing group. R.sup.6 and
R.sup.7 may be linked to each other to form a ring, and R.sup.10
and R.sup.11 may be linked to each other to form a ring.
[0097] In a preferred embodiment of the present invention (2), in
the Formula [1-2], R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each a
hydrogen.
[0098] In a preferred embodiment of the present invention (2), the
produced propylene-based copolymer (B1) contains a propylene
component in an amount of 95 to 51 mol %, contains an
.alpha.-olefin component, which is at least one selected from
ethylene, 1-butene, 4-methylpentene-1,1-hexene, 1-octene and
1-decene, in an amount of 5 to 49 mol %, and contains a polyene
component, which is at least one selected from conjugated or
non-conjugated dienes and non-conjugated trienes, in an amount of 0
to 20 mol %, provided that the sum of amounts of the .alpha.-olefin
component and the polyene component is 5 to 49 mol %.
[0099] In a preferred embodiment of the present invention (2), the
produced propylene-based copolymer (B1) contains a propylene
component in an amount of 95 to 51 mol %, contains an
.alpha.-olefin component, which is at least one selected from
ethylene, 1-butene and 1-octene, in an amount of 5 to 49 mol %, and
contains a polyene component, which is at least one selected from
dienes having a norbornene skeleton, 4,8-dimethyl-1,4,8-decatriene
and 4-ethylidene-8-methyl-1,7-nonadiene (EMND), in an amount of 0
to 20 mol %, provided that the sum of amounts of the .alpha.-olefin
component and the polyene component is 5 to 49 mol %.
[0100] In the method for production described above, when the molar
fraction of the constituent units derived from ethylene of the
produced propylene-based copolymer (B1) is designated as P.sub.E,
and the molar fraction of an .alpha.-olefin having 4 or more carbon
atoms is designated as P.sub.HAO, the value of P.sub.E/P.sub.HAO is
preferably 0 to 0.80.
[0101] In a preferred embodiment of the present invention (2), the
propylene-based copolymer (B1) is produced under the conditions
such as a polymerization temperature of 40.degree. C. to
200.degree. C. and a polymerization pressure of 0.5 MPa to 10
MPa.
[0102] The propylene polymer of the present invention (3) is a
propylene-based polymer (provided that the sum of amounts of the
constituent units is 100 mol %) containing constituent units
derived from propylene in an amount of more than 90 mol % (provided
that the total amount of the constituent units in the polymer (A)
is 100 mol %), and is a syndiotactic propylene polymer which
satisfies the following requirements [1] and [2-1]. The
propylene-based polymer is preferably a syndiotactic propylene
polymer which contains constituent units derived from propylene in
an amount of more than 90 mol % to less than or equal to 100 mol %,
and constituent units derived from at least one selected from
ethylene and an .alpha.-olefin having 4 to 20 carbon atoms in an
amount of more than or equal to 0 mol % to less than 10 mol %
(provided that the sum of amounts of the constituent units is 100
mol %), and satisfies the following requirements [1], [2-2] and
[3](In the following description, the term "propylene polymer" may
be used as a term encompassing propylene copolymers with the
.alpha.-olefin as well as homopolymer. Also, the propylene polymer
of the present invention may be occasionally referred to as
"syndiotactic propylene polymer (A)")
[0103] [1] The syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or greater.
[0104] [2-1] The melting point (Tm) determined by differential
scanning calorimetry (DSC) is 145.degree. C. or higher.
[0105] [2-2] The melting point (Tm) is 145.degree. C. or higher,
and the heat of fusion (.DELTA.H) is 40 mJ/mg or greater, each
determined by differential scanning calorimetry (hereinafter,
referred to as DSC).
[0106] [3] When the isothermal crystallization temperature
determined by differential scanning calorimetry is designated as
T.sub.iso, and the half-crystallization time at the isothermal
crystallization temperature T.sub.iso is designated as t.sub.1/2,
the following Equation (Eq-1) is satisfied within the range of
110.ltoreq.T.sub.iso.ltoreq.150 (.degree. C.):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.5.-
56.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-1)
[0107] The syndiotactic propylene polymer (A) of the present
invention preferably satisfies the following requirement [4] in
addition to the above-described requirements.
[0108] [4] The amount of the n-decane-soluble part is 1 wt % or
less.
[0109] Furthermore, in the following description, a syndiotactic
propylene polymer (A) which satisfies the requirement [4] in
addition to the requirements [1] to [3] may be particularly
referred to as syndiotactic propylene polymer (A').
[0110] The syndiotactic propylene polymer (A) of the present
invention preferably simultaneously satisfies the following
requirements [a] to [d], in addition to the above-described
requirements [1] to [4].
[0111] [a] The tensile modulus is in the range of 500 to 2,000
MPa.
[0112] [b] The breaking tensile strength is 20 MPa or larger.
[0113] [c] The internal haze value of a press sheet having a
thickness of 1 mm is 50% or less.
[0114] [d] The needle penetration temperature is 145.degree. C. or
higher.
[0115] Furthermore, in the following description, a syndiotactic
propylene polymer which satisfies requirements [.alpha.] to
[.delta.], in addition to the requirements [1] to [4] may be
particularly referred to as syndiotactic propylene polymer
(A'').
[0116] The present invention (3) also includes molded products
obtained from the above-described syndiotactic propylene polymers
(A), (A') and (A'').
[0117] Furthermore, the propylene-based polymer composition of the
present invention contains the syndiotactic propylene polymer (A).
The molded product of the present invention (3) is obtained from
the aforementioned composition.
[0118] The propylene-based polymer composition (X1) of the present
invention (4) is a propylene polymer composition (X1) which
comprises:
[0119] 10 to 95 parts by weight of a syndiotactic propylene polymer
(AA) and
[0120] 90 to 5 parts by weight of a propylene..alpha.-olefin
copolymer (B2) (provided that the sum of amounts of (AA) and (B2)
is 100 parts by weight),
[0121] wherein the polymer (AA) satisfies the following requirement
(a), and the copolymer (B2) satisfies the following requirement
(b):
[0122] (a) the syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or greater, the melting point (Tm)
as determined by DSC is 145.degree. C. or higher, and constituent
units derived from propylene are contained in an amount of more
than 90 mol % (provided that the total amount of the constituent
units in the polymer (AA) is 100 mol %);
[0123] (b) constituent units derived from propylene are contained
in an amount of 55 to 90 mol %, constituent units derived from at
least one olefin selected from .alpha.-olefins having 2 to 20
carbon atoms (excluding propylene) are contained in an amount of 10
to 45 mol % (provided that the sum of amounts of the constituent
units derived from propylene and the constituent units derived from
the .alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene) is 100 mol %), the MFR measured according to JIS K-6721
at 230.degree. C. under a load of 2.16 kg is in the range of 0.01
to 100 g/10 min, and at least one of the following requirements
(b-1) and (b-2) is satisfied;
[0124] (b-1) the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater; and
[0125] (b-2) the intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
[0126] Examples of preferred embodiments of the propylene-based
polymer composition (X1) of the present invention (4) include a
propylene-based polymer composition comprising:
[0127] 50 parts by weight or more and 95 parts by weight or less of
the syndiotactic propylene polymer (AA), and
[0128] parts by weight or more and 50 parts by weight or less of
the propylene..alpha.-olefin copolymer (B2) (the sum of amounts of
(AA) and (B2) is 100 parts by weight) (hereinafter, this
composition may be referred to as "composition (X1i)"), and
[0129] a propylene-based polymer composition comprising:
[0130] 10 parts by weight or more and less than 50 parts by weight
of the syndiotactic propylene polymer (AA), and
[0131] more than 50 parts by weight and 90 parts by weight or less
of the propylene..alpha.-olefin copolymer (B2) (the sum of amounts
of (AA) and (B2) is 100 parts by weight) (hereinafter, this
composition may be referred to as composition (X1ii)).
[0132] It is preferable for the composition (X1), (X1i) or (X1ii)
that (1) the half-crystallization time (t.sub.1/2) during
isothermal crystallization at 110.degree. C. as determined by
differential scanning calorimetry is in the range of 1,000 sec or
less.
[0133] It is preferable for the composition (X1), (X1i) or (X1ii)
that (2) the needle penetration temperature is 145.degree. C. or
higher.
[0134] It is particularly preferable for the propylene-based
polymer composition (X1i) that (2) the needle penetration
temperature is 145.degree. C. or higher, (3) the Izod impact
strength at 0.degree. C. is 50 J/m or larger, (4) the tensile
modulus is in the range of 100 MPa to 2000 MPa, and (5) the
internal haze value of a press sheet having a thickness of 1 mm is
50% or less.
[0135] It is particularly preferable for the propylene-based
polymer composition (X1ii) that (2) the needle penetration
temperature is 145.degree. C. or higher, (4) the tensile modulus is
in the range of 1 MPa to 400 MPa, and (5) the internal haze value
of a press sheet having a thickness of 1 mm is 30% or less.
[0136] With regard to the propylene-based polymer composition (X1),
composition (X1i) or (X1ii), it is preferable for the syndiotactic
propylene polymer (AA) that the intrinsic viscosity [.eta.]
measured in decalin at 135.degree. C. is in the range of 0.1 to 10
dL/g, and the heat of fusion (.DELTA.H) determined by differential
scanning calorimetry (DSC) is 40 mJ/mg or greater.
[0137] With regard to the propylene-based polymer composition (X1),
composition (X1i) and (X1ii), it is preferable that the
propylene..alpha.-olefin.polymer (B2) has a molecular weight
distribution (Mw/Mn, Mn: number average molecular weight, Mw:
weight average molecular weight) as determined by GPC, of 3.5 or
less.
[0138] The propylene-based polymer composition (Y) related to
another embodiment of the present invention (4) comprises:
[0139] 99.7 to 70.0 mol % of constituent units derived from
propylene, and
[0140] 0.3 to 30.0 mol % of constituent units derived from an
.alpha.-olefin having 2 to 20 carbon atoms (excluding propylene)
(the amount of the constituent units derived from the
.alpha.-olefin having 2 to 20 carbon atoms (including propylene) is
100 ml %), and has:
[0141] (2) a needle penetration temperature of 145.degree. C. or
higher,
[0142] (3) an Izod impact strength at 0.degree. C. of 50 J/m or
larger,
[0143] (4) a tensile modulus is in the range of 100 MPa to 2,000
MPa, and
[0144] (5) an internal haze value of a press sheet having a
thickness of 1 mm is 50% or less.
[0145] Furthermore, the propylene-based polymer composition (Z)
related to another embodiment of the present invention (4)
comprises:
[0146] 95.0 to 55.0 mol % of constituent units derived from
propylene, and
[0147] 5.0 to 45.0 mol % of constituent units derived from an
.alpha.-olefin having 2 to 20 carbon atoms (excluding propylene)
(the amount of the constituent units derived from the
.alpha.-olefin having 2 to 20 carbon atoms (including propylene) is
100 ml %), and has:
[0148] (2) a needle penetration temperature of 145.degree. C. or
higher,
[0149] (3) a tensile modulus in the range of 1 MPa to 400 MPa,
and
[0150] (4) an internal haze value of a press sheet having a
thickness of 1 mm of 30% or less.
[0151] Also, the molded product of the present invention (4) can be
obtained using the propylene-based polymer composition described
above.
[0152] The pellets of the present invention (4) are pellets
comprising a propylene-based polymer composition (W), said
composition (W) comprising:
[0153] 1 to 65 parts by weight of a syndiotactic propylene polymer
(AA1), and
[0154] 99 to 35 parts by weight of a propylene..alpha.-olefin
copolymer (B21) (provided that the sum of amounts of (AA1) and
(B21) is 100 parts by weight),
[0155] wherein the polymer (AA1) satisfies the following
requirement (a1), and the copolymer (B21) satisfies the following
requirement (b1):
[0156] (a1) the syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or greater, the melting point (Tm)
as determined by DSC is 145.degree. C. or higher, and constituent
units derived from propylene are contained in an amount of more
than 90 mol % (provided that the total amount of the constituent
units in the polymer (AA1) is 100 mol %),
[0157] (b1) constituent units derived from propylene are contained
in an amount of 55 to 90 mol %, constituent units derived from at
least one olefin selected from .alpha.-olefins having 2 to 20
carbon atoms (excluding propylene) are contained in an amount of 10
to 45 mol % (provided that the sum of amounts of the constituent
units derived from propylene and the constituent units derived from
the .alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene) is 100 mol %), the MFR measured according to JIS K-6721
at 230.degree. C. under a load of 2.16 kg is in the range of 0.01
to 100 g/10 min, and at least one of the following requirements
(b1-1) and (b1-2) is satisfied:
[0158] (b1-1): the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater.
[0159] (b1-2) the intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20).
[0160] The modifier for thermoplastic polymer of the present
invention (4) comprises the above-described pellets.
[0161] The method for producing a thermoplastic polymer composition
of the present invention (4) comprises kneading the modifier for
thermoplastic polymer and a thermoplastic polymer.
[0162] The propylene-based polymer composition (X2) of the present
invention (5) comprises:
[0163] 100 to 25 parts by weight of a syndiotactic propylene
polymer (AA),
[0164] 0 to 75 parts by weight of a propylene..alpha.-olefin
copolymer (B2) (provided that the sum of amounts of (AA) and (B2)
is 100 parts by weight), and
[0165] 1 to 100 parts by weight of an ethylene..alpha.-olefin
copolymer (C0) based on 100 parts by weight of the sum of amounts
of (AA) and (B2),
[0166] wherein the polymer (AA) satisfies the following requirement
(a), the polymer (B2) satisfies the following requirement (b), and
the copolymer (C0) satisfies the following requirement (c):
[0167] (a) the syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or greater, the melting point (Tm)
as measured by DSC is 145.degree. C. or higher, and constituent
units derived from propylene are contained in an amount of more
than 90 mol % (provided that the total amount of the constituent
unit in the polymer (AA) is 100 mol %),
[0168] (b) constituent units derived from propylene are contained
in an amount of 55 to 90 mol %, constituent units derived from at
least one olefin selected from .alpha.-olefins having 2 to 20
carbon atoms (excluding propylene) are contained in an amount of 10
to 45 mol % (provided that the sum of amounts of the constituent
units derived from propylene and the constituent units derived from
the .alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene) is 100 mol %), the MFR measured according to JIS K-6721
at 230.degree. C. under a load of 2.16 kg is in the range of 0.01
to 100 g/10 min, and at least one of the following requirements
(b-1) and (b-2) is satisfied:
[0169] (b-1) the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater, and
[0170] (b-2) the intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
[0171] (c) constituent units derived from ethylene are contained in
an amount of 50 to 99 mol %, and constituent units derived from an
.alpha.-olefin having 3 to 20 carbon atoms other than ethylene are
contained in an amount of 1 to 50 mol % (provided that the sum of
amounts of the constituent units derived from ethylene and the
constituent units derived from the .alpha.-olefin having 3 to 20
carbon atoms is 100 mol %).
[0172] Examples of preferred embodiments of the propylene-based
polymer composition of the present invention (5) include:
[0173] a propylene-based polymer composition (X2) (hereinafter,
this composition may be referred to as "composition (X2i)")
comprising:
[0174] 98 to 40 parts by weight of the syndiotactic propylene
polymer (AA);
[0175] 2 to 60 parts by weight of the propylene..alpha.-olefin
copolymer (B2) (provided that the sum of amounts of (AA) and (B2)
is 100 parts by weight); and
[0176] 1 to 100 parts by weight of the ethylene..alpha.-olefin
copolymer (C0) based on 100 parts by weight of the sum of amounts
of (AA) and (B2),
[0177] wherein the polymer (AA) satisfies the following requirement
(a), the copolymer (B2) satisfies the following requirement (b'),
and the copolymer (C0) satisfies the following requirement
(c'):
[0178] (a) the syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or greater, the melting point (Tm)
as determined by DSC is 145.degree. C. or higher, and constituent
units derived from propylene are contained in an amount of more
than 90 mol % (provided that the total amount of the constituent
units in the polymer (AA) is 100 mol %),
[0179] (b') constituent units derived from propylene are contained
in an amount of 65 to 90 mol %, constituent units derived from at
least one olefin selected from .alpha.-olefins having 2 to 20
carbon atoms (excluding propylene) are contained in an amount of 10
to 35 mol % (provided that the sum of amounts of the constituent
units derived from propylene and the constituent units derived from
the .alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene) is 100 mol %), the MFR as measured according to JIS
K-6721 at 230.degree. C. under a load of 2.16 kg is in the range of
0.01 to 100 g/10 min, and at least one of the following
requirements (b-1) and (b-2) is satisfied:
[0180] (b-1) the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater, and
[0181] (b-2) the intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20),
[0182] (c') constituent units derived from ethylene are contained
in an amount of 60 to 95 mol %, and constituent units derived from
an .alpha.-olefin having 3 to 20 carbon atoms other than ethylene
are contained in an amount of 5 to 40 mol % (provided that the sum
of amounts of the constituent units derived from ethylene and the
constituent units derived from the .alpha.-olefin having 3 to 20
carbon atoms is 100 mol %).
[0183] Examples of preferred embodiments of the present invention
(5) include:
[0184] a propylene-based polymer composition (X2) (hereinafter,
this composition may be referred to as "composition (X2ii)")
comprising:
[0185] 100 parts by weight of the syndiotactic propylene polymer
(AA); and
[0186] 1 to 100 parts by weight of the ethylene..alpha.-olefin
copolymer (C0),
[0187] wherein the polymer (AA) satisfies the following requirement
(a), and the copolymer (C0) satisfies the following requirement
(c'):
[0188] (a) the syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or greater, the melting point (Tm)
as determined by DSC is 145.degree. C. or higher, and constituent
units derived from propylene are contained in an amount of more
than 90 mol % (provided that the total amount of the constituent
units in the polymer (AA) is 100 mol %), and
[0189] (c') constituent units derived from ethylene are contained
in an amount of 60 to 95 mol %, and constituent units derived from
an .alpha.-olefin having 3 to 20 carbon atoms other than ethylene
are contained in an amount of 5 to 40 mol % (provided that the sum
of amounts of the constituent units derived from ethylene and the
constituent units derived from the .alpha.-olefin having 3 to 20
carbon atoms is 100 mol %).
[0190] It is preferable for the composition (X2), (X2i) or (X2ii)
that, for example, (1) the half-crystallization time (t.sub.1/2)
during isothermal crystallization at 110.degree. C. as determined
by differential scanning calorimetry is in the range of 1,000 sec
or less.
[0191] It is also preferable for the composition (X2), (X2i) or
(X2ii) that the needle penetration temperature is 145.degree. C. or
higher.
[0192] It is preferable for the propylene..alpha.-olefin polymer
(B2) that the intrinsic viscosity [.eta.] as measured in decalin at
135.degree. C. is in the range of 0.1 to 10 dL/g, and the molecular
weight distribution (Mw/Mn, Mn: number average molecular weight,
Mw: weight average molecular weight) as measured by GPC is 3.5 or
less.
[0193] It is preferable for the ethylene..alpha.-olefin copolymer
(C0) that the MFR measured according to JIS K-6721 at 190.degree.
C. under a load of 2.16 kg is in the range of 0.01 to 100 g/10 min,
and the density is 0.910 to 0.850 (g/cm.sup.3).
[0194] The molded product of the present invention (5) is formed
using the above-described propylene-based polymer composition
(X2).
[0195] The propylene-based polymer composition (X3) of the present
invention (6) comprises:
[0196] 10 to 95 parts by weight of a syndiotactic propylene polymer
(AA), and
[0197] 90 to 5 parts by weight of a propylene..alpha.-olefin
copolymer (B3) (provided that the sum of amounts of (AA) and (B3)
is 100 parts by weight),
[0198] wherein the polymer (AA) satisfies the following requirement
(a) and the copolymer (B3) satisfies the following requirement
(b):
[0199] (a) the syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or greater, the melting point (Tm)
as determined by DSC is 145.degree. C. or higher, and constituent
units derived from propylene are contained in an amount of more
than 90 mol % (provided that the total amount of the constituent
unit in the polymer (AA) is 100 mol %), and
[0200] (b) constituent units derived from propylene are contained
in an amount of 30 to 90 mol %, constituent units derived from at
least one olefin selected from .alpha.-olefins having 2 to 20
carbon atoms (excluding propylene) are contained in an amount of 10
to 70 mol % (provided that the sum of amounts of the constituent
units derived from propylene and the constituent units derived from
the .alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene) is 100 mol %), the MFR measured according to JIS K-6721
at 230.degree. C. under a load of 2.16 kg is in the range of 0.01
to 100 g/10 min, and at least one of the following requirements
(b-1) and (b-2) is satisfied:
[0201] (b-1) the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater, and
[0202] (b-2) the intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20).
[0203] Examples of preferred embodiments of the propylene-based
polymer composition (X3) of the present invention (6) (hereinafter,
simply referred to as "composition (X3)") include:
[0204] a propylene-based polymer composition (hereinafter, this
composition may be referred to as "composition (X3i)") further
comprising 0.1 to 100 parts by weight of one or more resins (c1)
selected from the group consisting of rosin-based resins,
terpene-based resins and petroleum resins, based on 100 parts by
weight of the sum of amounts of the syndiotactic propylene polymer
(AA) and the propylene..alpha.-olefin copolymer (B3).
[0205] Examples of preferred embodiments of the composition (X3)
and composition (X3i) include:
[0206] a propylene-based polymer composition (X3) in which the
propylene..alpha.-olefin copolymer (B3) is a copolymer of
propylene, ethylene and .alpha.-olefin having 4 to 20 carbon atoms,
comprising constituent units derived from propylene in an amount of
30 to 90 mol %, and constituent units derived from ethylene and
constituent units derived from an .alpha.-olefin having 4 to 20
carbon atoms in a total amount of 10 to 70 mol % (the sum of
amounts of the constituent units derived from propylene, the
constituent units derived from ethylene and constituent units
derived from the .alpha.-olefin having 4 to 20 carbon atoms is 100
mol %), and satisfies P.sub.E.ltoreq.P.sub.HAO when the proportion
of the constituent units derived from ethylene is designated as
P.sub.E (mol %), and the proportion of the constituent units
derived from the .alpha.-olefin is designated as P.sub.HAO (mol
%).
[0207] Examples of a preferred embodiment of the propylene-based
polymer composition (X3) of the present invention (6) include:
[0208] the propylene-based polymer composition according to claim 1
(hereinafter, this composition may be referred to as "composition
(X3ii)"), further comprising 0.1 to 500 parts by weight of a
non-crosslinked or partially crosslinked olefin-based thermoplastic
elastomer (C2), based on 100 parts by weight of the sum of amounts
of the syndiotactic propylene polymer (AA) and
propylene..alpha.-olefin copolymer (B3).
[0209] In the composition (X3), it is preferable that the
syndiotactic propylene polymer (AA) has an intrinsic viscosity
[.eta.] measured in decalin at 135.degree. C. in the range of 0.1
to 10 dL/g, and a heat of fusion (.DELTA.H) determined by
measurement of differential scanning calorimetry (DSC) of 40 mJ/mg
or greater.
[0210] In the composition (X3), it is preferable that the molecular
weight distribution (Mw/Mn, Mn: number average molecular weight,
Mw: weight average molecular weight) of the
propylene..alpha.-olefin polymer (B3) as measured by GPC is 3.5 or
less.
[0211] The molded product of the present invention (6) is formed
using the composition (X3).
[0212] The polypropylene-based resin film of the present invention
(7) has a thickness of 10 to 500 .mu.m and satisfies the following
requirements (1) to (3):
[0213] (1) Young's modulus as measured according to JIS K 6781 is
in the range of 10 to 500 MPa,
[0214] (2) Tensile impact strength measured at 0.degree. C. is in
the range of 50 to 1,000 kJ/m.sup.2, and
[0215] (3) Light transmittance is in the range of 85 to 99%, and
the rate of decrease in light transmittance after hot water
treatment at 120.degree. C. for 30 minutes is in the range of 0 to
15%.
[0216] The polypropylene-based resin film preferably further
satisfies the following requirement (4):
[0217] (4) Tm as measured by DSC is 145.degree. C. or higher.
[0218] The polypropylene-based resin film preferably satisfies the
following requirement (5):
[0219] (5) The polypropylene-based resin film comprises a
propylene-based polymer composition comprising:
[0220] (7A) 85 to 25 parts by weight of syndiotactic propylene
polymer satisfying the following requirement (a); and
[0221] (7B) 15 to 75 parts by weight of propylene..alpha.-olefin
copolymer satisfying the following requirement (b) (provided that
the sum of amounts of (7A) and (7B) is 100 parts by weight):
[0222] (a): the syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or more, the melting point (Tm) as
measured by differential scanning calorimetry (DSC) is 145.degree.
C. or higher, and propylene units are contained in an amount of
more than 90 mol % (provided that the total amount of constituent
units in the polymer (7A) is 100 mol %),
[0223] (b): propylene units are contained in an amount of 55 to 90
mol % (provided that the total amount of constituent units in the
copolymer (7B) is 100 mol %), .alpha.-olefin units of at least one
kind selected from .alpha.-olefins having 2 to 20 carbon atoms
(excluding propylene) are contained in an amount of 10 to 45 mol %
(provided that the sum of amounts of the propylene units and the
units of .alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene) is 100 mol %), the MFR measured according to JIS K-6721
at 230.degree. C. under a load of 2.16 kg is in the range of 0.01
to 100 g/10 min, and at least one of the following requirements
(b-1) and (b-2) is satisfied:
[0224] (b-1): the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or more, and
[0225] (b-2): the intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20).
[0226] The propylene-based polymer composition may also contain 1
to 100 parts by weight of an ethylene..alpha.-olefin copolymer (7C)
satisfying the following requirement (c), based on 100 parts by
weight of the sum of amounts of (7A) and (7B):
[0227] (c): the copolymer contains 50 to 99 mol % of ethylene
units, and 1 to 50 mol % of units of .alpha.-olefin having 3 to 20
carbon atoms (provided that the total amount of the constituent
units in the copolymer (7C) is 100 mol %).
[0228] The polypropylene-based resin film preferably further
satisfies the following requirement (6):
[0229] (6) The polypropylene-based resin film comprises a
polypropylene-based resin having a propylene unit concentration
(S.sub.p) of 40 to 95 mol %, an ethylene unit concentration
(S.sub.E) of 60 to 5 mol %, and a C4-10 .alpha.-olefin unit
concentration (S.sub..alpha.) of 0 to 15 mol % (provided that
S.sub.p+S.sub.E+S.sub..alpha..times.100 mol %, and
S.sub.p/S.sub.e>1).
[0230] The polypropylene-based resin film preferably further
satisfies the following requirement (6):
[0231] (7) The intrinsic viscosity of a n-decane-soluble component
(Dsol) which is soluble in n-decane at room temperature is from 1.5
to 4.0 (dl/g).
[0232] The polypropylene-based resin film is preferably molded by
an inflation or extrusion method.
[0233] A multilayer film of the present invention (7) is obtained
by laminating the polypropylene-based resin film described above as
a base layer, and an outer layer comprising a polyolefin-based
resin on at least one side of the base layer.
[0234] A food container of the present invention (7) comprises the
polypropylene-based resin film or the multilayer film.
[0235] A medical container of the present invention (7) comprises
the polypropylene-based resin film or the multilayer film.
Effects of the Invention
[0236] When .alpha.-olefins having 3 or more carbon atoms such as
propylene are polymerized using the catalyst (1) for olefin
polymerization of the present invention (1), an .alpha.-olefin
polymer having high melting point and sufficiently high molecular
weight can be obtained with good activity under high temperature
conditions as well as under normal temperature conditions.
Furthermore, even when .alpha.-olefins including at least ethylene
are polymerized under high temperature conditions using the same
catalyst, an ethylene polymer having good activity and sufficiently
high molecular weight can be obtained. That is, the catalyst shows
high performance in the production of a wide range of olefin
polymers.
[0237] Furthermore, by producing olefin polymers using such
catalyst for olefin polymerization, .alpha.-olefin polymers having
high melting point and sufficiently high molecular weight can be
obtained with good activity even under high temperature conditions.
Also, even when .alpha.-olefins including at least ethylene are
polymerized under high temperature conditions using the same
catalyst, ethylene polymers having sufficiently high molecular
weight can be obtained with good activity.
[0238] According to the method for producing a propylene-based
copolymer (B1) of the present invention (2), a propylene-based
copolymer (B1) having high molecular weight can be obtained with
excellent copolymerizability. Thus, a propylene copolymer having
high molecular weight, which could not be achieved by existing
solution polymerization, can be efficiently produced. Moreover,
even upon producing a propylene copolymer having the same molecular
weight, since polymerization at higher temperatures is made
possible compared to the cases of using existing catalysts for
olefin polymerization, a propylene copolymer can be efficiently
produced.
[0239] According to the present invention (3), a syndiotactic
propylene polymer having excellent moldability and heat resistance,
and particularly having excellent moldability, heat resistance,
transparency, rigidity and breaking tensile strength, and molded
products comprising the polymer can be provided.
[0240] The composition containing the syndiotactic propylene
polymer (A) of the present invention (3) has excellent moldability
and heat resistance. The molded products obtained from the
composition containing the syndiotactic propylene polymer (A) of
the present invention have excellent heat resistance.
[0241] The propylene-based polymer composition of the present
invention (4) has excellent moldability and heat resistance, and
also has excellent transparency, flexibility and scratch
resistance.
[0242] The molded products of the present invention (4) have
excellent heat resistance, and also have excellent transparency,
flexibility and scratch resistance.
[0243] Using the pellets of the present invention (4), a
thermoplastic polymer composition having excellent moldability and
heat resistance, and also having excellent flexibility,
transparency and scratch resistance can be obtained.
[0244] When the modifier for thermoplastic polymer of the present
invention (4) is used, a thermoplastic polymer composition having
excellent moldability and heat resistance, and also having
excellent flexibility, transparency and scratch resistance can be
obtained. The method for producing a thermoplastic resin
composition of the present invention (4) can produce with good
productivity, a thermoplastic polymer composition having excellent
moldability and heat resistance, and also having excellent
flexibility, transparency and scratch resistance.
[0245] The propylene-based polymer composition (X2) of the present
invention (5) has excellent moldability and heat resistance, and
also has excellent transparency, flexibility and low temperature
impact resistance.
[0246] The molded products of the present invention (5) have
excellent heat resistance, and excellent transparency, flexibility
and low temperature impact resistance.
[0247] The propylene-based polymer composition (X3) of the present
invention (6) has excellent moldability and heat resistance.
[0248] When the propylene-based polymer composition (X3) of the
present invention (6) satisfies P.sub.E S P.sub.HAO in which the
proportion of constituent units derived from ethylene is designated
as PE (mol %), and the proportion of constituent units derived from
an .alpha.-olefin having 4 to 20 carbon atoms is designated as
P.sub.HAO (mol %), the composition has excellent moldability, heat
resistance, scratch resistance, abrasion resistance, and damping
properties.
[0249] Furthermore, when the propylene-based polymer composition
(X3) of the present invention (6) contains one or more resins
selected from the group consisting of rosin-based resins,
terpene-based resins and petroleum resins, the composition has
excellent moldability, heat resistance, scratch resistance,
abrasion resistance, damping properties and flexibility.
[0250] When the propylene-based polymer composition (X3) of the
present invention (6) contains a thermoplastic elastomer, the
composition has excellent moldability, heat resistance, scratch
resistance, abrasion resistance, flexibility and low temperature
impact resistance.
[0251] The polypropylene-based resin film of the present invention
(7) is excellent in heat resistance, transparency, flexibility, and
low temperature impact resistance.
[0252] By the use of the polypropylene-based resin film of the
present invention (7), monolayer and multilayer polypropylene-based
resin films having a film transparency that does not deteriorate by
a sterilization treatment at high temperature as well as excellent
impact resistance at low temperature and flexibility can be
provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0253] FIG. 1 is a diagram plotting the relationship between the
specific isothermal crystallization temperature (T.sub.iso) and the
half-crystallization time (t.sub.1/2) at the temperature, for the
syndiotactic propylene polymers described in Examples and
Comparative Examples of the present invention (3). The part
surrounded by bold line indicates a region defined by the parameter
inequality expression (Eq-1) defined in the requirement [3].
[0254] FIG. 2 is a diagram plotting the relationship between the
specific isothermal crystallization temperature (T.sub.iso) and the
half-crystallization time (t.sub.1/2) at the temperature, for the
syndiotactic propylene polymers described in Examples and
Comparative Examples of the present inventions (4) to (6). The part
surrounded by bold line indicates a region defined by the
inequality expression (Eq-1), which is a preferred property of the
syndiotactic propylene polymer (AA) used in the present inventions
(4) to (6).
[0255] FIG. 3 is a diagram plotting the relationship between MFR
and [.eta.] for the polymers corresponding to the component (AA) or
component (B2) used in the present inventions (4) and (5), and
isotactic propylene polymers. The part surrounded by bold line
indicates a region defined by the requirement (b-2) which is one of
the preferred properties of the component (B2) used in the present
inventions (4) and (5), and broken line indicates a preferred range
of (b-2).
[0256] FIG. 4 is a diagram plotting the relationship between MFR
and [.eta.] for the polymers corresponding to the component (AA) or
component (B3) used in the present invention (6), and isotactic
propylene polymers. The part surrounded by bold line indicates a
region defined by the requirement (b-2) which is one of the
preferred properties of the component (B3) used in the present
invention (6), and broken line indicates a preferred range of
(b-2).
[0257] FIG. 5 is a diagram plotting the relationship between the
specific isothermal crystallization temperature (T.sub.iso) and the
half-crystallization time (t.sub.1/2) at the temperature, for the
syndiotactic propylene polymers described in Examples and
Comparative Examples of the present invention. The part surrounded
by bold line indicates a region defined by the parameter inequality
expression (Eq-1), which is a preferred property of the
syndiotactic propylene polymer (7A) of the present invention. In
addition, for reference, plots with respect to a polymer (7AA-2)
belonging to (7A), which is not used in Examples, are also
indicated.
[0258] FIG. 6 is a diagram plotting the relationship between MFR
and [.eta.] for polymers belonging to the component (7A) or
component (7B) (7AA-3 and 7AA-6 do not belong to the component
(7A)) that are preferred embodiments of the present invention, and
isotactic propylene polymers. The part surrounded by bold line
indicates a region defined by the requirement (b-2) which is one of
the preferred properties of the component (7B) of the present
invention, and broken line indicates a preferred range of
(b-2).
BEST MODE FOR CARRYING OUT THE INVENTION
[0259] <Catalyst for Olefin Polymerization (1)>
[0260] First, the catalyst (1) for olefin polymerization of the
present invention (1) will be described in detail.
[0261] The catalyst (1) for olefin polymerization of the present
invention (1) is characterized in comprising:
[0262] (a-1) a bridged metallocene compound represented by the
above Formula [1-1]; and
[0263] (b) at least one compound selected from:
[0264] (b-1) an organoaluminum oxy compound,
[0265] (b-2) a compound which reacts with the bridged metallocene
compound (a-1) to form an ion pair, and
[0266] (b-3) an organoaluminum compound.
[0267] Hereinafter, the bridged metallocene compound (a-1) used in
the catalyst (1) for olefin polymerization of the present invention
(1), the catalyst (1) for olefin polymerization containing the
bridged metallocene compound (a-1), and a method for polymerizing
olefin in the presence of this catalyst for olefin polymerization
(1) will be described in order by way of preferred embodiments for
carrying out the present invention.
[0268] (a-1) Bridged Metallocene Compound
[0269] The bridged metallocene compound (a-1) represented by the
above Formula [1-1](in the present specification, may also be
referred to as "component (a-1)") has the following chemical
structural features [m1-1] to [m1-2].
[0270] [m1-1] Of the two ligands, one is a cyclopentadienyl group
which may be substituted, and the other is a fluorenyl group which
is substituted (hereinafter, may be referred to as "substituted
fluorenyl group").
[0271] [m1-2] The transition metal (M) constituting the metallocene
compound is titanium, zirconium or hafnium.
[0272] Hereinafter, the cyclopentadienyl group which may be
substituted, the substituted fluorenyl group and a bridging part,
which are chemical structural features of the bridged metallocene
compound (a-1) used in the present invention (1), and other
features will be described in order, and preferred bridged
metallocene compounds [1-1] having all of the features, and
examples thereof, and finally the method for polymerization of the
present invention (1) using the bridged metallocene compound (a-1)
will be described in detail.
[0273] Cyclopentadienyl Group which May be Substituted
[0274] The cyclopentadienyl group may be substituted and may be
unsubstituted. The unsubstituted cyclopentadienyl group is a
cyclopentadienyl group in which R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 possessed by the cyclopentadienyl group moiety in the above
Formula [1-1] are all hydrogen atoms, and the substituted
cyclopentadienyl group may be a cyclopentadienyl group in which any
one or more of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be a
hydrocarbon group (f1), or a silicon-containing group (f2). In the
case of a group in which two or more of R.sup.1, R.sup.2, R.sup.3
and R.sup.4 are groups other than hydrogen atom, these groups may
be identical to or different from each other.
[0275] The hydrocarbon group (f1) used for R.sup.1 to R.sup.4 is
preferably exemplified, in the case where the substituent does not
form a ring together with another substituent, by a hydrocarbon
group having 1 to 20 carbon atoms in total (hereinafter, may also
be referred to as "hydrocarbon group (f1')").
[0276] When R.sup.2 and R.sup.3 are hydrocarbon groups (f1),
R.sup.2 and R.sup.3 may be linked to each other to form a ring
(hereinafter, may also be referred to as "ring (f''')"). In this
case, it is more preferable that only R.sup.2 and R.sup.3 among
R.sup.1 to R.sup.4 form a ring, from the viewpoint that, for
example, syndiotactic poly-.alpha.-olefin having high
stereoregularity can be produced.
[0277] In the case where, for example, substituents R.sup.2 and
R.sup.3 are linked to each other to form a ring, regardless of the
fact that each of the above-mentioned R.sup.2 and R.sup.3
preferably has 1 to 20 carbon atoms, the sum of amounts of the
carbon atoms of the two substituents forming a ring is preferably 2
to 40, more preferably 3 to 30, and even more preferably 4 to
20.
[0278] Also in the case where the substituents R.sup.2 and R.sup.3
are linked to each other to form a ring, a part of the hydrogen
atoms directly attached to carbon atoms of the substituents may be
substituted by a halogen atom, an oxygen-containing group, a
nitrogen-containing group or a silicon-containing group, and in
this case, the sum of amounts of the carbon atoms of the two
substituents forming a ring includes the number of carbon atoms
contained in the oxygen-containing group, the nitrogen-containing
group and the silicon-containing group.
[0279] The hydrocarbon group (f1') having 1 to 20 carbon atoms in
total means an alkyl group, an alkenyl group, an alkynyl group or
an aryl group, which is constituted only with carbon and
hydrogen.
[0280] The hydrocarbon group (f1') having 1 to 20 carbon atoms in
total includes a heteroatom-containing hydrocarbon group in which a
part of the hydrogen atoms are substituted with a halogen atom, an
oxygen-containing group, a nitrogen-containing group or a
silicon-containing group, in addition to the alkyl group, alkenyl
group, alkynyl group or aryl group constituted only with carbon and
hydrogen. Examples of such hydrocarbon group (f1') include:
[0281] straight-chained hydrocarbon groups such as a methyl group,
an ethyl group, an n-propyl group, an allyl group, an n-butyl
group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an
n-octyl group, an n-nonyl group, and an n-decanyl group;
[0282] branched hydrocarbon groups such as an isopropyl group, a
t-butyl group, an amyl group, a 3-methylpentyl group, a
1,1-diethylpropyl group, a 1,1-dimethylbutyl group,
1-methyl-1-propylbutyl group, a 1,1-propylbutyl group, a
1,1-dimethyl-2-methylpropyl group, and a
1-methyl-1-isopropyl-2-methylpropyl group;
[0283] saturated cyclic hydrocarbon groups such as a cyclopentyl
group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group,
a norbornyl group, and an adamantyl group;
[0284] unsaturated cyclic hydrocarbon groups such as a phenyl
group, a naphthyl group, a biphenyl group, a phenanthryl group, and
an anthracenyl group, and nuclear alkyl-substituted products
thereof;
[0285] saturated hydrocarbon groups substituted with an aryl group
such as a benzyl group, and a cumyl group; and
[0286] heteroatom-containing hydrocarbon groups such as a methoxy
group, an ethoxy group, a phenoxy group, an N-methylamino group, a
trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl
group, a pentafluorophenyl group, a fluorophenyl group, a
chlorophenyl group, a bromophenyl group, a chlorobenzyl group, a
fluorobenzyl group, a bromobenzyl group, a dichlorobenzyl group, a
difluorobenzyl group, a trichlorobenzyl group, and a
trifluorobenzyl group.
[0287] The silicon-containing group (f2) is a group having a
silicon atom which is covalently bonded to a ring carbon of the
cyclopentadienyl group, and is specifically an alkylsilyl group or
an arylsilyl group. A preferred silicon-containing group (f2), in
the case where the substituent does not form a ring together with
another substituent, is exemplified by a silicon-containing group
(f2') having 1 to 20 carbon atoms in total such as a trimethylsilyl
group, and a triphenylsilyl group.
[0288] In this cyclopentadienyl group, it is preferable that
R.sup.1 and R.sup.4 are identical atoms or identical groups, and
that R.sup.2 and R.sup.3 are linked to form a ring, or they are
identical atoms or identical groups. It is more preferable that
R.sup.1 and R.sup.4 are hydrogen atoms, and it is particularly
preferable that all of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are
hydrogen atoms.
[0289] Substituted Fluorenyl Group
[0290] The first important feature for the fluorenyl group moiety
in the chemical structure represented by the above Formula [1-1]
used in the method for polymerization of the present invention (1),
is that the four groups of R.sup.6, R.sup.7, R.sup.10 and R.sup.11
in the above Formula [1-1] are not hydrogen atoms. R.sup.6,
R.sup.7, R.sup.10 and R.sup.11 are selected from a hydrocarbon
group and a silicon-containing group, and each may be the
hydrocarbon group (f1) described above, or the silicon-containing
group (f2) described above.
[0291] The second important feature for the fluorenyl group moiety
is that R.sup.6 and R.sup.7, and R.sup.10 and R.sup.11 are not
linked to each other to form rings. Since the four groups of
R.sup.6, R.sup.7, R.sup.10 and R.sup.11 are not hydrogen atoms, and
also R.sup.6 and R.sup.7 are not linked to each other to form rings
and R.sup.10 and R.sup.11 are not linked to each other to form
rings in the bridged metallocene compound (a-1), a polymerization
activity can be achieved, which could not be achieved by existing
polymerization processes, and it is possible to produce a polymer
of an .alpha.-olefin having 3 or more carbon atoms, for example, a
propylene polymer, which has a high melting point.
[0292] Furthermore, R.sup.5, R.sup.8, R.sup.9 and R.sup.12 may be
atoms or groups that are identical to or different from each other,
and selected from a hydrogen, the hydrocarbon group (f1) and the
silicon-containing group (f2), and in the one or more combinations
of adjacent groups selected from R.sup.5 and R.sup.6, R.sup.7 and
R.sup.8, Re and R.sup.9, R.sup.9 and R.sup.10, and R.sup.11 and
R.sup.12, the adjacent groups may be linked to each other to form a
ring.
[0293] Examples of the hydrocarbon group (f1) used in the
substituents R.sup.5 to R.sup.12 include, in the case where the
substituent is a group not forming a ring together with another
substituent, the hydrocarbon group having 1 to 20 carbon atoms in
total (hydrocarbon group (f1')).
[0294] When the substituents R.sup.5 to R.sup.12 are each the
hydrocarbon group (f1), the substituent may be linked to another
substituent among the substituents R.sup.5 to R.sup.12 within the
range of the above-described combinations of adjacent groups, to
form a ring. In this case, the adjacent substituents among R.sup.5
to R.sup.12 are linked to each other to form a ring (ring
(f''')).
[0295] Furthermore, when adjacent substituents among the
substituents R.sup.5 to R.sup.12 are linked to each other within
the range of the above-described combinations of adjacent groups,
to form a ring, it is preferable that two adjacent groups among the
substituents R.sup.5 to R.sup.12 are linked to each other to form a
ring.
[0296] For example, when two adjacent substituents are linked to
each other to form a ring (when one or more adjacent combinations
of adjacent groups selected from R.sup.5 and R.sup.6, R.sup.7 and
R.sup.8, R.sup.8 and R.sup.9, R.sup.9 and R.sup.10, R.sup.11 and
R.sup.12 form a ring), regardless of the fact that the preferred
number of carbon atoms for each of the above-described R.sup.5 to
R.sup.12 is 1 to 20, the sum of carbon atoms in the two
substituents forming a ring is preferably 2 to 40, more preferably
3 to 30, and even more preferably 4 to 20.
[0297] When adjacent substituents are linked to each other to form
a ring, a part of the hydrogen atoms directly attached to carbon
atoms of the substituent may also be substituted by a halogen atom,
an oxygen-containing group, a nitrogen-containing group or a
silicon-containing group, and the sum of carbon atoms in a
plurality of substituents forming a ring includes the number of
carbon atoms contained in the oxygen-containing group, the
nitrogen-containing group and the silicon-containing group.
[0298] From the viewpoint of synthesis of the catalyst of the
present invention (1), it is preferable that R.sup.6 and R.sup.11
are identical atoms or identical groups, and R.sup.7 and R.sup.10
are identical atoms or identical groups. Preferred group as the
hydrocarbon group (f1) is the aforementioned hydrocarbon group
(f1') having 1 to 20 carbon atoms in total, and the ring structure
(f'''). Preferred examples of the silicon-containing group (f2)
include the silicon-containing group (f2') having 1 to 20 carbon
atoms in total in the case where the substituent described above
does not form a ring with another substituent.
[0299] According to the present invention (1), from the viewpoint
that a polymer of an .alpha.-olefin having 3 or more carbon atoms,
which has a melting point higher than or equal to the melting point
of conventional polymers, and has a high molecular weight, can be
obtained under the conditions of high temperature polymerization as
well as under the conditions of polymerization at normal
temperature, it is particularly preferable that R.sup.6 and
R.sup.11 are any one of the following (1) and (2):
[0300] (1) hydrocarbon groups, and in the case where they do not
form a ring with adjacent groups, they are each independently a
hydrocarbon group having 2 or more carbon atoms, more preferably 3
or more carbon atoms, and particularly preferably 4 or more carbon
atoms; and
[0301] (2) respectively silicon-containing groups.
[0302] Furthermore, among the silicon-containing groups, a
silicon-containing group of which the sum of carbon atoms and
silicon atoms is 3 or more, and preferably 4 or more, is preferred.
In order to enhance the effect of the present invention,
[0303] when R.sup.6 is a hydrocarbon group which does not form a
ring with its adjacent group, and R.sup.7 is a hydrocarbon group
which does not form a ring together with an adjacent group, it is
preferable that the number of carbon atoms of R.sup.6 is equal to
or larger than the number of carbon atoms of R.sup.7;
[0304] when R.sup.6 is a silicon-containing group, and R.sup.7 is a
silicon-containing group, it is preferable that the total number of
silicon atoms and carbon atoms of R.sup.6 is equal to or larger
than the total number of silicon atoms and carbon atoms of
R.sup.7;
[0305] when R.sup.6 is a hydrocarbon group which does not form a
ring with an adjacent group, and R.sup.7 is a silicon-containing
group, it is preferable that the number of carbon atoms of R.sup.6
is equal to or larger than the total number of silicon atoms and
carbon atoms of R.sup.7; and
[0306] when R.sup.6 is a silicon-containing group, and R.sup.7 is a
hydrocarbon group which does not form a ring, it is preferable that
the total number of silicon atoms and carbon atoms of R.sup.6 is
equal to or larger than the number of carbon atoms of R.sup.7.
[0307] As R.sup.6 and R.sup.11, an aryl group or a substituted aryl
group is preferred, and specific examples thereof include a phenyl
group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a
t-butylphenyl group, a naphthyl group, a dimethylphenyl group, a
trimethylphenyl group, a biphenyl group, an o-fluorophenyl group,
an m-fluorophenyl group, a p-fluorophenyl group, an o-chlorophenyl
group, an m-chlorophenyl group, a p-chlorophenyl group, an
o-trifluorophenyl group, an m-trifluorophenyl group, and a
p-trifluorophenyl group.
[0308] When R.sup.6 and R.sup.11 of the substituted fluorenyl group
is one of the above-described (1) and (2), there can be obtained a
polymer of an .alpha.-olefin having 3 or more carbon atoms, whose
melting point is higher, and whose molecular weight is equal to or
larger than conventional polymers, as compared in terms of
polymerization under the same polymerization conditions.
Alternatively, even under high temperature polymerization
conditions as well as under polymerization conditions at normal
temperature, there can be obtained a polymer of an .alpha.-olefin
having 3 or more carbon atoms, whose melting point is equal to or
higher than that of conventional polymers, as compared in terms of
polymerization under the same polymerization conditions. In
particular, an .alpha.-olefin polymer having excellent in the
balance of performance can be produced.
[0309] Covalently Bonded Bridge
[0310] The main chain part of the bond connecting the
cyclopentadienyl group which may be substituted and the substituted
fluorenyl group is a divalent covalently bonded bridge containing
one carbon atom or silicon atom.
[0311] An important feature in the covalently bonded bridge part in
the bridged metallocene compound (a-1) used in the present
invention (1), is that the bridging atom Y in the above Formula
[1-1] has R.sup.13 and R.sup.14, and these are atoms or
substituents selected from a hydrogen atom, a hydrocarbon group
excluding a methyl group, and a silicon atom-containing group,
which may be identical to and different from each other, and the
substituents may be linked to each other to form a ring.
[0312] When Y is carbon, R.sup.13 and R.sup.14 are each preferably
a hydrocarbon group excluding a methyl group, or a
silicon-containing group. When Y is silicon, R.sup.13 and R.sup.14
are each preferably a hydrocarbon group excluding a methyl
group.
[0313] Among these, it is desirable that Y is carbon, and R.sup.13
and R.sup.14 are each a hydrocarbon group having 2 to 20 carbon
atoms.
[0314] Since such covalently bonded bridge is combined with the
substituted fluorenyl group, production of a propylene polymer
having high melting point under high temperature polymerization
conditions, which could not be achieved in existing polymerization
processes, is now possible.
[0315] Preferred examples of the hydrocarbon group excluding a
methyl group, used in R.sup.13 and R.sup.14 include, in the case
where R.sup.13 and R.sup.14 are not linked to form a ring, a
hydrocarbon group having 2 to 20 carbon atoms in total
(hereinafter, may also be referred to as "hydrocarbon group
(f1'')"). Furthermore, when R.sup.13 and R.sup.14 are each a
hydrocarbon group, R.sup.13 and R.sup.14 may be linked to each
other to form a ring (ring (f'''')).
[0316] The hydrocarbon group having 2 to 20 carbon atoms in total
(f1'') means the resultant of excluding a methyl group from the
hydrocarbon group having 1 to 20 carbon atoms in total (f1').
[0317] When R.sup.13 and R.sup.14 are linked to each other to form
a ring, regardless of the preferred scope that the R.sup.13 and
R.sup.14 each have 2 to 20 carbon atoms, it is preferable that the
total number of carbon atoms of R.sup.13 and R.sup.14 forming a
ring structure is 4 to 40, and this ring structure is also
preferred as well as the hydrocarbon group.
[0318] When R.sup.13 and R.sup.14 are linked to each other to form
a ring, a part of the hydrogen atoms directly attached to carbon of
the R.sup.13 or R.sup.14 may also be substituted with a halogen
atom, an oxygen-containing group, a nitrogen-containing group or a
silicon-containing group. In this case, the sum of carbon atoms in
the plurality of substituents forming a ring includes the number of
carbon atoms included in the oxygen-containing group, the
nitrogen-containing group and the silicon-containing group.
[0319] Preferred examples of the hydrocarbon group (f1'') include
an alkyl group, a substituted alkyl group (including a
halogen-substituted alkyl group), a cycloalkyl group, a substituted
cycloalkyl group (including a halogen-substituted alkyl group), an
arylalkyl group, a substituted arylalkyl group (including a
halogen-substituted arylalkyl group and an arylalkyl group
substituted with a halogenated alkyl group), an alkylaryl group, a
substituted alkylaryl group (including a halogen-substituted
alkylaryl group, and an alkylaryl group substituted with a
halogenated alkyl group), an aryl group (an aromatic group), a
divalent hydrocarbon group (which means the structure where
R.sup.13 and R.sup.14 are linked to form a ring), and a divalent
substituted hydrocarbon group. Preferred examples of the thereof
also include a substituted aryl group (including a
halogen-substituted aryl group, and an aryl group substituted with
a halogenated alkyl group). With regard to the substituted
arylalkyl group and the substituted alkylaryl group, the
substituent may be attached to the aryl moiety or may be attached
to the alkyl moiety.
[0320] The silicon-containing group (f2) is a group having a
silicon atom which is covalently bonded to a ring carbon of the
cyclopentadienyl group, and is specifically an alkylsilyl group or
an arylsilyl group. For example, when the substituent does not form
a ring with another substituent, the silicon-containing group (f2')
having 1 to 20 carbon atoms in total is exemplified by a
trimethylsilyl group, a triethylsilyl group, a triphenylsilyl
group, or the like.
[0321] As R.sup.13 and R.sup.14, inter alia, preferred are
[0322] alkyl groups such as an ethyl group, an n-propyl group, an
isopropyl group, an n-butyl group, an isobutyl group, and a
tert-butyl group;
[0323] cycloalkyl groups such as a cyclopentyl group, a cyclohexyl
group, and a cycloheptyl group;
[0324] aryl groups such as a phenyl group, a biphenyl group, and a
naphthyl group;
[0325] alkylaryl groups such as an o-tolyl group, an m-tolyl group,
and a p-tolyl group;
[0326] arylalkyl groups such as a benzyl group, and a phenylbenzyl
group;
[0327] substituted aryl groups substituted with a group having a
halogen atom, such as an m-(trifluoromethyl)phenyl group, a
p-(trifluoromethyl)phenyl group, a bis(trifluoromethyl)phenyl
group, an m-chlorophenyl group, a p-chlorophenyl group, and a
dichlorophenyl group; and
[0328] substituted alkylaryl groups substituted with a group having
a halogen atom, such as an m-chlorobenzyl group, a p-chlorobenzyl
group, an m-fluorobenzyl group, a p-fluorobenzyl group, an
m-bromobenzyl group, a p-bromobenzyl group, a dichlorobenzyl group,
a difluorobenzyl group, a trichlorobenzyl group, and a
trifluorobenzyl group. In the case of having a substituent in the
aromatic moiety of the aryl group or arylalkyl group, the group
having their substituent at the meta-position and/or para-position
is preferred.
[0329] Among these, an alkyl group, an arylalkyl group, a
substituted arylalkyl group (including a halogen-substituted
arylalkyl group and an arylalkyl group substituted with a
halogenated alkyl group), and an alkylaryl group are more
preferred. Particularly in this case, in addition to the features
described above, an .alpha.-olefin polymer having a higher melting
point and a larger molecular weight can be produced at a
temperature above or equal to normal temperature.
[0330] As the bridged metallocene compound (a-1) used in the
present invention (1), a compound having in which R.sup.13 and
R.sup.14 are the same is preferably used in view of the ease in
production.
[0331] Other Features of Bridged Metallocene Compound (a-1)
[0332] In the above formula [1-1], Q is selected from a halogen, a
hydrocarbon group having 1 to 10 carbon atoms, a neutral,
conjugated or non-conjugated diene having 10 or fewer carbon atoms,
an anion ligand, and a neutral ligand capable of coordination with
a lone electron pair, in identical or different combinations.
Specific examples of the halogen include fluorine, chlorine,
bromine and iodine, and specific examples of the hydrocarbon group
include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl,
1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl,
1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl,
tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl,
cyclohexylmethyl, cyclohexyl, and 1-methyl-1-cyclohexyl.
[0333] Specific examples of the neutral, conjugated or
non-conjugated diene having 10 or fewer carbon atoms include s-cis
or s-trans-.eta..sup.4-1,3-butadiene, s-cis or
s-trans-.eta..sup.4-1,4-diphenyl-1,3-butadiene, s-cis or
s-trans-.eta..sup.4-3-methyl-1,3-pentadiene, s-cis or
s-trans-.eta..sup.4-1,4-dibenzyl-1,3-butadiene, s-cis or
s-trans-.eta..sup.4-2, 4-hexadiene, s-cis or
s-trans-.eta..sup.4-1,3-pentadiene, s-cis or
s-trans-.eta..sup.4-1,4-ditolyl-1,3-butadiene, and s-cis or
s-trans-.eta..sup.4-1,4-bis(trimethylsilyl)-1,3-butadiene.
[0334] Specific examples of the anion ligand include alkoxy groups
such as methoxy, tert-butoxy, and phenoxy, carboxylate groups such
as acetate, and benzoate, and sulfonate groups such as mesylate,
and tosylate.
[0335] Specific examples of the neutral ligand capable of
coordination with a lone electron pair include organophosphorus
compounds such as trimethylphosphine, triethylphosphine,
triphenylphosphine, and diphenylmethylphosphine, and ethers such as
tetrahydrofuran, diethyl ether, dioxane, and
1,2-dimethoxyethane.
[0336] j is an integer from 1 to 4, and when j is 2 or greater, Q
may be identical to or different from each other.
[0337] Preferred Bridged Metallocene Compound (a-1) and Examples
Thereof
[0338] Specific examples of the Group 4 transition metal compound
represented by the above Formula [1-1] will be shown in the
following, but the scope of the present invention (1) is not
intended to be limited particularly to these.
[0339] Examples thereof include
[0340] di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,
6-di-tert-butylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl(2,7-di(2,4,6-trimethyl
phenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluor-
enyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-di(3,5-dimethylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluorenyl)z-
irconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-di(4-methylphenyl)-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-di-naphthyl-3,6-di-tert-butylfl-
uorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-di(4-tert-butylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
[0341] diisobutylmethylene(cyclopentadienyl)(2,7-dimethyl-3,
6-di-tert-butylfluorenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl(2,7-di(2,4,6-trimethyl
phenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluor-
enyl)zirconium dichloride, diisobutylmethylene
(cyclopentadienyl)(2,7-di(3,5-dimethylphenyl)-3,6-di-tert-butylfluorenyl)-
zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluorenyl)z-
irconium dichloride, diisobutylmethylene
(cyclopentadienyl)(2,7-di(4-methylphenyl)-3,6-di-tert-butylfluorenyl)zirc-
onium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-di-naphthyl-3,6-di-tert-butylfl-
uorenyl)zirconium dichloride, diisobutylmethylene
(cyclopentadienyl)(2,7-di(4-tert-butylphenyl)-3,6-di-tert-butylfluorenyl)-
zirconium dichloride,
[0342]
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride [also referred to as
1,3-diphenylisopropylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride, the same applies hereinafter],
dibenzylmethylene
(cyclopentadienyl(2,7-di(2,4,6-trimethylphenyl)-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di(3,5-dimethylphenyl)-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluorenyl)zir-
conium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di(4-methylphenyl)-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di-naphthyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di(4-tert-butylphenyl)-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
[0343]
diphenethylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
diphenethylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
di(benzhydryl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(benzhydryl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(cumyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluore-
nyl)zirconium dichloride,
di(cumyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluore-
nyl)zirconium dichloride,
di(1-phenyl-ethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(1-phenyl-ethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(cyclohexylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(cyclohexylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(cyclopentylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(cyclopentylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
[0344]
(benzyl)(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-te-
rt-butylfluorenyl)zirconium dichloride,
(benzyl)(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
(benzyl)(cumyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butyl-
fluorenyl)zirconium dichloride,
(benzyl)(cumyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butyl-
fluorenyl)zirconium dichloride,
cyclopropylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclopropylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclobutylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cyclobutylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cyclopentylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclopentylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclohexylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cycloheptylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cycloheptylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
[0345]
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butyl-
fluorenyl)zirconium dichloride, di-n-butylmethylene
(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butylfluorenyl)zirconium
dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dicumyl-butylfluoren-
yl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dicumyl-butylfluor-
enyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di(trimethylsilyl)-b-
utylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di(trimethylsilyl)-
-butylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-diphenyl-butylfluore-
nyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-diphenyl-butylfluo-
renyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dibenzyl-butylfluore-
nyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dibenzyl-butylfluo-
renyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butylfluore-
nyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butylfluo-
renyl)zirconium dichloride,
[0346]
diphenylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-te-
rt-butylfluorenyl)zirconium dichloride,
di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-te-
rt-butylfluorenyl)zirconium dichloride,
di(p-n-butyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(p-n-butyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
[0347]
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(1-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(1-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-isopropylphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(p-isopropylphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride, diphenylsilylene
(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluorenyl)zirconium
dichloride,
diphenylsilylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
[0348]
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-dime-
thyl-butylfluorenyl)zirconium dichloride,
di(3-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-dimethyl-b-
utylfluorenyl)zirconium dichloride,
di(4-bromobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-dimethyl-bu-
tylfluorenyl)zirconium dichloride,
di(3-bromobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-dimethyl-bu-
tylfluorenyl)zirconium dichloride,
di(4-fluorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-dimethyl-b-
utylfluorenyl)zirconium dichloride,
di(3-fluorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-dimethyl-b-
utylfluorenyl)zirconium dichloride,
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-b-
utylfluorenyl)zirconium dichloride,
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-di-naphthyl-3,6-dimethy-
lbutylfluorenyl)zirconium dichloride,
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-di{p-tolyl}-3,6-dimethy-
l-butylfluorenyl)zirconium dichloride,
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-di{o-tolyl}-3,6-dimethy-
l-butylfluorenyl)zirconium dichloride,
di(4-phenylbenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di{p-chlorophenyl}-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride, and
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-di{p-chlorophenyl}-3,6--
di-tert-butylfluorenyl)zirconium dichloride
[0349] Furthermore, a compound resulting from replacing the
"zirconium" of the compound described above with "hafnium" or
"titanium", a metallocene compound resulting from replacing the
"dichloride" of the compound described above with "difluoride",
"dibromide" or "diiodide", or resulting from replacing the
"dichloride" of the compound described above with "dimethyl" or
"methylethyl", and the like are also likewise the metallocene
compound related to the catalyst (1) for olefin polymerization of
the present invention (1). In particular, by using a metallocene
compound having a Cs-symmetric structure, among the catalyst
structures described above, a syndiotactic .alpha.-olefin polymer
having a high melting point can be synthesized.
[0350] The bridged metallocene compound (a-1) described above can
be produced by a known method, and the method for production is not
particularly limited. The known method for production is
exemplified by the methods for production described in the
pamphlets of WO 2001/27124 and WO 2004/087775 filed by the present
applicant.
[0351] The metallocene compound as described above can be used
alone or in combination of two or more species.
[0352] Catalyst for Olefin Polymerization
[0353] Next, preferred embodiments of using the bridged metallocene
compound (a-1) described above as a polymerization catalyst in the
method for olefin polymerization of the present invention (1), will
be described.
[0354] In the case of using the bridged metallocene compound (a-1)
as a catalyst for olefin polymerization, the catalyst component
comprises:
[0355] (a-1) a bridged metallocene compound represented by the
above Formula [1-1]; and
[0356] (b) at least one compound selected from:
[0357] (b-1) an organoaluminum oxy compound, (b-2) a compound which
reacts with the bridged metallocene compound (a-1) to form an ion
pair, and (b-3) an organoaluminum compound,
[0358] and if necessary, further comprises a particulate support
(c).
[0359] Hereinafter, each component will be described in detail.
[0360] (b-1) Organoaluminum Oxy Compound
[0361] As the organoaluminum oxy compound (b-1) described above (in
the present specification, may also be referred to as "component
(b-1)"), a known aluminoxane may be directly used, and specific
examples thereof include a compound represented by the following
Formula [2]:
##STR00004##
wherein in the above Formula [2], R's each independently represent
a hydrocarbon group having 1 to 10 carbon atom; and n represents an
integer of 2 or more,
[0362] and/or by Formula [3]:
##STR00005##
wherein in the above Formula [3], R represents a hydrocarbon group
having 1 to 10 carbon atoms; and n represents an integer of 2 or
more. In particular, methylaluminoxane in which R is a methyl group
and n is 3 or more, preferably 10 or more, is used. These
aluminoxanes may have some amount of an organoaluminum compound
incorporated therein.
[0363] The characteristic feature in a high temperature solution
polymerization of the present invention (1) is that the
benzene-insoluble organoaluminum oxy compounds as illustrated in
JP-A No. 2-78687 can be also applied. The organoaluminum oxy
compounds described in JP-A No. 2-167305, aluminoxanes having 2 or
more kinds of alkyl groups as described in JP-A Nos. 2-24701 and
3-103407, and the like are also appropriately used. The
"benzene-insoluble" organoaluminum oxy compound means an
organoaluminum oxy compound which is insoluble or poorly soluble in
benzene to the extent that the Al component soluble in benzene at
60.degree. C. is contained in an amount of generally 10% or less,
preferably 5% or less, and particularly preferably 2% or less,
relative to Al atoms.
[0364] Examples of the organoaluminum oxy compound (b-1) also
include modified methylaluminoxane as represented by the following
Formula [4] and the like:
##STR00006##
wherein R represents a hydrocarbon group having 1 to 10 carbon
atoms; and m and n each independently represent an integer of 2 or
more.
[0365] This modified methylaluminoxane is prepared using
trimethylaluminum and an alkylaluminum other than
trimethylaluminum. Such modified methylaluminoxane is generally
referred to as MMAO. MMAO can be prepared by the methods disclosed
in U.S. Pat. No. 4,960,878 and U.S. Pat. No. 5,041,584. In
addition, such a compound in which R is an isobutyl group, which
compound is prepared using trimethylaluminum and
triisobutylaluminum, is also commercially produced by Tosoh
Finechem Corporation and the like under the product name of MMAO or
TMAO. Such MMAO is an aluminoxane having improved solubility in
various solvents and storage stability, and specifically, the
compound is soluble in aliphatic hydrocarbons and alicyclic
hydrocarbons, unlike the aluminoxanes that are insoluble or poorly
soluble in benzene, such as the compounds represented by Formula
[2] or [3] mentioned.
[0366] Furthermore, examples of the organoaluminum oxy compound
(b-1) also include an organoaluminum oxy compound containing boron,
represented by the following Formula [5].
##STR00007##
wherein in the Formula [5], R.sup.c represents a hydrocarbon group
having 1 to 10 carbon atoms; R.sup.d's, which may be identical to
or different from each other, each represent a hydrogen atom, a
halogen atom, or a hydrocarbon group having 1 to 10 carbon
atoms.
[0367] (b-2) Compound which Reacts with the Bridged Metallocene
Compound (a-1) to Form an Ion Pair
[0368] Examples of the compound (b-2) which reacts with the bridged
metallocene compound (a-1) to form an ion pair (hereinafter, may be
referred to as "ionic compound (b-2)" or "compound (b-2)") include
Lewis acids, ionic compounds, borane compounds and carborane
compounds described in JP-A No. 1-501950, JP-A No. 1-502036, JP-A
No. 3-179005, JP-A No. 3-179006, JP-A No. 3-207703, JP-A No.
3-207704, U.S. Pat. No. 5,321,106, and the like. Examples thereof
also include heteropoly compounds and isopoly compounds.
[0369] An ionic compound (b-2) preferably employed in the present
invention is a compound represented by the following Formula
[6].
##STR00008##
wherein in the Formula [6], R.sup.e+ is exemplified by H.sup.+, a
carbenium cation, an oxonium cation, an ammonium cation, a
phosphonium cation, a cycloheptyltrienyl cation, a ferrocenium
cation having a transition metal, or the like; R.sup.f to R.sup.i
may be identical to or different from each other, and are each an
organic group, preferably an aryl group.
[0370] Specific examples of the carbenium cation include
trisubstituted carbenium cations such as triphenylcarbenium cation,
tris(methylphenyl)carbenium cation, and
tris(dimethylphenyl)carbenium cation.
[0371] Specific examples of the ammonium cation include
trialkylammonium cations such as trimethylammonium cation,
triethylammonium cation, tri(n-propyl)ammonium cation,
triisopropylammonium cation, tri(n-butyl)ammonium cation, and
triisobutylammonium cation; N,N-dialkylanilinium cations such as
N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and
N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations
such as diisopropylammonium cation, and dicyclohexylammonium
cation.
[0372] Specific examples of the phosphonium cation include
triarylphosphonium cations such as triphenylphosphonium cation,
tris(methylphenyl)phosphonium cation, and
tris(dimethylphenyl)phosphonium cation.
[0373] Among them, R.sup.e+ is preferably a carbenium cation, an
ammonium cation, or the like, and particularly preferably a
triphenylcarbenium cation, an N,N-dimethylanilinium cation, an
N,N-diethylanilinium cation, or the like.
[0374] Specific examples of a carbenium salt include
triphenylcarbenium tetraphenylborate, triphenylcarbenium
tetrakis(pentafluorophenyl)borate, triphenylcarbenium
tetrakis(3,5-ditrifluoromethylphenyl)borate,
tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate,
and tris(3,5-dimethylphenyl)carbenium
tetrakis(pentafluorophenyl)borate.
[0375] Examples of an ammonium salt include trialkyl-substituted
ammonium salts, and N,N-dialkylanilinium salts, dialkylammonium
salts.
[0376] Specific examples of the trialkyl-substituted ammonium salt
include triethylammonium tetraphenylborate, tripropylammonium
tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,
trimethylammoniumtetrakis(p-tolyl)borate, trimethylammonium
tetrakis(o-tolyl)borate, tri(n-butyl)ammonium
tetrakis(pentafluorophenyl)borate, triethylammonium
tetrakis(pentafluorophenyl)borate, tripropylammonium
tetrakis(pentafluorophenyl)borate, tripropylammonium
tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(4-trifluoromethylphenyl)borate, tri(n-butyl) ammonium
tetrakis(3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(o-tolyl)borate, dioctadecylmethylammonium
tetraphenylborate, dioctadecylmethylammonium
tetrakis(p-tolyl)borate, dioctadecylmethylammonium
tetrakis(o-tolyl)borate, dioctadecylmethylammonium
tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium
tetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammonium
tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammonium
tetrakis(4-trifluoromethylphenyl)borate, dioctadecylmethylammonium
tetrakis(3,5-ditrifluoromethylphenyl)borate, and
dioctadecylmethylammonium.
[0377] Specific examples of an N,N-dialkylanilinium salt include
N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium
tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylanilinium
tetraphenylborate, N, N-diethylanilinium
tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium
tetrakis(3,5-ditrifluoromethylphenyl)borate,
N,N-2,4,6-pentamethylanilinium tetraphenylborate, and
N,N-2,4,6-pentamethylanilinium
tetrakis(pentafluorophenyl)borate.
[0378] Specific examples of an dialkylammonium salt include
di(1-propyl)ammonium tetrakis(pentafluorophenyl)borate, and
dicyclohexylammonium tetraphenylborate.
[0379] In addition to these, ionic compounds disclosed by the
present applicant (JP-A No. 2004-51676) can also be used without
limitation.
[0380] The ionic compound (b-2) as described above can be used as a
mixture of two or more species.
[0381] (b-3) Organoaluminum Compound
[0382] Examples of the organoaluminum compound (b-3) (in the
present specification, may also be referred to as "component
(b-3)") forming the catalyst for olefin polymerization include an
organoaluminum compound represented by the following Formula [7],
and a complex alkylated product of Group 1 transition metal and
aluminum represented by the following Formula [8].
R.sup.a.sub.mAl(OR.sup.b).sub.nH.sub.pX.sub.q [7]
wherein in the Formula [7], R.sup.a and R.sup.b, which may be
identical to or different from each other, each represent a
hydrocarbon group having 1 to 15, preferably 1 to 4, carbon atoms;
X represents a halogen atom; m is a number satisfying
0<m.ltoreq.3, n is a number satisfying 0.ltoreq.n<3, p is a
number satisfying 0.ltoreq.p<3, and q is a value satisfying
0.ltoreq.q<3; and m+n+p+q=3.
[0383] Specific examples of such compound include
tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum,
tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum;
[0384] tri-branched-alkylaluminums such as triisopropylaluminum,
triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum,
tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and
tri-2-ethylhexylaluminum;
[0385] tricycloalkylaluminums such as tricyclohexylaluminum, and
tricyclooctylaluminum;
[0386] triarylaluminums such as triphenylaluminum, and
tritolylaluminum;
[0387] dialkylaluminum hydrides such as diisopropylaluminum
hydride, and diisobutylaluminum hydride;
[0388] alkenylaluminums represented by general formula:
(i-C.sub.4H.sub.9).sub.xAl.sub.y(C.sub.5H.sub.10).sub.z (wherein x,
y and z are positive numbers, and z.ltoreq.2x), such as
isoprenylaluminum;
[0389] alkylaluminum alkoxides such as isobutylaluminum methoxide,
and isobutylaluminum ethoxide;
[0390] dialkylaluminum alkoxides such as dimethylaluminummethoxide,
diethylaluminumethoxide, and dibutylaluminumbutoxide;
[0391] alkylaluminum sesquialkoxides such as ethylaluminum
sesquiethoxide, and butylaluminum sesquibutoxide;
[0392] partially alkoxylated alkylaluminums having an average
composition represented by general formula:
Ra.sub.2.5Al(ORb).sub.0.5 and the like;
[0393] alkylaluminum aryloxides such as diethylaluminum phenoxide,
and diethylaluminum(2,6-di-t-butyl-4-methylphenoxide);
[0394] dialkylaluminum halides such as dimethylaluminum chloride,
diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum
bromide, and diisobutylaluminum chloride;
[0395] alkylaluminum sesquihalides such as ethylaluminum
sesquichloride, butylaluminum sesquichloride, and ethylaluminum
sesquibromide;
[0396] partially halogenated alkylaluminums such as alkylaluminum
dihalide such as ethylaluminum dichloride;
[0397] dialkylaluminum hydrides such as diethylaluminum hydride,
and dibutylaluminum hydride;
[0398] partially hydrogenated alkylaluminums such as alkylaluminum
dihydride such as ethylaluminum dihydride, and propylaluminum
dihydride;
[0399] partially alkoxylated and halogenated alkylaluminums such as
ethylaluminum ethoxychloride, butylaluminum butoxychloride, and
ethylaluminum ethoxybromide.
M.sup.2AlR.sup.a.sub.4 [8]
wherein in Formula [8], M.sup.2 represents Li, Na or K; and R.sup.a
represents a hydrocarbon group having 1 to 15, preferably 1 to 4,
carbon atoms.
[0400] Such compound is exemplified by LiAl(C.sub.2H5).sub.4,
LiAl(C.sub.7H.sub.15).sub.4 or the like.
[0401] A compound similar to the compound represented by the
Formula [8] can also be used, and examples thereof include an
organoaluminum compound in which two or more aluminum compounds are
bound with a nitrogen atom interposed therebetween. Specifically,
such compound is exemplified by
(C.sub.2H.sub.5).sub.2AlN(C.sub.2H.sub.5)Al(C.sub.2H.sub.5).sub.2
or the like.
[0402] As the organoaluminum compound (b-3), trimethylaluminum and
triisobutylaluminum are preferably used from the aspect of easy
availability.
[0403] Furthermore, in the catalyst (1) for olefin polymerization,
if necessary, a support (c) may be used along with the (a-1)
bridged metallocene compound represented by the Formula [1-1], and
(b) at least one compound selected from (b-1) the organoaluminum
oxy compound, (b-2) the compound which reacts with the bridged
metallocene compound (a-1) to form an ion pair, and (b-3) the
organoaluminum compound.
[0404] (c) Support
[0405] The support (c) (in the present specification, may be
referred to as "component (c)") is an inorganic or organic
compound, and is a granular or microparticulate solid. Among these,
the inorganic compound is preferably a porous oxide, an inorganic
halide, a clay, a clay mineral, or an ion exchangeable lamellar
compound.
[0406] As the porous oxide, specifically SiO.sub.2,
Al.sub.2O.sub.3, MgO, ZrO, TiO.sub.2, B.sub.2O.sub.3, CaO, ZnO,
BaO, ThO.sub.2 and the like, or complexes or mixtures containing
these, for example, natural or synthetic zeolites, SiO.sub.2--MgO,
SiO.sub.2--Al.sub.2O.sub.3, SiO.sub.2--TiO.sub.2,
SiO.sub.2--V.sub.2O.sub.5, SiO.sub.2--Cr.sub.2O.sub.3,
SiO.sub.2--TiO.sub.2--MgO and the like can be used. Among these, it
is preferable to use SiO.sub.2 and/or Al.sub.2O.sub.3 as the main
component.
[0407] The above-mentioned inorganic oxide may contain a small
amount of carbonate, sulfate, nitrate or oxide component, such as
Na.sub.2CO.sub.3, K.sub.2CO.sub.3, CaCO.sub.3, MgCO.sub.3,
Na.sub.2SO.sub.4, Al.sub.2(SO.sub.4).sub.3, BaSO.sub.4, KNO.sub.3,
Mg(NO.sub.3).sub.2, Al(NO.sub.3).sub.3, Na.sub.2O, K.sub.2O, and
Li.sub.2O.
[0408] Such porous oxide may vary in the properties depending on
the type and method for production. The support (c) has a particle
size of 3 to 300 .mu.m, preferably 10 to 300 .mu.m, and more
preferably 20 to 200 .mu.m, a specific surface area in the range of
50 to 1000 m.sup.2/g, preferably 100 to 700 m.sup.2/g, and a pore
volume preferably in the range of 0.3 to 3.0 cm.sup.3/g. Such
support is calcined as necessary at 100 to 1000.degree. C., and
preferably 150 to 700.degree. C., and used.
[0409] As the inorganic halide, MgCl.sub.2, MgBr.sub.2, MnCl.sub.2,
MnBr.sub.2 and the like are used. The inorganic chloride may be
used directly, or may be used after grinding with a ball mill or a
vibration mill. Furthermore, a halide obtained by dissolving the
inorganic halide in a solvent such as alcohol, and then
precipitating the compound into a microparticulate form using a
precipitating agent, can also be used.
[0410] The clay is usually constituted of a clay mineral as the
main component. The ion exchangeable lamellar compound is a
compound having a crystal structure in which the planes constituted
of ionic bonding are stacked on one another in parallel with weak
bonding strength, and in which the ions contained can be exchanged.
Most of the clay minerals are ion exchangeable lamellar compounds.
The clay, clay mineral and ion exchangeable lamellar compound are
not limited to natural products, and artificially synthesized
products can also be used. Furthermore, examples of the clay, clay
mineral or ion exchangeable lamellar compound include clays, clay
minerals, and ion crystalline compounds having lamellar crystal
structures such as hexagonal close packed type, antimony type,
CdCl.sub.2 type, and CdI.sub.2 type.
[0411] Examples of the clay and clay mineral include kaolin,
bentonite, kibushi clay, gairome clay, allophane, hisingerite,
pyrophyllite, mica group, montmorillonite group, vermiculite,
phyllite group, palygorskite, kaolinite, nacrite, dickite, and
halloysite. Examples of the ion exchangeable layer compound include
crystalline acid salts of multivalent metals such as
.alpha.-Zr(HAsO.sub.4).sub.2H.sub.2O, .alpha.-Zr(HPO.sub.4).sub.2,
.alpha.-Zr(KPO.sub.4).sub.2.3H.sub.2O, .alpha.-Ti(HPO.sub.4).sub.2,
.alpha.-Ti(HAsO.sub.4).sub.2.H.sub.2O,
.alpha.-Sn(HPO.sub.4).sub.2.H.sub.2O, .gamma.-Zr(HPO.sub.4).sub.2,
.gamma.-Ti(HPO.sub.4).sub.2, and
.gamma.-Ti(NH.sub.4PO.sub.4).sub.2.H.sub.2O.
[0412] It is preferable for such clay, clay mineral or ion
exchangeable lamellar compound that the volume of pores having a
radius of 20 .ANG. or more as measured by mercury porosimetry is
preferably 0.1 cc/g or larger, and particularly preferably 0.3 to 5
cc/g. The pore volume is measured for the pore radius in the range
of 20 to 3.times.10.sup.4 .ANG. according to the mercury
porosimetry using the mercury porosimeter.
[0413] When a support having a pore volume with 20 .ANG. radius or
more of 0.1 cc/g or less is used, there is a tendency that high
polymerization activity is hardly obtained.
[0414] The clay and clay mineral may preferably be subjected to a
chemical treatment. Any of the chemical treatment such as a surface
treatment which removes impurities attached on the surface, and
treatments giving an effect on the crystal structure of the clay,
can be used. Specific examples of the chemical treatment include an
acid treatment, an alkali treatment, a treatment with salts, and a
treatment with organic compound. The acid treatment removes
impurities on a surface, and also increases the surface area by
eluting a positive ion such as Al, Fe, and Mg in the crystal
structure. The alkali treatment destroys the crystal structure of
the clay, and brings a structural change in the clay. The treatment
with salts and the treatment with organic compound form an ionic
complex, molecular complex, organic derivative or the like, and can
change the surface area and the interlayer distance.
[0415] The ion exchangeable lamellar compound may be a lamellar
compound with the interlayer distance enlarged by exchanging the
interlayer exchangeable ion with another bulky ion using its ion
exchangeability. Such bulky ion plays a supportive role to support
a lamellar structure, and is generally called as a pillar. Also,
the introduction of other substance to the interlayer space of the
lamellar compound is known as intercalation. Examples of the guest
compound for intercalation include a positive ion inorganic
compound such as TiCl.sub.4 and ZrCl.sub.4, a metal alkoxide
(wherein R is a hydrocarbon group or the like) such as
Ti(OR).sub.4, Zr(OR).sub.4, PO(OR).sub.3, and B(OR).sub.3, a metal
hydroxide ion such as [Al.sub.13O.sub.4(OH).sub.24].sup.7+,
[Zr.sub.4(OH).sub.14].sup.2+, and
[Fe.sub.3O(OCOCH.sub.3).sub.6].sup.+. These compounds may be used
alone or in combination of two or more species. When allowing these
compounds to undergo intercalation, a polymer obtained by
hydrolyzing metal alkoxide such as Si(OR).sub.4, Al(OR).sub.3 and
Ge(OR).sub.4 (R's are each a hydrocarbon group, or the like), a
colloidal inorganic compound such as SiO.sub.2, or the like can be
allowed to coexist. Examples of the pillar include oxides produced
by conducting thermal dehydration of the above-mentioned metal
hydroxide ion after intercalation thereof. Among them, preferred
are clays and clay minerals and particularly preferred are
montmorillonite, vermiculite, pectolite, tainiolite, and synthetic
mica.
[0416] The clays, clay minerals, and ion-exchangeable layer
compounds may be used directly, or used after being subjected to a
treatment with ball mill, screening or the like. Or alternatively,
they may be used after adsorbing newly added water thereonto, or
after being subjected to thermal dehydration treatment. They may be
used alone or in combination of two or more-species.
[0417] In the case of using an ion-exchangeable lamellar silicate,
it is possible to reduce the amount of use of an organoaluminum oxy
compound such as alkylaluminoxane, by using the ion exchangeable
property and lamellar structure, in addition to the function as a
support. Ion exchangeable lamellar silicate is mainly obtained in
nature as a main component of a clay mineral, but without imposing
any particular limitation to natural products, artificially
synthesized products can also be used. Specific examples of the
clay, the clay mineral, and ion exchangeable layer silicate include
kaolinite, montmorillonite, hectorite, bentonite, smectite,
vermiculite, tiniolite, synthetic mica, and synthetic
hectorite.
[0418] The organic compound may be exemplified by a granular solid
or a microparticulate solid having a particle size in the range of
3 to 300 .mu.m, and preferably 10 to 300 .mu.m. Specific examples
thereof include (co)polymers produced from an .alpha.-olefin having
2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and
4-methyl-1-pentene as the main component; a (co)polymer produced
from vinylcyclohexane, styrene as the main component; and polymers
or modified products having a polar functional group obtained by
copolymerizing or graft polymerizing a polar monomer such as
acrylic acid, acrylic ester and maleic acid anhydride, into the
above-mentioned copolymer or a polymer. These particulate supports
may be used alone or in combination of two or more species.
[0419] Furthermore, the catalyst for olefin polymerization of the
present invention (1) may also contain a specific organic compound
component (d) that will be described later according to necessity,
along with the (a-1) bridged metallocene compound represented by
the Formula [1-1], (b) at least one compound selected from (b-1)
the organoaluminum oxy compound, (b-2) the compound which reacts
with the bridged metallocene compound (a-1) to form an ion pair,
and (b-3) the organoaluminum compound, and optional (c) the
support.
[0420] (d) Organic Compound Component
[0421] In the present invention, the organic compound component (d)
(in the present specification, may be referred to as "component
(d)") is used if needed, for the purpose of improving the
polymerization performance and properties of the produced obtained.
Such organic compound component (d) is exemplified by alcohols,
phenolic compounds, carboxylic acids, phosphorus compounds,
sulfonates and the like, but the compound is not limited to
these.
[0422] In the present invention (1), the method of using each
component, and the order of addition are arbitrarily selected, and
the following methods may be mentioned as the methods of
polymerization.
[0423] (1) A method comprising adding the component (a-1) alone
into the polymerization vessel.
[0424] (2) A method comprising adding the component (a-1) and
component (b) into the polymerization vessel in an arbitrary
order.
[0425] (3) A method comprising adding a catalyst component in which
the component (a-1) is supported on the support (c), and the
component (b) into the polymerization vessel in an arbitrary
order.
[0426] (4) A method comprising adding a catalyst component in which
the component (b) is supported on the support (c), and the
component (a-1) into the polymerization vessel in an arbitrary
order.
[0427] (5) A method comprising adding a catalyst component in which
the component (a-1) and the component (b) are supported on the
support (c) into the polymerization vessel.
[0428] In the respective methods of (2) to (5) described above, at
least two or more of the catalyst components may be brought into
contact with each other in advance.
[0429] In the respective methods of (4) and (5) described above
using supported component (b), unsupported component (b) may be
added in any order, as necessary. In this case, the components (b)
may be identical to or different from each other.
[0430] Furthermore, the solid catalyst component having the
component (a-1) supported on the component (c), and the solid
catalyst component having the component (a-1) and component (b)
supported on the component (c) may have a prepolymerized olefin, or
a prepolymerized solid catalyst component may further have the
catalyst component supported thereon.
[0431] In the method for polymerizing olefin of the present
invention (1), olefin is polymerized or copolymerized in the
presence of the catalyst for olefin polymerization as described
above, to obtain an olefin polymer.
[0432] In the present invention (1), polymerization can be carried
out by any of a liquid phase polymerization method such as a
solution polymerization, and a suspension polymerization, and a gas
phase polymerization method. Specific examples of the inert
hydrocarbon medium used in the liquid phase polymerization method
include aliphatic hydrocarbons such as propane, butane, pentane,
hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic
hydrocarbons such as cyclopentane, cyclohexane, and
methylcyclopentane; aromatic hydrocarbons such as benzene, toluene,
and xylene; halogenated hydrocarbons such as ethylene chloride,
chlorobenzene, and dichloromethane, and mixtures thereof. The
olefin to be polymerized may also be used per se as the
solvent.
[0433] When polymerization of olefin is performed using the
catalyst for olefin polymerization as described above, the
component (a-1) is usually used in an amount of 10.sup.-9 to
10.sup.-1 moles, and preferably 10.sup.-8 to 10.sup.-2 moles, per
liter of the reaction volume.
[0434] The component (b-1) is used in an amount such that the molar
ratio [(b-1)/M] of the component (b-1) and the total transition
metal atoms (M) in the component (a-1) is usually 0.01 to 5,000,
and preferably 0.05 to 2,000. The component (b-2) is used in an
amount such that the molar ratio [(b-2)/M] of the component (b-2)
and the transition metal atoms (M) in the component (a-1) is
usually 1 to 10, and preferably 1 to 5. The component (b-3) is used
in an amount such that the molar ratio [(b-3)/M] of the aluminum
atoms in the component (b-3) and the total transition metal (M) in
the component (a-1) is usually 10 to 5,000, and preferably 20 to
2,000.
[0435] The component (d) is used, in the case where the component
(b) is component (b-1), in an amount such that the molar ratio
[(d)/(b-1)] is usually 0.01 to 10, and preferably 0.1 to 5; in the
case where the component (b) is component (b-2), in an amount such
that the molar ratio [(d)/(b-2)] is usually 0.01 to 10, and
preferably 0.1 to 5; in the case where the component (b) is
component (b-3), the molar ratio [(d)/(b-3)] is usually 0.01 to 2,
and preferably 0.005 to 1.
[0436] The temperature for olefin polymerization using the catalyst
for olefin polymerization is generally within the range from -50 to
+200.degree. C., preferably from 0 to 170.degree. C., more
preferably from 25 to 170.degree. C., and even more preferably from
40 to 170.degree. C. The polymerization pressure is under the
condition of generally from normal pressure to 10 MPa gauge
pressure, and preferably from normal pressure to 5 MPa gauge
pressure, and the polymerization reaction can be carried out either
batchwise, semicontinuously or continuously. The polymerization can
be carried out by dividing the process into two or more stages
having different reaction conditions. The molecular weight of the
resulting propylene polymer can be also regulated by allowing
hydrogen to exist in the polymerization system or by varying the
polymerization temperature. Moreover, the molecule weight can be
regulated according to the amount of the component (b) used. When
adding hydrogen, the suitable amount to be added is from about
0.001 to 100 NL per 1 kg of the olefin.
[0437] In the present invention (1), the olefin supplied to the
polymerization reaction is one or more monomers selected from
.alpha.-olefins having two or more carbon atoms. The .alpha.-olefin
is a straight-chained or branched .alpha.-olefin having 2 to 20
carbon atoms, and is exemplified by ethylene, propylene, 1-butene,
2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene,
4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene
or the like.
[0438] In the method of polymerization of the present invention
(1), there may be used cyclic olefins having 3 to 30 carbon atoms,
preferably 3 to 20 carbon atoms, such as cyclopentene,
cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene
and
2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene;
[0439] polar monomers, for example, .alpha.,.beta.-unsaturated
carboxylic acids such as acrylic acid, methacrylic acid, fumaric
acid, maleic anhydride, itaconic acid, itaconic anhydride and
bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic anhydride, and metal
salts thereof such as sodium salt, potassium salt, lithium salt,
zinc salt, magnesium salt, calcium salt and aluminum salt;
[0440] .alpha.,.beta.-unsaturated carboxylic esters such as methyl
acrylate, n-butyl acrylate, n-propyl acrylate, isopropyl acrylate,
n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate,
2-n-butylhexyl acrylate, methyl methacrylate, n-butyl methacrylate,
n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate
and isobutyl methacrylate; vinyl esters such as vinyl acetate,
vinyl propionate,
[0441] vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate
and vinyl trifluoroacetate;
[0442] unsaturated glycidyls such as glycidyl acrylate, glycidyl
methacrylate and itaconic acid monoglycidyl ester; and the
like.
[0443] Furthermore, vinylcyclohexane, dienes and polyenes;
[0444] aromatic vinyl compounds, for example, mono- or
polyalkylstryenes such as styrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene,
o-n-butylstyrene, m-n-butylstyrene, and p-n-butylstyrene;
[0445] styrene derivatives containing a functional group, such as
methoxystyrene, ethoxystyrene, vinyl benzoate, methylvinyl
benzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene,
p-chlorostyrene and divinyl benzene; and
[0446] 3-phenylpropylene, 4-phenylpropylene, .alpha.-methylstyrene
and the like may be allowed to coexist in the reaction system to
facilitate the polymerization.
[0447] The method for production of the present invention (1) can
be used, for example, in the production of a polymer comprising 100
to 90 mol %, preferably 100 to 91 mol %, and more preferably 100 to
96 mol %, of constituent units derived from one monomer (for
example, propylene) selected from .alpha.-olefins having 3 to 20
carbon atoms; and 10 to 0 mol %, preferably 9 to 0 mol %, and more
preferably 4 to 0 mol %, of constituent units derived from one or
more selected from .alpha.-olefins having 2 to carbon atoms
(excluding propylene), which monomer is different from the
above-described monomer. Examples thereof include production of
propylene homopolymer. Such .alpha.-olefin polymer preferably has a
syndiotactic structure, and for example, its rrrr value measured by
the method that will be described later is preferably 70% or
greater, and preferably 85% or greater.
[0448] The method for production of the present invention (1) can
be used, for example, in the production of a polymer comprising 100
to 50 mol % of constituent units derived from ethylene, and 50 to 0
mol % of constituent units derived from one or more monomers
selected from .alpha.-olefins having 3 to 20 carbon atoms. Examples
thereof include production of ethylene homopolymer.
[0449] The method for production of the present invention (1) can
also be used in the production of other polymers.
[0450] Next, methods for measuring the properties of the polymer
obtained by the polymerization of olefin in the presence of a
catalyst containing a transition metal compound of the present
invention (1), will be described.
[0451] [Intrinsic Viscosity ([.eta.])]
[0452] It is a value measured at 135.degree. C. using a decalin
solvent.
[0453] Specifically, about 20 mg of granulated pellets are
dissolved in 15 ml of decalin, and the specific viscosity .eta.sp
is measured in an oil bath at 135.degree. C. 5 ml of the decalin
solvent is added to this decalin solution for dilution, and than
the specific viscosity .eta.sp is measured in the same manner. This
dilution operation is additionally repeated two times, and the
value of .eta.sp/C of when the concentration (C) is extrapolated to
0 is determined as the intrinsic viscosity.
[.eta.]=lim(.eta.sp/C)(C.fwdarw.0).
[0454] [Melting Point (Tm)]
[0455] A polymer sample maintained at 200.degree. C. for 10 minutes
is cooled to 30.degree. C., maintained for 5 minutes, and then
heated at a rate of 10.degree. C./min by differential scanning
calorimetry (DSC), and the melting point is calculated from the
crystal melting peak obtained therefrom. For the propylene polymer
described in Example I here, one or two peaks are observed, and
when two peaks are detected, the peak on the lower temperature side
is indicated as Tm.sub.1, and the peak on the higher temperature
side is indicated as Tm.sub.2. If there is one peak, the peak is
indicated as Tm.sub.2.
[0456] Furthermore, the stereoregularity (rrrr) is calculated from
the determination of .sup.13C-NMR spectrum.
[0457] The rrrr fraction is determined from the absorption
intensities of Prrrr (absorption intensity resulting from the
methyl group of the third unit at a site of 5 propylene units being
sequentially syndiotactically bound) and Pw (absorption intensity
resulting from all the methyl groups of propylene units), by the
following formula (1).
rrrr fraction (%)=100.times.Prrrr/Pw (1)
[0458] NMR measurement is carried out, for example, in the
following manner. Specifically, 0.35 g of a sample is heated to
melt in 2.0 ml of hexachlorobutadiene. This solution is filtered
through a glass filter (G2), subsequently, 0.5 ml of deuterated
benzene is added, and the mixture is placed in an NMR tube having
an internal diameter of 10 mm. Then, .sup.13C-NMR measurement is
performed at 120.degree. C. using a GX-500 type NMR measuring
apparatus manufactured by JEOL, Ltd. The accumulation times are
10,000 or greater.
[0459] <Method for Producing Propylene-Based Copolymer
(B1)>
[0460] Next, the method for producing the propylene-based copolymer
(B1) of the present invention (2) will be described in detail.
[0461] The method for producing the propylene-based copolymer (B1)
of the present invention (2) is characterized in polymerizing
propylene and at least one monomer selected from .alpha.-olefins
and polyenes, in the presence of a catalyst (2) for olefin
polymerization comprising:
[0462] (a-2) a bridged metallocene compound represented by the
above Formula [1-2]; and
[0463] (b) at least one compound selected from:
[0464] (b-1) an organoaluminum oxy compound,
[0465] (b-2) a compound which reacts with the bridged metallocene
compound (a-2) to form an ion pair, and
[0466] (b-3) an organoaluminum compound.
[0467] [1](a-2) Bridged Metallocene Compound
[0468] The bridged metallocene compound (a-2) represented by the
above Formula [1-2](in the present specification, may also be
referred to as "component (a-2)") has the following chemical
structural features [m2-1] to [m2-3].
[0469] [m2-1] Of the two ligands, one is a cyclopentadienyl group
which may be substituted, and the other is a fluorenyl group which
is substituted (hereinafter, may be referred to as "substituted
fluorenyl group").
[0470] [m2-2] The two ligands are bound by a covalently bonded
bridge containing a carbon atom or silicon atom having an aryl
group or a substituted aryl group (hereinafter, may be referred to
as "covalently bonded bridge containing an aryl group or a
substituted aryl group").
[0471] [m2-3] The transition metal (M) constituting the metallocene
compound is titanium, zirconium or hafnium.
[0472] Hereinafter, the cyclopentadienyl group which may be
substituted, the substituted fluorenyl group and the bridging part,
which are chemical structural features of the bridged metallocene
compound (a-2), and other features will be described in order, and
preferred bridged metallocene compounds having these features, and
examples thereof, and finally the method for polymerization of the
present invention (2) using the bridged metallocene compound (a-2)
will be described in detail.
[0473] Cyclopentadienyl Group which May be Substituted
[0474] The cyclopentadienyl group may or may not be substituted. An
unsubstituted cyclopentadienyl group is a cyclopentadienyl group in
which R.sup.1, R.sup.2, R.sup.3 and R.sup.4 possessed by the
cyclopentadienyl group moiety in the above Formula [1-2] are all
hydrogen atoms, and a substituted cyclopentadienyl group may be a
cyclopentadienyl group in which any one or more of R.sup.1,
R.sup.2, R.sup.3 and R.sup.4 may be substituted with a hydrocarbon
group (f1), or a silicon-containing group (f2). In the case of a
group in which two or more of R.sup.1, R.sup.2, R.sup.3 and R.sup.4
are groups other than hydrogen atom, these groups may be identical
to or different from each other.
[0475] The hydrocarbon group (f1) used for R.sup.1 to R.sup.4 may
be preferably exemplified, in the case where the substituent does
not form a ring together with another substituent, by a hydrocarbon
group having 1 to 20 carbon atoms in total (hereinafter, may also
be referred to as "hydrocarbon group (f1')").
[0476] When R.sup.2 and R.sup.3 are each the hydrocarbon group
(f1), R.sup.2 and R.sup.3 may be linked to each other to form a
ring (hereinafter, may also be referred to as "ring (f''')"). When
substituents R.sup.2 and R.sup.3 are linked to each other to form a
ring, it is more preferable that only R.sup.2 and R.sup.3 among
R.sup.1 to R.sup.4 form a ring.
[0477] In the case where, for example, substituents R.sup.2 and
R.sup.3 are linked to each other to form a ring, regardless of the
fact that each of the above-mentioned R.sup.2 and R.sup.3
preferably has 1 to carbon atoms, the sum of the carbon atoms of
the two substituents forming a ring is preferably 2 to 40, more
preferably 3 to 30, and even more preferably 4 to 20.
[0478] Even in the case where the substituents R.sup.2 and R.sup.3
are linked to each other to form a ring, a part of the hydrogen
atoms directly attached to carbon atoms of the substituents may be
substituted by a halogen atom, an oxygen-containing group, a
nitrogen-containing group or a silicon-containing group, and in
this case, the sum of the carbon atoms of the two substituents
forming a ring includes the number of carbon atoms contained in the
oxygen-containing group, the nitrogen-containing group and the
silicon-containing group.
[0479] The hydrocarbon group (f1') having 1 to 20 carbon atoms in
total means an alkyl group, an alkenyl group, an alkynyl group or
an aryl group, which is constituted only with carbon and
hydrogen.
[0480] The hydrocarbon group (f1') having 1 to 20 carbon atoms' in
total includes, in addition to the alkyl group, alkenyl group,
alkynyl group or aryl group constituted only with carbon and
hydrogen, a heteroatom-containing hydrocarbon group in which a part
of the hydrogen atoms are substituted with a halogen atom, an
oxygen-containing group, a nitrogen-containing group or a
silicon-containing group. Examples of such hydrocarbon group (f1')
include:
[0481] straight-chained hydrocarbon groups such as a methyl group,
an ethyl group, an n-propyl group, an allyl group, an n-butyl
group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an
n-octyl group, an n-nonyl group, and an n-decanyl group;
[0482] branched hydrocarbon groups such as an isopropyl group, a
t-butyl group, an amyl group, a 3-methylpentyl group, a
1,1-diethylpropyl group, a 1,1-dimethylbutyl group,
1-methyl-1-propylbutyl group, a 1,1-propylbutyl group, a
1,1-dimethyl-2-methylpropyl group, and a
1-methyl-1-isopropyl-2-methylpropyl group;
[0483] saturated cyclic hydrocarbon groups such as a cyclopentyl
group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group,
a norbornyl group, and an adamantyl group;
[0484] unsaturated cyclic hydrocarbon groups such as a phenyl
group, a naphthyl group, a biphenyl group, a phenanthryl group, and
an anthracenyl group, and nuclear alkyl-substituted products
thereof;
[0485] saturated hydrocarbon groups substituted with an aryl group
such as a benzyl group, and a cumyl group; and
[0486] heteroatom-containing hydrocarbon groups such as a methoxy
group, an ethoxy group, a phenoxy group, an N-methylamino group, a
trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl
group, a pentafluorophenyl group, a fluorophenyl group, a
chlorophenyl group, a bromophenyl group, a chlorobenzyl group, a
fluorobenzyl group, a bromobenzyl group, a dichlorobenzyl group, a
difluorobenzyl group, a trichlorobenzyl group, and a
trifluorobenzyl group.
[0487] The silicon-containing group (f2) is a group having a
silicon atom which is covalently bonded to a ring carbon of the
cyclopentadienyl group, and is specifically an alkylsilyl group or
an arylsilyl group. A preferred silicon-containing group (f2), in
the case where the substituent does not form a ring together with
another substituent, may be exemplified by a silicon-containing
group (f2') having 1 to 20 carbon atoms in total, and examples
thereof include a trimethylsilyl group, and a triphenylsilyl
group.
[0488] In this cyclopentadienyl group, it is preferable that
R.sup.1 and R.sup.4 are identical atoms or identical groups, and
R.sup.2 and R.sup.3 are linked to form a ring, or are identical
atoms or identical groups. It is more preferable that R.sup.1 and
R.sup.4 are hydrogen atoms, and it is particularly preferable that
all of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are hydrogen
atoms.
[0489] Substituted Fluorenyl Group
[0490] Important features for the fluorenyl group moiety in the
chemical structure represented by the above Formula [1-2] used in
the method for polymerization of the present invention (1), are
that R.sup.6 and R.sup.11 are identical atoms or identical groups
selected from hydrogen, a hydrocarbon group, and a
silicon-containing group; R.sup.7 and R.sup.10 are identical atoms
or identical groups selected from hydrogen, a hydrocarbon group and
a silicon-containing group; R.sup.6, R.sup.7, R.sup.10 and R.sup.11
are not simultaneously hydrogen atoms. Therefore, R.sup.6, R.sup.7,
R.sup.10, R.sup.11 may be each the hydrocarbon group (f1) described
above, or the silicon-containing group (f2) described above.
[0491] Furthermore, R.sup.5, R.sup.8, R.sup.9 and R.sup.12 may be
atoms or groups that may be identical to or different from each
other, and selected from hydrogen, the hydrocarbon group (f1) and
the silicon-containing group (f2), and adjacent groups among
R.sup.5 to R.sup.12 may be linked to each other to form a ring.
[0492] Examples of the hydrocarbon group (f1) used in the
substituents R.sup.5 to R.sup.12 include, in the case where the
substituent is a group not forming a ring together with another
substituent, a hydrocarbon group having 1 to 20 carbon atoms in
total (the hydrocarbon group (f1')).
[0493] When the substituents R.sup.5 to R.sup.12 are each the
hydrocarbon group (f1), the substituent may be linked to another
substituent among the substituents R.sup.5 to R.sup.12 within the
range of the above-described combinations of adjacent groups, to
form a ring. In this case, the adjacent substituents among R.sup.5
to R.sup.12 are linked to each other to form a ring (ring
(f''')).
[0494] Furthermore, when adjacent substituents among the
substituents R.sup.5 to R.sup.12 are linked to each other within
the range of the above-described combinations of adjacent groups,
to form a ring, two, three, or four adjacent substituents among
substituents R.sup.5 to R.sup.12 may be linked to each other to
form a ring(s), and it is preferable that two adjacent groups among
the substituents R.sup.5 to R.sup.12 are linked to each other to
form a ring.
[0495] For example, when two adjacent substituents among
substituents R.sup.5 to R.sup.12 are linked to each other to form a
ring (for example, when R.sup.6 and R.sup.7 are linked to each
other to form a ring, etc.), regardless of the fact that the
preferred number of carbon atoms for each of the above-described
R.sup.5 to R.sup.12 is 1 to 20, the sum of the carbon atoms in the
two substituents forming a ring is preferably 2 to 40, more
preferably 3 to 30, and even more preferably 4 to 20.
[0496] For example, when three adjacent substituents among
substituents R.sup.5 to R.sup.12 are linked to each other to form
rings (for example, R.sup.5, R.sup.6 and R.sup.7 are linked to each
other form rings, etc.), regardless of the fact that the preferred
number of carbon atoms for each of the above-described R.sup.5 to
R.sup.12 is 1 to 20, the sum of the carbon atoms in the three
substituents forming a ring is preferably 3 to 60, more preferably
5 to 40, and even more preferably 7 to 30.
[0497] For example, when four adjacent substituents among
substituents R.sup.5 to R.sup.12 are linked with one another to
form rings (for example, R.sup.5 and R.sup.6, and R.sup.7 and
R.sup.8 are linked to each other to form rings, etc.), regardless
of the fact that the preferred number of carbon atoms for each of
the above-described R.sup.5 to R.sup.12 is 1 to 20, the sum of
carbon atoms in the two substituents forming a ring is preferably 4
to 80, more preferably 7 to 60, and even more preferably 10 to
40.
[0498] Even in the case where adjacent substituents are linked to
each other to form a ring(s), a part of the hydrogen atoms directly
attached to carbon atoms of the substituent may be substituted by a
halogen atom, an oxygen-containing group, a nitrogen-containing
group or a silicon-containing group, and in this case, the sum of
carbon atoms in a plurality of substituents forming a ring includes
the number of carbon atoms contained in the oxygen-containing
group, the nitrogen-containing group or the silicon-containing
group.
[0499] From the viewpoint of polymerization activity or increasing
the molecular weight of the produced polymer in the present
invention (2), it is preferable that R.sup.6, R.sup.7, R.sup.10 and
R.sup.11 are all groups other than hydrogen atom, that is, R.sup.6
and R.sup.11 are identical groups selected from a hydrocarbon group
and a silicon-containing group, and R.sup.7 and R.sup.10 are
identical groups selected from a hydrocarbon group and a
silicon-containing group.
[0500] It is particularly preferable that R.sup.6 and R.sup.11 are
any one of the following (1) to (3):
[0501] (1) hydrocarbon groups not forming a ring with adjacent
groups, and each independently having 2 or more carbon atoms, more
preferably 3 or more carbon atoms, and particularly preferably 4 or
more carbon atoms;
[0502] (2) hydrocarbon groups, wherein R.sup.6 forms a ring with
R.sup.7, and R.sup.11 forms a ring with R.sup.10; and
[0503] (3) respectively silicon-containing groups.
[0504] Furthermore, among the silicon-containing groups, a
silicon-containing group of which the sum of carbon atoms and
silicon atoms is 3 or more, and preferably 4 or more, is preferred.
In order to enhance the effect of the present invention,
[0505] when R.sup.6 is a hydrocarbon group which does not form a
ring with its adjacent group, and R.sup.7 is a hydrocarbon group
which does not form a ring together with an adjacent group, it is
preferable that the number of carbon atoms of R.sup.6 is equal to
or larger than the number of carbon atoms of R.sup.7;
[0506] when R.sup.6 is a silicon-containing group, and R.sup.7 is a
silicon-containing group, it is preferable that the total number of
silicon atoms and carbon atoms of R.sup.6 is equal to or larger
than the total number of silicon atoms and carbon atoms of
R.sup.7;
[0507] when R.sup.6 is a hydrocarbon group which does not form a
ring with an adjacent group, and R.sup.7 is a silicon-containing
group, it is preferable that the number of carbon atoms of R.sup.6
is equal to or larger than the total number of silicon atoms and
carbon atoms of R.sup.7; and
[0508] when R.sup.6 is a silicon-containing group, and R.sup.7 is a
hydrocarbon group which does not form a ring, it is preferable that
the total number of silicon atoms and carbon atoms of R.sup.6 is
equal to or larger than the number of carbon atoms of R.sup.7.
[0509] The hydrocarbon group or silicon-containing group of
R.sup.6, R.sup.7, R.sup.10, and R.sup.11 may be the above-mentioned
groups, and the hydrocarbon group (f1'), the ring (f'''), the
silicon-containing group (f2') having 1 to 20 carbon atoms in
total, and the like are preferred. Particularly preferable examples
of specific substituents include a tert-butyl group, a
methylcyclohexyl group, a methyladamantyl group, a phenyl group,
and a naphthyl group. Furthermore, as described above, R.sup.6,
R.sup.7, R.sup.10, and R.sup.11 may not respectively exist as
individual substituents, R.sup.6 and R.sup.7 may also be linked to
each other to form rings, and R.sup.10 and R.sup.11 may also be
linked to each other to form rings, and this is one of the most
preferred embodiment of the substituted fluorenyl group of the
bridged metallocene compound (a-2).
[0510] Covalently Bonded Bridge Containing Aryl Group or
Substituted Aryl Group
[0511] The main chain part of the bond connecting the
cyclopentadienyl group which may be substituted and the substituted
fluorenyl group is a divalent covalently bonded bridge containing
one carbon atom or silicon atom. An important feature in the method
for polymerization of the present invention (2) is that the
bridging atom Y in the covalently bonded bridging part has specific
groups which may be identical to and different from each other,
preferably specific aryl groups or substituted aryl groups
[R.sup.13 and R.sup.14]. By introducing the specific groups which
may be identical to and different from each other, preferably
specific aryl groups or substituted aryl groups, to the bridging
atom (Y), an olefin polymer having a high molecular weight that
could not be achieved by conventional polymerization processes can
be efficiently produced by the method for polymerization of the
present invention (2).
[0512] R.sup.13 and R.sup.14 are each selected from an aryl group
having 6 to 18 carbon atoms, an alkyl group having 1 to 40 carbon
atoms, an alkylaryl group having 6 to 40 carbon atoms, a fluoroaryl
group having 6 to 20 carbon atoms, a fluoroalkylaryl group having 7
to 40 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms,
a chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl
group having 6 to 20 carbon atoms, a bromoalkylaryl group having 7
to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms,
and an iodoalkylaryl group having 7 to 40 carbon atoms, and may be
identical to and different from each other. At least one of
R.sup.13 and R.sup.14 is selected from an aryl group having 7 to 18
carbon atoms, a chloroaryl group having 6 to 20 carbon atoms, a
chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl
group having 6 to 20 carbon atoms, a bromoalkylaryl group having 7
to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms,
an iodoalkylaryl group having 7 to 40 carbon atoms and a
fluoroalkylaryl group having 7 to carbon atoms.
[0513] Preferably, R.sup.13 and R.sup.14 are each selected from an
aryl group having 6 to 18 carbon atoms, a fluoroalkylaryl group
having 7 to 40 carbon atoms, a chloroaryl group having 6 to 20
carbon atoms, a chloroalkylaryl group having 7 to 40 carbon atoms,
a bromoaryl group having 6 to 20 carbon atoms, a bromoalkylaryl
group having 7 to 40 carbon atoms, an iodoaryl group having 6 to 20
carbon atoms, and an iodoalkylaryl group having 7 to 40 carbon
atoms, and may be identical to and different from each other. At
least one of R.sup.13 and R.sup.14 is selected from an aryl group
having 7 to 18 carbon atoms, a chloroaryl group having 6 to 20
carbon atoms, a chloroalkylaryl group having 7 to 40 carbon atoms,
a bromoaryl group having 6 to 20 carbon atoms, a bromoalkylaryl
group having 7 to 40 carbon atoms, an iodoaryl group having 6 to 20
carbon atoms, an iodoalkylaryl group having 7 to 40 carbon atoms
and a fluoroalkylaryl group having 7 to carbon atoms.
[0514] Examples of the aryl group or substituted aryl group include
an aryl group having 6 to 18 carbon atoms, such as a phenyl group,
a naphthyl group, an anthryl group and a phenanthryl group, and
groups resulting from substitution of one or more of their aromatic
hydrogens (sp2-hydrogen) with substituents.
[0515] Preferred examples among these include an aryl group having
6 carbon atoms, such as a phenyl group; an aryl group having 10
carbon atoms, such as a naphthyl group; an aryl group having 11 to
18 carbon atoms, preferably 11 to 14 carbon atoms, such as a
biphenyl group, an anthryl group, and a phenanthryl group; a
chloroaryl group having 6 to 20 carbon atoms, such as a
chlorophenyl group, and a dichlorophenyl group; a bromoaryl group
having 6 to 20 carbon atoms, such as a bromophenyl group and a
dibromophenyl group; an iodoaryl group having 6 to 20 carbon atoms,
such as an iodophenyl group and a diiodophenyl group; a
chloroalkylaryl group having 7 to 40 carbon atoms, preferably 7 to
20 carbon atoms, such as a (trichloromethyl)phenyl group, and a
bis(trichloromethyl)phenyl group; a bromoalkylaryl group having 7
to 40 carbon atoms, preferably 7 to 20 carbon atoms, such as a
(tribromomethyl)phenyl group, and a bis(tribromomethyl)phenyl
group; an iodoalkylaryl group preferably 7 to 40 carbon atoms,
preferably 7 to 20 carbon atoms, such as a (triiodomethyl)phenyl
group, and a bis(triiodomethyl)phenyl group; a fluoroalkylaryl
group having 7 to 40 carbon atoms, preferably 7 to 20 carbon atoms,
such as a (trifluoromethyl)phenyl group, a
bis(trifluoromethyl)phenyl group. It is particularly preferable
that a substituted phenyl group having their substituents located
at the meta-position and/or para-position.
[0516] In the present invention (2), particularly preferable
examples among these include an aryl group having 11 to 18 carbon
atoms, a chloroaryl group having 6 to 20 carbon atoms, a
chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl
group having 6 to 20 carbon atoms, a bromoalkylaryl group having 7
to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms,
an iodoalkylaryl group having 7 t o 40 carbon atoms, and a
fluoroalkylaryl group having 7 to 40 carbon atoms.
[0517] More preferred examples include specifically an m-biphenyl
group, a p-biphenyl group, an m-chlorophenyl group, a
p-chlorophenyl group, an m-trifluorophenyl group, a
p-trifluorophenyl group, a p-chlorophenyl group, a p-iodophenyl
group, a 3,5-ditrifluorophenyl group, a 5-chloronaphthyl group, and
a 6-chloronaphthyl group.
[0518] Furthermore, in the present invention (2), R.sup.13 and
R.sup.14 are each selected from an aryl group having 6 to 18 carbon
atoms, a chloroaryl group having 6 to 20 carbon atoms, a
chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl
group having 6 to 20 carbon atoms, a bromoalkylaryl group having 7
to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms,
an iodoalkylaryl group having 7 to 40 carbon atoms and a
fluoroalkylaryl group having 7 to 40 carbon atoms, and may be
identical to and different from each other. It is preferable that
at least one of R.sup.13 and R.sup.14 is selected from an aryl
group having 11 to 18 carbon atoms, a chloroaryl group having 6 to
carbon atoms, a chloroalkylaryl group having 7 to 40 carbon atoms,
a bromoaryl group having 6 to 20 carbon atoms, a bromoalkylaryl
group having 7 to 40 carbon atoms, an iodoaryl group having 6 to 20
carbon atoms, an iodoalkylaryl group having 7 to 40 carbon atoms
and a fluoroalkylaryl group having 7 to carbon atoms.
[0519] In particular, it is preferable that both of R.sup.13 and
R.sup.14 are selected from an aryl group having 7 to 18 carbon
atoms, a chloroaryl group having 6 to 20 carbon atoms, a
chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl
group having 6 to 20 carbon atoms, a bromoalkylaryl group having 7
to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms,
an iodoalkylaryl group having 7 to 40 carbon atoms and a
fluoroalkylaryl group having 7 to 40 carbon atoms, and may be
identical to or different from each other. It is preferred that
both of R.sup.13 and R.sup.14 are selected from an aryl group
having 11 to 18 carbon atoms, a chloroaryl group having 6 to 20
carbon atoms, chloroalkylaryl group having 7 to 40 carbon atoms, a
bromoaryl group having 6 to 20 carbon atoms, a bromoalkylaryl group
having 7 to 40 carbon atoms, an iodoaryl group having 6 to 20
carbon atoms, an iodoalkylaryl group having 7 to 40 carbon atoms
and a fluoroalkylaryl group having 7 to 40 carbon atoms, and may be
identical to or different from each other.
[0520] The bridged metallocene compound (a-2) having identical
R.sup.13 and R.sup.14 is preferably used in terms of ease of
production.
[0521] Other Features of Bridged Metallocene Compound (a-2)
[0522] In the Formula [1-2], Q is selected from a halogen, a
hydrocarbon group (preferably hydrocarbon groups having 1 to carbon
atoms), a neutral, conjugated or non-conjugated diene having 10 or
fewer carbon atoms, an anion ligand, and a neutral ligand capable
of coordination with a lone electron pair, in identical or
different combinations.
[0523] Specific examples of the halogen include fluorine, chlorine,
bromine and iodine.
[0524] Specific examples of the hydrocarbon group include methyl,
ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl,
2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl,
1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl,
1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl,
cyclohexylmethyl, cyclohexyl, and 1-methyl-1-cyclohexyl.
[0525] Specific examples of the neutral, conjugated or
non-conjugated diene having 10 or fewer carbon atoms include s-cis
or s-trans-.eta..sup.4-1,3-butadiene, s-cis or
s-trans-.eta..sup.4-1,4-diphenyl-1,3-butadiene, s-cis or
s-trans-.eta..sup.4-3-methyl-1,3-pentadiene, s-cis or
s-trans-.eta..sup.4-1,4-dibenzyl-1,3-butadiene, s-cis or
s-trans-.eta..sup.4-2,4-hexadiene, s-cis or
s-trans-.eta..sup.4-1,3-pentadiene, s-cis or
s-trans-.eta..sup.4-1,4-ditolyl-1,3-butadiene, and s-cis or
s-trans-.eta..sup.4-1,4-bis(trimethylsilyl)-1,3-butadiene.
[0526] Specific examples of the anion ligand include alkoxy groups
such as methoxy, tert-butoxy, and phenoxy; carboxylate groups such
as acetate, and benzoate; and sulfonate groups such as mesylate,
and tosylate.
[0527] Specific examples of the neutral ligand capable of
coordination with a lone electron pair include organophosphorus
compounds such as trimethylphosphine, triethylphosphine,
triphenylphosphine, diphenylmethylphosphine and the like; and
ethers such as tetrahydrofuran, diethyl ether, dioxane, and
1,2-dimethoxyethane.
[0528] j is an integer from 1 to 4, and when j is 2 or greater, Q
may be identical to or different from each other.
[0529] Preferred Bridged Metallocene Compound (a-2) and Examples
Thereof
[0530] Hereinafter, specific examples of the bridged metallocene
compound (a-2) represented by the General Formula [1-2] will be
described, but the scope of the present invention (2) is not
particularly limited to these. Hereinafter,
octamethyloctahydrodibenzofluorene refers to a structure
represented by Formula [10],
octamethyltetrahydrodicyclopentafluorene refers to a structure
represented by Formula [11], and dibenzofluorene refers to a
structure represented by Formula [12].
##STR00009##
[0531] The specific examples include
[0532]
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluo-
renyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)-
zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclo-
pentafluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-d-
i-tert-butylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di-
-tert-butylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylflu-
orenyl)zirconium dichloride,
[0533]
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluo-
renyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)-
zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclo-
pentafluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-d-
i-tert-butylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di-
-tert-butylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluo-
renyl)zirconium dichloride,
[0534]
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluor-
enyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)z-
irconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofl-
uorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclop-
entafluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-(trimethyl
phenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluo-
renyl)zirconium dichloride,
[0535]
di(m-bromophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluor-
enyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)z-
irconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofl-
uorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclop-
entafluorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-di-
-tert-butylfluorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluo-
renyl)zirconium dichloride,
[0536]
di(p-iodophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluore-
nyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zi-
rconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzoflu-
orenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclope-
ntafluorenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-buty-
lfluorenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-buty-
lfluorenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluor-
enyl)zirconium dichloride,
[0537]
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-
-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahyd-
rodibenzofluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahy-
drodicyclopentafluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)-
zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphen-
yl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-ter-
t-butylfluorenyl)zirconium dichloride,
[0538]
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-
-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahyd-
rodibenzofluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahy-
drodicyclopentafluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)-
zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphen-
yl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-ter-
t-butylfluorenyl)zirconium dichloride,
[0539]
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-
-butylfluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahyd-
rodibenzofluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahy-
drodicyclopentafluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)-
zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphen-
yl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-ter-
t-butylfluorenyl)zirconium dichloride,
[0540]
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-
-butylfluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahyd-
rodibenzofluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahy-
drodicyclopentafluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)-
zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphen-
yl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-ter-
t-butylfluorenyl)zirconium dichloride,
[0541]
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di--
tert-butylfluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)
(3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)
(octamethyloctahydrodibenzofluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)
(octamethyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)
(dibenzofluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)
(2,7-dimethyl-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)
(2,7-(trimethylphenyl)-3,6-di-tert-butylfluorenyl)zirconium
dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)
(2,7-(dimethylphenyl)-3,6-di-tert-butylfluorenyl)zirconium
dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)
(2,3,6,7-tetratert-butylfluorenyl)zirconium dichloride,
[0542]
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-ter-
t-butylfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-buty-
lfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahy-
drodibenzofluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrah-
ydrodicyclopentafluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl-
)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylph-
enyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-te-
rt-butylfluorenyl)zirconium dichloride,
[0543]
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfl-
uorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenz-
ofluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyc-
lopentafluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconiu-
m dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylf-
luorenyl)zirconium dichloride,
[0544]
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfl-
uorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenz-
ofluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyc-
lopentafluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconiu-
m dichloride, di(3-chloronaphthyl)methylene(cyclopentadienyl)
(2,7-diphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,3,6,
7-tetra-tert-butylfluorenyl)zirconium dichloride,
[0545]
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfl-
uorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenz-
ofluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyc-
lopentafluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconiu-
m dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylf-
luorenyl)zirconium dichloride,
[0546]
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluore-
nyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibe-
nzofluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodic-
yclopentafluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zircon-
ium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3-
,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,-
6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-buty-
lfluorenyl)zirconium dichloride,
[0547]
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluore-
nyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibe-
nzofluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodic-
yclopentafluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zircon-
ium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3-
,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,-
6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-buty-
lfluorenyl)zirconium dichloride,
[0548]
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di--
tert-butylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-b-
utylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloct-
ahydrodibenzofluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltet-
rahydrodicyclopentafluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluore-
nyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl--
3,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl--
3,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethy-
lphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethyl-
phenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,
7-tetra-tert-butylfluorenyl)zirconium dichloride,
[0549] naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)
(2,7-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodi-
benzofluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrod-
icyclopentafluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirc-
onium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-
-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)--
3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-bu-
tylfluorenyl)zirconium dichloride,
[0550]
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-but-
ylfluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodi-
benzofluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrod-
icyclopentafluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirc-
onium dichloride,
naphthyl(m-chlorophenyl).methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-
-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)--
3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-bu-
tylfluorenyl)zirconium dichloride,
[0551]
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-d-
i-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethylo-
ctahydrodibenzofluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethylt-
etrahydrodicyclopentafluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluo-
renyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dipheny-
l-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethy-
l-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimet-
hylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimeth-
ylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tet-
ra-tert-butylfluorenyl)zirconium dichloride,
[0552]
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-bu-
tylfluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylflu-
orenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrod-
ibenzofluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydro-
dicyclopentafluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zir-
conium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl-
)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-
-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-b-
utylfluorenyl)zirconium dichloride,
[0553]
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-bu-
tylfluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylflu-
orenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrod-
ibenzofluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydro-
dicyclopentafluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zir-
conium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl-
)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-
-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-b-
utylfluorenyl)zirconium dichloride,
[0554]
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7--
di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyl-
octahydrodibenzofluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyl-
tetrahydrodicyclopentafluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzoflu-
orenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphen-
yl-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimeth-
yl-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trime-
thylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimet-
hylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-te-
tra-tert-butylfluorenyl)zirconium dichloride,
[0555]
di(4-biphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoreny-
l)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirc-
onium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluor-
enyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopent-
afluorenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(4-biphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-di-te-
rt-butylfluorenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluoren-
yl)zirconium dichloride [the above compounds may all be referred to
as "bridged metallocene compounds (a-2a)" ], and
[0556]
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoreny-
l)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirc-
onium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluor-
enyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopent-
afluorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-di-te-
rt-butylfluorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluoren-
yl)zirconium dichloride,
[0557]
di(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl)(o-
ctamethyloctahydrodibenzofluorenyl)zirconium dichloride,
di(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl)(octamet-
hyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
di(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl)(dibenzo-
fluorenyl)zirconium dichloride,
di(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl)(2,7-dip-
henyl-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl)(2,7-dim-
ethyl-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl))(2,7-(t-
rimethylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl)(2,7-(di-
methylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl)(2,3,6,7-
-tetra-tert-butylfluorenyl)zirconium dichloride,
[0558]
di(4-[p-chlorophenyl]-phenyl)methylene(cyclopentadienyl)(octamethyl-
octahydrodibenzofluorenyl)zirconium dichloride,
di(4-[p-chlorophenyl]-phenyl)methylene(cyclopentadienyl)(octamethyltetrah-
ydrodicyclopentafluorenyl)zirconium dichloride,
di(4-[p-chlorophenyl]-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl-
)zirconium dichloride,
di(4-[p-chlorophenyl]-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(4-[p-chlorophenyl]-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(4-[p-chlorophenyl]-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylph-
enyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(4-[p-chlorophenyl]-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride, and
di(4-[p-chlorophenyl]-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetrater-
t-butylfluorenyl)zirconium dichloride [the above compounds may all
be referred to as "bridged metallocene compounds (a-2b)" ].
[0559] Furthermore, a compound resulting from replacing the
"zirconium" of the compound described above (bridged metallocene
compound (a-2a) and (a-2b)) with "hafnium" or "titanium", a
metallocene compound resulting from replacing the "dichloride" of
the compound described above (bridged metallocene compound (a-2a)
and (a-2b)) with "difluoride", "dibromide" or "diiodide", or
replacing the "dichloride" of the compound described above (bridged
metallocene compound (a-2a) and (a-2b)) with "dimethyl" or
"methylethyl", and the like are also likewise the metallocene
compound represented by the Formula [1-2].
[0560] The bridged metallocene compound (a-2) described above can
be produced by referring to a known method. Examples of the known
method for production include the method for production described
in the pamphlet of WO 2004/029062 filed by the present
applicant.
[0561] The metallocene compound as described above can be used
alone or in combination of two or more species.
[0562] [2] Catalyst for Olefin Polymerization (2)
[0563] Next, preferred embodiments of using the bridged metallocene
compound (a-2) described above as a polymerization catalyst in the
method for olefin polymerization of the present invention (2), will
be described.
[0564] In the case of using the bridged metallocene compound (a-2)
as a catalyst for olefin polymerization, the catalyst component
comprises:
[0565] (a-2) the bridged metallocene compound (a-2) represented by
the above Formula [1-2]; and
[0566] (b) at least one compound selected from: (b-1) the
organoaluminum oxy compound, (b-2) the compound which reacts with
the bridged metallocene compound (a-2) to form an ion pair, and
(b-3) the organoaluminum compound.
[0567] The "compound (b-2) which reacts with the bridged
metallocene compound (a-2) to form an ion pair" is the same as the
"compound (b-2) reacting with the bridged metallocene compound
(a-1) to form an ion pair (ionic compound (b-2)), and details of
the organoaluminum oxy compound (b-1), the ionic compound (b-2) and
the organoaluminum compound (b-3) are as described above.
[0568] Furthermore, the catalyst (2) for olefin polymerization may
also contain a support (c) according to necessity, along with the
(a-2) bridged metallocene compound represented by the Formula
[1-2], and (b) at least one compound selected from (b-1) the
organoaluminum oxy compound, (b-2) the compound which reacts with
the bridged metallocene compound (a-2) to form an ion pair, and
(b-3) the organoaluminum compound. The respective components may be
used after being supported on the above-described support (c)
having a particulate form.
[0569] The catalyst (2) for olefin polymerization may contain the
above-described organic compound component (d) according to
necessity, as a catalyst component.
[0570] Details of the support (c) and the organic compound
component (d) are as described above in the description of the
catalyst (1) for olefin polymerization of the present invention
(1).
[0571] Method for Producing Propylene-Based Copolymer (B1)
[0572] For polymerization of the propylene-based copolymer (B1),
the method of using each component, and the order of addition are
arbitrarily selected, and the following methods may be mentioned as
the methods of polymerization.
[0573] (1) A method comprising adding the component (a-2) and
component (b) into the polymerization vessel in an arbitrary
order.
[0574] (2) A method comprising adding the component (a-2) and
component (b) into the polymerization vessel in an arbitrary
order.
[0575] (3) A method comprising adding a catalyst component in which
the component (a-2) is supported on the support (c), and the
component (b) into the polymerization vessel in an arbitrary
order.
[0576] (4) A method comprising adding a catalyst component in which
the component (b) is supported on the support (c), and the
component (a-2) into the polymerization vessel in an arbitrary
order.
[0577] (5) A method comprising adding a catalyst component in which
the component (a-2) and the component (b) are supported on the
support (c) into the polymerization vessel.
[0578] In the respective methods of (2) to (5) described above, at
least two or more of the catalyst components may be brought into
contact with each other in advance.
[0579] In the respective methods of (4) and (5) described above
using supported component (b), unsupported component (b) may be
added in any order, as necessary. In this case, the components (b)
may be identical to or different from each other.
[0580] Furthermore, the solid catalyst component having the
component (a-2) supported on the component (c), and the solid
catalyst component having the component (a-2) and component (b)
supported on the component (c) may have a prepolymerized olefin, or
a prepolymerized solid catalyst component may further have the
catalyst component supported thereon.
[0581] In the production of the propylene-based copolymer (B1)
described above, polymerization can be carried out by any of a
liquid phase polymerization method such as solution polymerization,
and a suspension polymerization, and a gas phase polymerization
method. Specific examples of the inert hydrocarbon medium used in
the liquid phase polymerization method include aliphatic
hydrocarbons such as propane, butane, pentane, hexane, heptane,
octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such
as cyclopentane, cyclohexane, and methylcyclopentane; aromatic
hydrocarbons such as benzene, toluene, and xylene; halogenated
hydrocarbons such as ethylene chloride, chlorobenzene, and
dichloromethane, and mixtures thereof. The olefin to be polymerized
may also be used per se as the solvent.
[0582] When polymerization of olefin is performed using the
catalyst for olefin polymerization as described above, the
component (a-2) is usually used in an amount of 10.sup.-9 to
10.sup.-1 moles, and preferably 10.sup.-8 to 10.sup.-2 moles, per
liter of the reaction volume.
[0583] The component (b-1) is used in an amount such that the molar
ratio [(b-1)/M] of the component (b-1) and the total transition
metal atoms (M) in the component (a-2) is usually 0.01 to 5,000,
and preferably 0.05 to 2,000. The component (b-2) is used in an
amount such that the molar ratio [(b-2)/M] of the aluminum atoms in
the component (b-2) and the total transition metal (M) in the
component (a-2) is usually 1 to 1,000, and preferably 1 to 500. The
component (b-3) is used in an amount such that the molar ratio
[(b-3)/M] of the component (b-3) and the transition metal atoms (M)
in the component (a-2) is usually 1 to 10,000, and preferably 1 to
5,000.
[0584] In the present invention (2), propylene and at least one
monomer selected from .alpha.-olefins and polyenes are usually
copolymerized in the liquid phase in the presence of the catalyst
for olefin polymerization (2) as described above. In this case,
hydrocarbon solvents are generally used, but .alpha.-olefins may
also be used as the solvent. Copolymerization can be performed in
any mode such as batch mode or continuous mode.
[0585] Examples of the .alpha.-olefin that can be used in the
polymerization include ethylene, 1-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, and 1-eicosene. The .alpha.-olefin can
be used alone, or in combination of two or more species.
[0586] Specific examples of the polyene that can be used in the
polymerization include non-conjugated dienes such as
1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene,
1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidenenorbornene,
vinylnorbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, and
4-ethylidene-8-methyl-1,7-nonadiene;
[0587] conjugated dienes such as butadiene, and isoprene;
[0588] non-conjugated trienes such as
6,10-dimethyl-1,5,9-undecatriene, 4,8-dimethyl-1,4,8-decatriene,
5,9-dimethyl-1,4,8-decatriene, 6,9-dimethyl-1,5,8-decatriene,
6,8,9-trimethyl-1,5,8-decatriene,
6-ethyl-10-methyl-1,5,9-undecatriene, 4-ethylidene-1,6,-octadiene,
7-methyl-4-ethylidene-1,6-octadiene,
4-ethylidene-8-methyl-1,7-nonadiene (EMND),
7-methyl-4-ethylidene-1,6-nonadiene,
7-ethyl-4-ethylidene-1,6-nonadiene,
6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,
7-dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-1,6-decadiene,
7-methyl-4-ethylidene-1,6-decadiene,
7-methyl-6-propyl-4-ethylidene-1,6-octadiene,
4-ethylidene-1,7-nonadiene, 8-methyl-4-ethylidene-1,7-nonadiene,
and 4-ethylidene-1,7-undecanediene; and conjugated trienes such as
1,3,5-hexatriene.
[0589] Such dienes can be used alone or in combination of two or
more species, and such trienes can be used alone or in combination
of two or more species. The trienes and the dienes can also be used
in combination.
[0590] Furthermore, the .alpha.-olefins and polyenes as described
above can also be used in combination.
[0591] When performing copolymerization in batch mode using the
catalyst for olefin polymerization, the concentration of the
metallocene compound in the polymerization system used is usually
0.00005 to 1 mmol, and preferably 0.0001 to 0.50 mmol, per 1 liter
of the polymerization volume.
[0592] The reaction time (average residence time in the case of
performing copolymerization in the continuous mode) may vary
depending on the conditions such as catalyst concentration, and
polymerization temperature, but it is usually 5 minutes to 3 hours,
and preferably 10 minutes to 1.5 hours.
[0593] Propylene and at least one monomer selected from the
.alpha.-olefins and the polyenes are respectively supplied in an
amount such that a propylene-based copolymer (B1) of specific
composition as described above can be obtained. Upon
copolymerization, a molecular weight adjusting agent such as
hydrogen can also be used.
[0594] When propylene and at least one monomer selected from the
.alpha.-olefins and the polyenes are copolymerized as described
above, the propylene-based copolymer (B1) is usually obtained as a
polymerization solution containing the same. This polymerization
solution is treated according to conventional methods to obtain the
propylene-based copolymer (B1).
[0595] The copolymerization reaction is usually performed under the
conditions of a temperature of 40.degree. C. to 200.degree. C.,
preferably 40.degree. C. to 180.degree. C., and more preferably
50.degree. C. to 150.degree. C., and of a pressure of greater than
0 to 10 MPa, preferably 0.5 to 10 MPa, and more preferably 0.5 to 7
MPa.
[0596] According to the present invention (2), for example, a
propylene copolymer having a high molecular weight (specifically,
[.eta.]>2.0) can be obtained even under the condition of a
polymerization temperature of 65.degree. C. or higher.
[0597] [3] Propylene-Based Copolymer (B1)
[0598] The intrinsic viscosity [.eta.](measured at 135.degree. C.
in decalin) of the propylene-based copolymer (B1) obtained by the
method for production of the present invention (2) is preferably
0.1 to 10 dl/g, more preferably 0.3 to 7 dl/g, and even more
preferably 0.5 to 5 dl/g. Also, the melt flow rate (MFR; ASTM D
1238, 190.degree. C., under a load of 2.16 kg) of the
propylene-based copolymer (B1) is preferably 0.01 to 200 g/10 min,
more preferably 0.05 to 100 g/10 min, even more preferably 0.05 to
80 g/10 min, and particularly preferably 0.05 to 20 g/10 min.
[0599] The propylene content in the propylene-based copolymer (B1)
(amount of constituent units derived from propylene in the
propylene-based copolymer (B1)) obtained by the method for
production of the present invention (2) is preferably in the range
of 95 to 51 mol %, more preferably 90 to 51 mol %, and even more
preferably 90 to 55 mol %.
[0600] The .alpha.-olefin component of the propylene-based
copolymer (B1) is preferably at least one selected from ethylene,
1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene, and
it is preferable that the constituent units derived from an
.alpha.-olefin in the propylene-based copolymer (B1) are in the
range of 5 to 49 mol %, preferably 10 to 49 mol %, and more
preferably 10 to 45 mol %. The .alpha.-olefin component may be
contained alone or as a mixture of two or more species.
[0601] In the propylene-based copolymer (B1), the sum of the
content of the constituent units derived from propylene and the
content of the constituent units derived from .alpha.-olefin is 100
mol %.
[0602] Furthermore, the polyene is preferably selected from a diene
and a triene, and the constituent units derived from the polyene
are preferably contained in the propylene-based copolymer (B1) in
the range of 0 to 20 mol %. In the case where the propylene-based
copolymer (B1) contains the polyene component, the constituent
units derived from the polyene are contained in the propylene-based
copolymer (B1) in an amount of greater than 0 mol % and less than
or equal to 20 mol %, based on 100 mol % of the sum of amounts of
propylene and the .alpha.-olefin (excluding propylene) (100 mol %
of the sum of amounts of the constituent units derived from
propylene and the constituent units derived from the .alpha.-olefin
(excluding propylene)).
[0603] The diene may be specifically exemplified by the
non-conjugated dienes and conjugated dienes as described above.
Among them, a diene having a norbornene skeleton is preferred.
[0604] There may be contained one or two or more species of the
constituent units derived from diene as described above.
[0605] The triene may be specifically exemplified by the
non-conjugated trienes or conjugated triene as described above.
Among them, 4,8-dimethyl-1,4,8-decatriene and
4-ethylidene-8-methyl-1,7-nonadiene (EMND) are preferred.
[0606] There may be contained one or two or more species of the
constituent units derived from triene as described above. Also,
constituent units derived from the triene and constituent units
derived from the diene may be contained together. Among these
polyene components, constituent units derived from a polyene having
a norbornene skeleton is particularly preferred.
[0607] The iodine value of the propylene-based copolymer (B1)
containing the polyene component as described above is usually 1 to
80, and preferably 5 to 60.
[0608] According to the method for production of the present
invention (2), a high molecular weight propylene copolymer
containing a large amount of an .alpha.-olefin having 4 or more
carbon atoms can be easily produced. For the propylene-based
copolymer (B1) obtained therefrom, for example, when the molar
fraction of the constituent units derived from ethylene is
designated as PE, and the molar fraction of an .alpha.-olefin
having 4 to 20 carbon atoms, such as 1-butene and 1-octene, is
designated as P.sub.HAO, the value of P.sub.E/P.sub.HAO is 0 to
0.80 for example, preferably 0 to 0.60, and more preferably 0 to
0.50. Also, when ethylene is to be essentially contained, the ratio
P.sub.E/P.sub.HAO is in the range of 0.05 to 0.80 for example,
preferably 0.06 to 0.60, and more preferably 0.10 to 0.50. An
embodiment not containing ethylene is also preferable.
[0609] <Syndiotactic Propylene Polymer (A)>
[0610] Next, the best embodiments for carrying out the present
invention for the syndiotactic propylene polymer (A) (propylene
polymer (A)) related to the present invention (3) and molded
products comprising the propylene polymer will be described.
[0611] Specifically, the characteristic properties of the
syndiotactic propylene polymer (A), a representative method for
production of the polymer, a method for molding the polymer, and
specific examples for them will be described.
[0612] Syndiotactic Propylene Polymer (A)
[0613] The syndiotactic propylene polymer (A) of the present
invention (3) is a propylene polymer comprising constituent units
derived from propylene in an amount of 90 mol % or greater
(provided that the sum of amounts of the constituent units is 100
mol %).
[0614] The syndiotactic propylene polymer (A) of the present
invention (3) may be homopolypropylene or may be a random copolymer
of propylene..alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene), or may be a propylene block copolymer, as long as it is
a propylene polymer satisfying the above-described requirements [1]
and [2-1], preferably the requirements [1], [2-2] and [3], and more
preferably the requirements [1] to [4], and further more
preferably, a propylene polymer satisfying the requirements [a] to
[d] in addition to the requirements [1] to [4]. However, the
polymer is preferably homopolypropylene or a random copolymer of
propylene..alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene), and particularly preferably homopolypropylene, a
copolymer of propylene with ethylene or an .alpha.-olefin having 4
to 10 carbon atoms, and a copolymer of propylene with ethylene and
an .alpha.-olefin having 4 to 10 carbon atoms.
[0615] The .alpha.-olefin having 2 to 20 carbon atoms other than
propylene is exemplified by ethylene, 1-butene, 3-methyl-1-butene,
1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, l-eicosene,
or the like.
[0616] The propylene polymer of the present invention (3) contains
more than 90 mol % of constituent units derived from propylene
(provided that the total amount of the constituents unit in the
polymer (A) is 100 mol %). The propylene polymer of the present
invention (3) is generally a propylene polymer containing more than
90 mol % to 100 mol % or less of constituents unit derived from
propylene, and 0 mol % or more and less than mol % of constituent
units derived from an .alpha.-olefin having 2 to 20 carbon atoms
(excluding propylene) (provided that the sum of amounts of the
constituent units is 100 mol %); preferably a propylene polymer
containing 91 mol % or more and 100 mol % or less of constituent
units derived from propylene, and 0 mol % or more and 9 mol % or
less of constituent units derived from an .alpha.-olefin having 2
to 20 carbon atoms (excluding propylene) (provided that the sum of
amounts of the constituent units is 100 mol %); and more preferably
a propylene polymer containing 96 mol % or more and 100 mol % or
less of constituent units derived from propylene, and 0 mol % or
more and 4 mol % or less of constituent units derived from an
.alpha.-olefin having 2 to 20 carbon atoms (excluding propylene)
(provided that the sum of amounts of the constituent units is 100
mol %).
[0617] When the syndiotactic propylene polymer of the present
invention (3) is a propylene..alpha.-olefin random copolymer, the
polymer preferably contains 94 to 99.9 mol % of constituent units
derived from propylene and 0.1 to 8 mol % of constituent units
derived from an .alpha.-olefin having 2 to 20 carbon atoms
(excluding propylene), more preferably 93 to 99.9 mol % of
constituent units derived from propylene and 0.1 to 7 mol % of
constituent units derived from an .alpha.-olefin having 2 to 20
carbon atoms (excluding propylene), and even more preferably 94 to
99.9 mol % of constituent units derived from propylene and 0.1 to 6
mol % of constituent units derived from an .alpha.-olefin having 2
to 20 carbon atoms (excluding propylene).
[0618] Among these syndiotactic propylene polymers,
homopolypropylene is more preferred from the viewpoint of heat
resistance and the like.
[0619] It is desirable that the intrinsic viscosity [.eta.] of the
syndiotacticpropylenepolymer (A) of the present invention (3) as
measured in decalin at 135.degree. C. is usually 0.01 to 10.00
dL/g, preferably 0.10 to 9.00 dL/g, more preferably 0.50 to 8.00
dL/g, even more preferably 0.95 to 8.00 dL/g, further more
preferably in the range of 1.00 to 8.00, particularly preferably in
the range of 1.40 to 8.00 dL/g, and inter alia, preferably in the
range of 1.40 to 5.00 dL/g.
[0620] The syndiotactic propylene polymer (A) of the present
invention (3) is characterized in satisfying the following
requirements [1] and [2-1], and preferably the following
requirements [1], [2-2] and [3].
[0621] [1] The syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or greater.
[0622] [2-1] The melting point (Tm) determined by differential
scanning calorimetry (DSC) is 145.degree. C. or higher.
[0623] [2-2] The melting point (Tm) is 145.degree. C. or higher,
and the heat of fusion (.DELTA.H) is 40 mJ/mg or greater, each
determined by differential scanning calorimetry (hereinafter,
referred to as DSC).
[0624] [3] When the isothermal crystallization temperature
determined by differential scanning calorimetry is designated as
T.sub.iso, and the half-crystallization time at the isothermal
crystallization temperature T.sub.iso is designated as t.sub.1/2,
the following Equation (Eq-1) is satisfied within the range of
110.ltoreq.T.sub.iso.ltoreq.150(.degree. C.):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.5.-
56.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-1)
[0625] Such syndiotactic propylene polymer (A) has excellent
moldability, heat resistance, transparency, rigidity and breaking
tensile strength when applied to molding. Hereinafter, the
requirements [1] to [3] will be described in detail.
[0626] Requirement [1]
[0627] The syndiotactic pentad fraction (rrrr fraction, pentad
syndiotacticity) of the syndiotactic propylene polymer used in the
present invention, as measured by NMR, is 85% or greater,
preferably 90% or greater, more preferably 93% or greater, and even
more preferably 94% or greater, and a syndiotactic propylene
polymer (A) having an rrrr fraction in this range is preferable
from the viewpoint of having excellent moldability, heat resistance
and transparency, and having good properties as a crystalline
polypropylene. There is no particular limitation on the rrrr
fraction, but it is 100% or less, and usually 99% or less, for
example.
[0628] This syndiotactic pentad fraction (rrrr fraction) is
measured as follows.
[0629] The rrrr fraction is determined from the absorption
intensities of Prrrr (the absorption intensity resulting from the
methyl group of the third unit at a site of five propylene units
being sequentially syndiotactically bonded) and Pw (the absorption
intensity resulting from all the methyl groups of propylene units)
in the .sup.13C-NMR spectrum according to the following equation
(1):
rrrr fraction (%)=100.times.Prrrr/Pw (1)
[0630] The NMR measurement is performed, for example, as follows.
Specifically, 0.35 g of a sample is dissolved under heating in 2.0
ml of hexachlorobutadiene. This solution is filtered through a
glass filter (G2), and then is introduced into an NMR tube having
an internal diameter of 10 mm after adding 0.5 ml of deuterated
benzene. Then, .sup.13C-NMR measurement is performed at 120.degree.
C. using a GX-500 NMR measuring apparatus manufactured JEOL, Ltd.
The accumulation times are 10,000 or more.
[0631] The syndiotactic propylene polymer having the rrrr fraction
in this range is preferable from the viewpoint having excellent
moldability, heat resistance and mechanical properties, and having
good properties as a crystalline polypropylene. By using the
catalyst system that will be described later and establishing the
polymerization conditions that will be described later, the
syndiotactic propylene polymer having the rrrr fraction within this
range can be produced.
[0632] Requirements [2-1] and [2-2]
[0633] The melting point of the syndiotactic propylene polymer (A)
that can be measured by differential scanning calorimetry (DSC) is
145.degree. C. or higher, preferably 150.degree. C. or higher, more
preferably 155.degree. C. or higher, and particularly preferably
156.degree. C. or higher. Moreover, the heat of fusion (.DELTA.H)
of the syndiotactic propylene polymer (A) measured at the same time
as the melting point, is preferably 40 mJ/mg or higher, more
preferably 50 mJ/mg ore higher, even more preferably 52 mJ/mg or
higher, and particularly preferably 55 mJ/mg. There is no
particular upper limit of Tm, but it is usually 170.degree. C. or
lower, for example.
[0634] The measurement of differential scanning calorimetry is
performed, for example, in the following manner. About 5 mg of a
sample is filled in an aluminum pan for exclusive use, and the
melting point is determined from an endothermic curve obtained by
heating the sample from 30.degree. C. to 200.degree. C. at a rate
of 320.degree. C./min, maintaining at 200.degree. C. for 5 minutes,
cooling from 200.degree. C. to 30.degree. C. at a rate of
10.degree. C./min, maintaining again at 30.degree. C. for 5
minutes, and heating again at a rate of 10.degree. C./min, using
DSCPyris1 or DSC7 manufactured by PerkinElmer, Inc. If a plurality
of peaks are detected during the DSC measurement, the peak detected
on the highest temperature side is defined as the melting point
(Tm).
[0635] The syndiotactic propylene polymer (A) having the melting
point (Tm) in this range is preferable from the viewpoint of having
excellent moldability, heat resistance and mechanical properties,
and having good properties as a crystalline polypropylene. By using
the catalyst system that will be described later and establishing
the polymerization conditions that will be described later, a
syndiotactic propylene polymer having the melting point within this
range can be produced.
[0636] Requirement [3]
[0637] The syndiotactic propylene polymer satisfies, when the
isothermal crystallization temperature determined by differential
scanning calorimetry (DSC) is designated as T.sub.iso, and the
half-crystallization time at the isothermal crystallization
temperature T.sub.iso is designated as t.sub.1/2, the following
Equation (Eq-1) in the range of
110.ltoreq.T.sub.iso.ltoreq.150(.degree. C.):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.5.-
56.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-1)
preferably satisfies the following equation (Eq-2):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.3.-
71.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-2)
and more preferably satisfies the following equation (Eq-3):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.2.-
23.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-3)
[0638] The half-crystallization time (t.sub.1/2) determined by
isothermal crystallization measurement is, when the area between
the DSC caloric curve and the baseline during the isothermal
crystallization process is considered as the total calories, the
time taken to reach 50% of the calories [see New Lectures on
Polymer Experiments, 8. Properties of Polymers (KYORITSU SHUPPAN
CO., LTD.)].
[0639] Measurement of the half-crystallization time (t.sub.1/2) is
performed as follows. About 5 mg of a sample is filled in an
aluminum pan for exclusive use, and the half-crystallization time
is determined from a DSC curve obtained by heating the sample from
30.degree. C. to 200.degree. C. at a rate of 320.degree. C./min,
maintaining at 200.degree. C. for 5 minutes, cooling from that
temperature (200.degree. C.) to the respective isothermal
crystallization temperature at a rate of 320.degree. C./min, and
maintaining at that isothermal crystallization temperature, using
DSCPyris1 or DSC7 manufactured by PerkinElmer, Inc. The
half-crystallization time (t.sub.1/2) is determined by setting the
initial time of the isothermal crystallization process (the time
when it reached to the isothermal crystallization temperature from
200.degree. C.) "t" as 0. For the syndiotactic propylene polymer of
the present invention, t.sub.1/2 can be determined as described
above, but when crystallization does not occur at an isothermal
crystallization temperature, for example, at 110.degree. C., the
measurement is taken for convenience at several points at an
isothermal crystallization temperature at or below 110.degree. C.,
and the half-crystallization time (t.sub.1/2) is determined from
the extrapolated value.
[0640] The syndiotactic propylene polymer satisfying the
requirement [3] is remarkably excellent in moldability compared to
existing syndiotactic propylene polymers. Moldability being
excellent indicates that, in the case of carrying out molding such
as injection molding, inflation molding, blow molding, extrusion or
press-molding, the time taken from the molten state to the solid
state is short. Such syndiotactic propylene polymer is also
excellent in molding cycle properties, shape stability, long-term
productivity and the like.
[0641] By using the catalyst system that will be described later
and establishing the polymerization conditions that will be
described later, a syndiotactic propylene polymer satisfying the
requirement [3] can be produced.
[0642] The syndiotactic propylene polymer (A) of the present
invention preferably simultaneously satisfies the requirement [4]
in addition to the requirements [1] to [3].
[0643] Requirement [4]
[0644] The amount of the n-decane-soluble part of the syndiotactic
propylene polymer is preferably 1 (wt %) or less, more preferably
0.8 (wt %) or less, and even more preferably 0.6 (wt %) or less.
This amount of n-decane-soluble part is an index closely related to
the blocking properties of the propylene random copolymer or the
molded products obtained therefrom, and a smaller amount of
n-decane-soluble part usually means a smaller amount of
low-crystalline components. That is, a syndiotactic propylene
polymer (A') satisfying the requirement [4] as well has very good
anti-blocking properties.
[0645] The syndiotactic propylene polymer (A) of the present
invention (3), preferably the syndiotactic propylene polymer (A'),
preferably also satisfies the following requirements [a] to
[d].
[0646] [a] The tensile modulus is in the range of 500 to 2,000
(MPa).
[0647] [b] The breaking tensile strength is 20 (MPa) or
greater.
[0648] [c] The internal haze value of a press sheet having a
thickness of 1 mm is 50% or less.
[0649] [d] The needle penetration temperature is 145.degree. C. or
higher.
[0650] Hereinafter, the requirements [a] to [d] will be described
in detail.
[0651] Requirement [a]
[0652] The tensile modulus of the syndiotactic propylene polymer
(A) of the present invention (3), preferably the syndiotactic
propylene polymer (A'), is in the range of 500 MPa to 2,000 MPa,
preferably 600 MPa to 1,800 MPa, and more preferably in the range
of 600 MPa to 1,500 MPa.
[0653] Specifically, this tensile modulus is a value measured by
the following procedure. First, a press sheet having a thickness of
1 mm is punched using an O-dumbbell for No. JIS 3 dumbbell
according to JIS K6301 to provide a specimen. The measurement is
performed, for example, by measuring the tensile modulus using a
tensile tester Inston 1123 manufactured by Instron, Inc. at a span
interval of 30 mm and a tensile rate of 30 mm/min at 23.degree. C.,
and an average value obtained from three runs is adopted
[0654] The syndiotactic propylene polymer having the tensile
modulus within in this range is preferable from the viewpoint of
having excellent mechanical properties and strength, and having
good properties as a crystalline polypropylene. By using the
catalyst system that will be described later and establishing the
polymerization conditions that will be described later, a polymer
having the tensile modulus within this range can be produced.
[0655] Requirement [b]
[0656] The breaking tensile strength of the syndiotactic propylene
polymer (A) of the present invention (3), preferably the
syndiotactic propylenepolymer (A'), is 20 (MPa) or greater,
preferably 22 (MPa) or greater, more preferably 25 (MPa) or
greater, and even more preferably 30 (MPa) or greater.
[0657] Specifically, this breaking tensile strength is a value
measured by the following procedure. First, a press sheet having a
thickness of 1 mm is punched using an O-dumbbell for No. JIS 3
dumbbell according to JIS K6301 to provide a specimen. The
measurement is performed, for example, by measuring the tensile
modulus using a tensile tester Inston 1123 manufactured by Instron,
Inc. at a span interval of 30 mm and a tensile rate of 30 mm/min at
23.degree. C., and an average value obtained from three runs is
adopted.
[0658] The syndiotactic propylene polymer having the breaking
tensile strength within this range is preferable from the viewpoint
of having excellent mechanical properties and strength, and having
good properties as a crystalline polypropylene. By using the
catalyst system that will be described later and establishing the
polymerization conditions that will be described later, a polymer
having the breaking tensile strength within this range can be
produced.
[0659] Requirement [c]
[0660] The internal haze of the syndiotactic propylene polymer (A)
of the present invention (3), preferably the syndiotactic propylene
polymer (A'), is 50% or lower, preferably 45% or lower, and more
preferably 30% or lower.
[0661] This internal haze value is an average value obtained from
two runs, in the case of being measured using a press sheet
specimen having a thickness of 1 mm with a digital turbidimeter
"NDH-20D" manufactured by Nippon Denshoku Industries Co., Ltd.
[0662] The syndiotactic propylene polymer having the internal haze
within this range is preferable from the viewpoint of having
excellent transparency, and having good properties as a crystalline
polypropylene. By using the catalyst system that will be described
later and establishing the polymerization conditions that will be
described later, a polymer having the internal haze within this
range can be produced.
[0663] Requirement [d]
[0664] The needle penetration temperature of the syndiotactic
propylene polymer (A) of the present invention (3), preferably the
syndiotactic propylene polymer (A'), is 145.degree. C. or higher,
and more preferably 150.degree. C. or higher.
[0665] The needle penetration temperature (may also be referred to
as softening temperature which is determined by TMA) can be
measured as follows.
[0666] The needle penetration temperature (.degree. C.) is
determined from a TMA curve recorded with a specimen of press sheet
having a thickness of 1 mm while pressing with a planar indentor of
1.8 mm.phi. at a pressure of 2 kgf/cm.sup.2 and heating at
5.degree. C./min using SS-120 manufactured by Seiko Co., Ltd. or
Q-400 manufactured by TA Instrument.
[0667] The syndiotactic propylene polymer having the needle
penetration temperature within this range is preferable from the
viewpoint of having excellent heat resistance and having good
properties as crystalline polypropylene. The polymer is also
preferable from the viewpoint of being excellent in heat
resistance, rigidity, material strength and the like, without
impairing transparency which is a characteristic of syndiotactic
propylene, and having good properties as crystalline polypropylene.
By using the catalyst system that will be described later and
establishing the polymerization conditions that will be described
later, a polymer having the property within this range can be
produced.
[0668] The present invention (3) relates to the molded products
obtained by molding the syndiotactic propylene polymer (A),
preferably the syndiotactic propylene polymer (A'), more preferably
a syndiotactic propylene polymer (A'').
[0669] Method for Producing Syndiotactic Propylene Polymer
[0670] As the catalyst (3) used in the production of the
syndiotactic polypropylene polymer (A) of the present invention
(3), and the syndiotactic propylene polymer (AA) used in the
present inventions (4), (5) and (6), a catalyst (cat-1) for
polymerization comprising:
[0671] (a-3) a bridged metallocene compound represented by the
following Formula [1-3](in the present specification, may be
referred to as "component (a-3)"), and
[0672] (b) at least one compound selected from:
[0673] (b-1) an organoaluminum oxy compound,
[0674] (b-2) a compound which reacts with the bridged metallocene
compound (a-3) to form an ion pair, and
[0675] (b-3) an organoaluminum compound, or a catalyst for
polymerization (cat-2) having the catalyst (cat-1) supported on a
particulate support, is suitably used.
[0676] However, as long as the produced polymer shows properties
that satisfy the requirements [1] to [3], the catalyst used in the
production of the syndiotactic polypropylene polymer (A) of the
present invention (3), and the catalyst used in the production of
the syndiotactic propylene polymer (AA) used in the present
inventions (4), (5) and (6) are not limited to such catalysts.
##STR00010##
[0677] In the Formula [1-3], R.sup.1, R.sup.2, R.sup.3 and R.sup.4
are each selected from a hydrogen atom, a hydrocarbon group and a
silicon-containing group; R.sup.2 and R.sup.3 may be linked to each
other to form a ring, R.sup.5, R.sup.6, R.sup.8, R.sup.9, R.sup.11
and R.sup.12 may be selected from hydrogen, a hydrocarbon group and
a silicon-containing group; the two groups of R.sup.7 and R.sup.10
are not hydrogen atoms, but are each selected from a hydrocarbon
group and a silicon-containing group, and may be identical to and
different from each other; and in one or more combinations of
adjacent groups selected from R.sup.5 and R.sup.6, R.sup.7 and
R.sup.8, R.sup.8 and R.sup.9, R.sup.9 and R.sup.10, and R.sup.11
and R.sup.12, the adjacent groups may be linked to each other to
form a ring.
[0678] R.sup.17 and R.sup.18 are each a hydrogen atom, a
hydrocarbon group having 1 to 20 carbon atoms or a silicon
atom-containing group, and may be identical to and different from
each other, while the substituents may be linked to each other to
form a ring.
[0679] M is Ti; Zr or Hf; Y is carbon; Q may be selected from a
halogen, a hydrocarbon group, an anion ligand and a neutral ligand
capable of coordination with a lone electron pair, in identical or
different combinations; and j is an integer from 1 to 4.
[0680] Hereinafter, specific examples of the component (bridged
metallocene compound) (a-3) satisfying this definition will be
given:
[0681]
cyclopropylidene(cyclopentadienyl)(3,6-di-tert-fluorenyl)zirconium
dichloride,
cyclobutylidene(cyclopentadienyl)(3,6-di-tert-fluorenyl)zirconium
dichloride,
cyclopentylidene(cyclopentadienyl)(3,6-di-tert-fluorenyl)zirconium
dichloride,
cyclohexylidene(cyclopentadienyl)(3,6-di-tert-fluorenyl)zirconium
dichloride,
cycloheptylidene(cyclopentadienyl)(3,6-di-tert-fluorenyl)zirconium
dichloride,
dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride,
dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluor-
enyl)zirconium dichloride, di-n-butylmethylene
(cyclopentadienyl(2,7-di(2,4,6-trimethylphenyl)-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluor-
enyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-di(3,5-dimethylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluorenyl)z-
irconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-di(4-methylphenyl)-3,6-di-tert--
butylfluorenyl)zirconium dichloride, di-n-butylmethylene
(cyclopentadienyl)(2,7-dinaphthyl-3,6-di-tert-butylfluorenyl)zirconium
dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-di(4-tert-butylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
[0682]
diisobutylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-buty-
lfluorenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl(2,7-di(2,4,6-trimethylphenyl)-3,6-di-
-tert-butylfluorenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluor-
enyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-di(3,5-dimethylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluorenyl)z-
irconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-di(4-methylphenyl)-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-dinaphthyl-3,6-di-tert-butylflu-
orenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-di(4-tert-butylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride [also referred to as
1,3-diphenylisopropylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride, the same applies hereinafter],
dibenzylmethylene(cyclopentadienyl(2,7-di(2,4,6-trimethylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di(3,5-dimethylphenyl)-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluorenyl)zir-
conium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di(4-methylphenyl)-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dinaphthyl-3,6-di-tert-butylfluor-
enyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di(4-tert-butylphenyl)-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
[0683]
diphenethylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
diphenethylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
di(benzhydryl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(benzhydryl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(cumyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluore-
nyl)zirconium dichloride,
di(cumyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluore-
nyl)zirconium dichloride,
di(1-phenyl-ethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(1-phenyl-ethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(cyclohexylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(cyclohexylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(cyclopentylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(cyclopentylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
[0684] (benzyl)
(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluore-
nyl)zirconium dichloride, (benzyl)
(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluore-
nyl)zirconium dichloride, (benzyl)
(cumyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride, (benzyl)
(cumyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclopropylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclopropylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclobutylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cyclobutylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cyclopentylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclopentylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclohexylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cycloheptylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cycloheptylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
[0685]
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butyl-
fluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butylfluo-
renyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dicumyl-butylfluoren-
yl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dicumyl-butylfluor-
enyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di(trimethylsilyl)-b-
utylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di(trimethylsilyl)-
-butylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-diphenyl-butylfluore-
nyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-diphenyl-butylfluo-
renyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dibenzyl-butylfluore-
nyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dibenzyl-butylfluo-
renyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butylfluore-
nyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butylfluo-
renyl)zirconium dichloride,
[0686]
diphenylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-te-
rt-butylfluorenyl)zirconium dichloride,
di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-te-
rt-butylfluorenyl)zirconium dichloride,
di(p-n-butyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(p-n-butyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
[0687]
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(1-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(1-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-isopropylphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(p-isopropylphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride, and
diphenylsilylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride.
[0688] Furthermore, examples thereof also include a compound
resulting from replacing the "zirconium" of the compound described
above with "hafnium" or "titanium", and a bridged metallocene
compound resulting from replacing the "dichloride" of the compound
described above with "difluoride", "dibromide" or "diiodide", or
resulting from replacing the "dichloride" of the compound described
above with "dimethyl" or "methylethyl".
[0689] The bridged metallocene compound (a-3) described above can
be produced by known methods, and the method for production is not
particularly limited. Examples of the known method for production
include the methods for production described in WO 2001/27124 and
WO 2004/087775 filed by the present applicant. Such bridged
metallocene compound (a-3) can be used alone or in combination of
two or more species.
[0690] The compound (b) is at least one compound selected from the
organoaluminum oxy compound (b-1), the compound which reacts with
the bridged metallocene compound (a-3) to form an ion pair (b-2),
and the organoaluminum compound (b-3).
[0691] The "compound which reacts with the bridged metallocene
compound (a-3) to form an ion pair (b-2)" is identical to the
"compound which reacts with the bridged metallocene compound (a-1)
to form an ion pair (b-2) (ionic compound (b-2))", and details of
the organoaluminum oxy compound (b-1), the compound (b-2) and the
organoaluminum compound (b-3) are as described above.
[0692] The catalyst (3) described above may contain, if necessary,
the above-described support (c), along with the (a-3) bridged
metallocene compound represented by the Formula [1-3], and the (b)
at least one compound selected from (b-1) the organoaluminum oxy
compound, (b-2) the compound which reacts with the bridged
metallocene compound (a-3) to form an ion pair, and (b-3) the
organoaluminum compound, and the respective components may be used
while being supported on the particulate support (c).
[0693] The catalyst (3) may contain the organic compound component
(d) as the catalyst component, if necessary.
[0694] Details of the support (c) and the organic compound
component (d) are as described above.
[0695] Method for Producing Syndiotactic Propylene Polymer (A)
[0696] For polymerization of the syndiotactic propylene polymer (A)
of the present invention (3), the method of using each component,
and the order of addition are arbitrarily selected, and the
following methods may be mentioned as the methods of
polymerization.
[0697] (1) A method comprising adding the component (a-3) alone
into the polymerization vessel.
[0698] (2) A method comprising adding the component (a-3) and
component (b) into the polymerization vessel in an arbitrary
order.
[0699] (3) A method comprising adding a catalyst component in which
the component (a-3) is supported on the support (c), and the
component (b) into the polymerization vessel in an arbitrary
order.
[0700] (4) A method comprising adding a catalyst component in which
the component (b) is supported on the support (c), and the
component (a-3) into the polymerization vessel in an arbitrary
order.
[0701] (5) A method comprising adding a catalyst component in which
the component (a-3) and the component (b) are supported on the
support (c) into the polymerization vessel.
[0702] According to the respective methods of (2) to (5) described
above, at least two or more of the catalyst components may be
brought into contact with each other in advance.
[0703] In the respective methods of (4) and (5) described above
using supported component (b), unsupported component (b) may be
added in any order, as necessary. In this case, the component (b)
may be identical to or different from each other.
[0704] Furthermore, the solid catalyst component having the
component (a-3) supported on the component (c), and the solid
catalyst component having the component (a-3) and component (b)
supported on the component (c) may have a prepolymerized olefin, or
a prepolymerized solid catalyst component may further have the
catalyst component supported thereon.
[0705] In the production of the syndiotactic propylene polymer (A)
of the present invention (3), polymerization can be carried out by
any of liquid phase polymerization method such as a solution
polymerization, and suspension polymerization, and a gas phase
polymerization method. Specific examples of the inert hydrocarbon
medium used in the liquid phase polymerization method include
aliphatic hydrocarbons such as propane, butane, pentane, hexane,
heptane, octane, decane, dodecane, and kerosene; alicyclic
hydrocarbons such as cyclopentane, cyclohexane, and
methylcyclopentane; aromatic hydrocarbons such as benzene, toluene,
and xylene; halogenated hydrocarbons such as ethylene chloride,
chlorobenzene, and dichloromethane, and mixtures thereof. The
olefin to be polymerized may also be used per se as the
solvent.
[0706] When polymerization of olefin is performed using the
catalyst for olefin polymerization as described above, the
component (a-3) is usually used in an amount of 10.sup.-9 to
10.sup.-1 moles, and preferably 10.sup.-8 to 10.sup.-2 moles, per
liter of the reaction volume.
[0707] The component (b-1) is used in an amount such that the molar
ratio [(b-1)/M] of the component (b-1) and the total transition
metal atoms (M) in the component (a-3) is usually 0.01 to 5,000,
and preferably 0.05 to 2,000. The component (b-2) is used in an
amount such that the molar ratio [(b-2)/M] of the component (b-2)
and the transition metal atoms (M) in the component (a-3) is
usually 1 to 10, and preferably 1 to 5. The component (b-3) is used
in an amount such that the molar ratio [(b-3)/M] of the aluminum
atoms in the component (b-3) and the total transition metal (M) in
the component (a-3) is usually 10 to 5,000, and preferably 20 to
2,000.
[0708] The component (d) is used, in the case where the component
(b) is component (b-1), in an amount such that the molar ratio
[(d)/(b-1)] is usually 0.01 to 10, and preferably 0.1 to 5; in the
case where the component (b) is component (b-2), in an amount such
that the molar ratio [(d)/(b-2)] is usually 0.01 to 10, and
preferably 0.1 to 5; and, in the case where the component (b) is
component (b-3), in an amount such that the molar ratio [(d)/(b-3)]
is usually 0.01 to 2, and preferably 0.005 to 1.
[0709] The temperature for olefin polymerization using the catalyst
for olefin polymerization is generally within the range from -50 to
+200.degree. C., and preferably from 0 to 170.degree. C. The
polymerization pressure is under the condition of generally from
normal pressure to 10 MPa gauge pressure, and preferably from
normal pressure to 5 MPa gauge pressure, and the polymerization
reaction can be carried out either batchwise, semicontinuously or
continuously. The polymerization can be carried out by dividing the
process into two or more stages having different reaction
conditions. The molecular weight of the resulting propylene polymer
can be also regulated by allowing hydrogen to exist in the
polymerization system or by varying the polymerization temperature.
Moreover, the molecule weight can be regulated according to the
amount of the component (b) used. When adding hydrogen, the
suitable amount to be added is from about 0.001 to 100 NL per 1 kg
of olefin.
[0710] The syndiotactic propylene polymer (A) obtained by the
above-described method for polymerization may have a part thereof
graft-modified by a polar monomer. This polar monomer may be
exemplified by a hydroxyl group-containing ethylenic unsaturated
compound, an amino group-containing ethylenic unsaturated compound,
an epoxy group-containing ethylenic unsaturated compound, an
aromatic vinyl compound, an unsaturated carboxylic acid or its
derivatives, a vinyl ester compound, vinyl chloride, a vinyl
group-containing organosilicon compound, a carbodiimide compound,
or the like.
[0711] As the polar monomer, in particular, the unsaturated
carboxylic acid or its derivatives are particularly preferred.
Examples of the unsaturated carboxylic acid or its derivatives
include an unsaturated compound having at least one carboxylic acid
group, an ester of a compound having a carboxylic acid group and an
alkyl alcohol, and an unsaturated compound having at least one
anhydrous carboxylic acid group, and examples of the unsaturated
group include a vinyl group, a vinylene group, and an unsaturated
cyclic hydrocarbon group. Specific examples of the compound include
unsaturated carboxylic acids such as acrylic acid, maleic acid,
fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic
acid, crotonic acid, isocrotonic acid, and Nadic acid [trade
name](endocis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid); and
derivatives thereof such as acid halides, amides, imides,
anhydrides, esters and the like. Specific examples of these
derivatives include malenyl chloride, maleimide, maleic anhydride,
citraconic anhydride, monomethyl maleate, dimethyl maleate,
glycidyl maleate. These unsaturated carboxylic acids and/or
derivatives thereof may be used alone or in combination of two or
more species. Among these, an unsaturated dicarboxylic acid or an
acid anhydride thereof is preferred, and particularly maleic acid,
Nadic acid [trade name] or acid anhydrides thereof are preferably
used.
[0712] A modified syndiotactic propylene polymer can be obtained by
graft polymerizing a polar monomer to the syndiotactic propylene
polymer (A) as described above. When graft polymerizing such polar
monomer to the syndiotactic propylene polymer, the polar monomer is
usually used in an amount of 1 to 100 parts by weight, and
preferably 5 to 80 parts by weight, based on 100 parts by weight of
the syndiotactic propylene polymer (A). This graft polymerization
is generally performed in the presence of a radical initiator.
[0713] As the radical initiator, an organic peroxide, an azo
compound or the like may be used.
[0714] The radical initiator can be used by directly mixing with
the syndiotactic propylene polymer and the polar monomer, but may
be used after dissolving the initiator in a small amount of an
organic solvent. This organic solvent is not particularly limited
for use, as long as it is an organic solvent which can dissolve the
radical initiator.
[0715] Upon graft polymerizing a polar monomer to the syndiotactic
propylene polymer (A), a reducing substance can be used. If a
reducing substance is used, the amount of the polar monomer to be
grafted can be enhanced.
[0716] Graft modification of the syndiotactic propylene polymer (A)
with a polar monomer can be performed by a conventionally known
method, and for example, can be performed by dissolving the
syndiotactic propylene polymer (A) in an organic solvent,
subsequently adding a polar monomer, a radical initiator and the
like to the solution, and allowing the mixture to react at a
temperature of 70 to 200.degree. C., and preferably 80 to
190.degree. C., for 0.5 to 15 hours, and preferably 1 to 10
hours.
[0717] A modified syndiotactic propylene polymer can also be
produced by reacting the syndiotactic propylene polymer (A) with a
polar monomer in the absence of solvent, using an extruder or the
like. This reaction is preferably performed at a temperature
usually above the melting point of an ethylene-based polymer,
specifically at a temperature of 120 to 250.degree. C., usually for
0.5 to 10 minutes.
[0718] The modification ratio of the modified syndiotactic
propylene polymer thus obtained (the grafting ratio of the polar
monomer) is preferably 0.1 to 50 wt %, more preferably 0.2 to 30 wt
%, and even more preferably 0.2 to 10 wt %.
[0719] When the modified syndiotactic propylene polymer is
contained in the syndiotactic propylene polymer (A) of the present
invention (3), adhesiveness to other resins and compatibility may
be excellent, and also the wettability of the surface of molded
products may be improved.
[0720] The modified syndiotactic propylene polymer of the invention
(3) may be preferably used, after crosslinking, in crosslinked
wire, and crosslinked pipes.
[0721] The syndiotactic propylene polymer (A) of the present
invention (3) may also contain a nucleating agent, which is a
specific arbitrary component, in order to improve the moldability,
that is, to increase the crystallization temperature and increase
the rate of crystallization. In this case, for example, the
nucleating agent is a dibenzylidene sorbitol-based nucleating
agent, phosphoric acid ester salt-based nucleating agent, a
rosin-based nucleating agent, a benzoic acid metal salt-based
nucleating agent, a fluorinated polyethylene, sodium
2,2-methylenebis(4,6-di-tert-butylphenyl)phosphate, pimelic acid or
a salt thereof, 2,6-naphthalenic acid dicarboxylic acid
dicyclohexylamide, or the like. The amount of mixing is not
particularly limited, but the amount is preferably about 0.1 to 1
part by weight based on 100 parts by weight of the syndiotactic
propylene polymer (A). The timing for mixing is not particularly
limited, and addition is possible during or after polymerization,
or during the molding process.
[0722] The syndiotactic propylene polymer (A) of the present
invention (3) may have incorporated, if necessary, within the scope
of not impairing the purpose of the present invention, additives
such as a weather resistant stabilizer, a heat resistant
stabilizer, an antistatic agent, an anti-slipping agent, an
anti-blocking agent, a foaming agent, a crystallization aid, an
anti-fogging agent, a transparent nucleating agent, a lubricant, a
dye, a pigment, a plasticizer, an anti-aging agent, a hydrochloric
acid absorbent, an antioxidant, a releasing agent, an impact
improving agent, and an anti-UV agent.
[0723] The syndiotactic propylene polymer (A) can be produced in
the scope described above by various methods that are known, for
example, by multi-stage polymerizing the respective components in
the continuous mode or batch mode in a slurry phase, solution phase
or gas phase, by mixing the respective components in a Henschel
mixer, a V-blender, a ribbon blender, a tumbler blender or the
like, or by melt kneading the respective components in a single
screw extruder, a twin screw extruder, a kneader, a Bunbury mixer
or the like, and then granulating or grinding.
[0724] A composition containing the propylene polymer (A) of the
present invention is not particularly limited, as long as it
contains (A).
[0725] Molding Methods and Molded Products Obtained According to
the Methods
[0726] The syndiotactic propylene polymer (A) obtained by the
above-described method, or a modified product thereof has excellent
moldability and heat resistance, and is capable of producing molded
products having excellent moldability, heat resistance,
transparency, rigidity and breaking tensile strength therefrom.
Thus, the syndiotactic propylene polymer (A) obtained by the
above-described method, or a modified product thereof can be widely
used in polyolefin applications for which it was practically
difficult to use conventional syndiotactic polypropylene. The
syndiotactic propylene polymer (A) in particular can be molded
into, for example, sheets, unstretched or stretched films,
filaments, and other molded products of various shapes.
[0727] Furthermore, in the molded products formed using the
syndiotactic propylene polymer (A), the syndiotactic propylene
polymer (A) may be contained in a part of the molded products, that
is, the syndiotactic propylene polymer (A) may be used in parts of
the molded products, and also the syndiotactic propylene polymer
(A) may be used in the entirety of the molded products. Examples of
using the syndiotactic propylene polymer (A) in parts of a molded
product include a multilayer laminate. Specific examples of the
multilayer laminate include multilayer films and sheets, multilayer
containers, and multilayer tubes, in which at least one layer is a
layer comprising the syndiotactic propylene polymer (A),
respectively; and multilayer coating film laminates where it is
contained in aqueous coating materials as one constituent
component.
[0728] The syndiotactic propylene polymer (A) of the present
invention (3) can be molded by known thermal molding methods such
as extrusion molding, injection molding, inflation molding,
extrusion lamination molding, cast molding, blow molding, extrusion
blow molding, injection blow molding, press molding, vacuum
molding, calender molding, expansion molding, and powder slash
molding. The polymer can be used in fibers, monofilaments,
non-woven fabrics and the like.
[0729] These molded products include those molded products
containing parts formed from the syndiotactic propylene polymer (A)
and parts formed from other resins (laminates, etc.). The
syndiotactic propylene polymer (A) used may be crosslinked during
the molding process.
[0730] Specific examples of the molded product include molded
products obtained by known thermal molding methods such as
extrusion molding, injection molding, inflation molding, blow
molding, extrusion blow molding, injection blow molding, press
molding, vacuum molding, calender molding, expansion molding, and
powder slash molding. Hereinafter, the molded products will be
described by way of some examples.
[0731] In the case where the molded product of the present
invention (3) is, for example, an extrusion molded product, the
shape and the product type are not particularly limited, but
preferred examples thereof include sheets, films (unstretched),
pipes, hoses, wire coatings, and tubes, and particularly preferred
are sheets (skin materials), films, tubes, catheters, and
monofilaments (non-woven fabrics).
[0732] The syndiotactic propylene polymer (A) obtained by the
above-described method, or a modified product thereof is excellent
in transparency, impact resistance, heat resistance, flexibility or
rigidity, abrasion resistance, surface hardness, contractability,
soundproofing properties, damping properties, cuttability, high
breakdown voltage, radiation resistance, degradation resistance,
uniform expandability, rubbery elasticity, kink resistance,
stretchability, creep properties, adhesiveness, flexible
modifiability, transparent modifiability and the like, and thus can
be preferably used in the following applications.
[0733] Examples of the application include, in general, food
containers, beverage bottles, pipes, food packaging materials,
retort containers, medical containers, infusion bags, apparel
cases, transparent substrates, transparent sealants, sealants,
automobile interior and exterior decorating materials, automobile
skin materials, abrasion resistant automobile interior and exterior
decorating materials, molding materials, automobile sealing
materials, dry skin materials, shrinkable films, wrapping films,
porous films, laminates, acoustic insulating materials, damping
materials, foam products, foaming materials, cushioning materials,
masking films, condenser films, protective films, reflective films,
dicing films, laminates (including glass), wire cables, stretched
films, shape memory materials, films for laminated glass,
bulletproof materials, bulletproof glass films, solar cell sealing
materials, radiation resistant films, .gamma.-ray resistant films,
flowmark modifiers, weld modifiers, non-woven fabrics, stretchable
non-woven fabrics, modifiers, adhesive materials, and
compatibilizers (graft modification).
[0734] Upon extrusion molding the syndiotactic propylene polymer
(A), conventionally known extrusion apparatuses and molding
conditions may be employed, and for example, using a single screw
extruder, a kneading extruder, a ram extruder, a gear extruder and
the like, a desired shape can be molded by extruding a molten
propylene composition through a certain die or the like.
[0735] A stretched film can be obtained by stretching an extruded
sheet or extruded film (unstretched) as described above by a known
stretching method such as a tentering method (longitudinal
transverse stretching, transverse longitudinal stretching), a
simultaneous biaxial stretching method, and a uniaxial stretching
method.
[0736] The draw ratio employed during stretching a sheet or an
unstretched film is typically about 20 to 70 times in the case of
biaxial stretching, and typically about 2 to 10 times in the case
of uniaxial stretching. It is preferable to obtain a stretched film
having a thickness of about 5 to 200 .mu.m by stretching.
[0737] An inflation film can also be produced as a film-shaped
molded product. Drawdown is unlikely to occur during the process of
inflation molding.
[0738] The sheet and film molded products formed using the
syndiotactic propylene polymer (A) are not likely to be statically
charged, and are excellent in mechanical properties, heat
resistance, stretchability, impact resistance, aging resistance,
transparency, visibility, gloss, rigidity, moisture-proof
properties and gas barrier properties. The products can be widely
used as packaging films and the like.
[0739] In this case, the sheet and film molded products formed
using the syndiotactic propylene polymer (A) may be multilayer
molded products, and may be used as multilayer laminates having at
least one layer of the syndiotactic propylene polymer.
[0740] A filament molded product can be produced by, for example,
extruding the molten syndiotactic propylene polymer (A) through a
spinneret. Specifically, a spun-bonding method or a melt blown
method is preferably used. A filament thus obtained may be further
stretched. This stretching may be performed to the extent that the
molecules become oriented in at least one axial direction of the
filament, and it is usually desirable to perform stretching at a
draw ratio of about 5 to 10 times. The filament obtained from the
thermoplastic composition according to the present invention is
hardly charged, and is excellent in transparency, rigidity, thermal
resistance, impact resistance and stretchability.
[0741] An injection molded product can be produced by injection
molding the syndiotactic propylene polymer (A) into various shapes
using conventionally known injection molding apparatuses and
employing known conditions. The injection molded product obtained
using the propylene composition is not likely to be statically
charged, is excellent in transparency, rigidity, thermal
resistance, impact resistance, surface gloss, chemical resistance,
abrasion resistance and the like, and can be used widely as a
trimming material for automobile interior decoration, a material
for automobile exterior decoration, housing for household electric
appliances, containers, and the like.
[0742] A blow molded product can be produced by blow molding the
syndiotactic propylene polymer (A) by using conventionally known
blow molding apparatuses and employing known conditions. In this
case, the blow molded product formed from the syndiotactic
propylene polymer (A) may be a multilayer molded product, and has
at least one layer of the syndiotactic propylene polymer (A).
[0743] For example, in extrusion blow molding, the syndiotactic
propylene polymer (A) is extruded from a die in a molten state at a
resin temperature of 100 to 300.degree. C. to form a tube-shaped
parison. Then, after retaining the parison in a mold of a desired
shape, air is blown in to make the parison fit the mold at a resin
temperature of 130 to 300.degree. C., and thereby a hollow molded
product can be produced. It is desirable that the draw (blow) ratio
is about 1.5 to 5 times in the transverse direction.
[0744] In injection blow molding, the syndiotactic propylene
polymer (A) is injected into a parison-mold at a resin temperature
of 100.degree. C. to 300.degree. C. After retaining the parison in
a mold of the desired shape, air is blown in to make the parison
fit the mold at a resin temperature of 120.degree. C. to
300.degree. C., and thereby a hollow molded product can be
produced. In obtaining the hollow molded product, it is desirable
that the draw (blow) ratio is 1.1 to 1.8 times in the longitudinal
direction and 1.3 to 2.5 times in the transverse direction.
[0745] Blow molded products formed using the syndiotactic propylene
polymer (A) has excellent transparency, rigidity or flexibility,
thermal resistance and impact resistance, and is also excellent in
moisture-proof properties.
[0746] Examples of a press molded product include mold stamping
molded products. For example, when a base material and a skin
material are simultaneously press molded to perform composite
integral molding (mold stamping molding) of the two materials, the
base material can be formed from the syndiotactic propylene polymer
(A).
[0747] Specific examples of such mold stamping molded product
include the materials for automobile interior decoration, such as
door trims, rear package trims, seat back garnishes, and instrument
panels.
[0748] Press molded products formed using the syndiotactic
propylene polymer (A) are not likely to be statically charged, and
are excellent in flexibility, thermal resistance, transparency,
impact resistance, aging resistance, surface gloss, chemical
resistance, abrasion resistance and the like.
[0749] Foamed molded products formed using the syndiotactic
propylene polymer (A) can be obtained at high foaming ratios, and
also have good injection moldability, as well as high rigidity and
material strength.
[0750] The syndiotactic propylene polymer (A) can be produced into
vacuum molded products such as interior decoration skin materials
for instrument panels, door trims and the like of automobiles. The
molded products are not likely to be statically charged, and are
excellent in flexibility, heat resistance, impact resistance, aging
resistance, surface gloss, chemical resistance, abrasion resistance
and the like.
[0751] By molding the propylene polymer (A) of the present
invention (3), powder slash molded products such as automobile
parts, electric appliance parts, toys, miscellaneous goods and the
like can be produced. The molded products are not likely to be
statically charged, and are excellent in flexibility, heat
resistance, impact resistance, aging resistance, surface gloss,
chemical resistance, abrasion resistance and the like.
[0752] Examples of the molded product of the present invention (3)
include a laminate having at least one layer comprising the
syndiotactic propylene polymer (A).
[0753] The propylene polymer of the present invention (3) is
particularly appropriate for extrusion molded products (films,
sheets, etc.), inflation molded products, injection molded
products, blow molded products, and fibers, and are particularly
appropriate for extrusion molded products, inflation molded
products, injection molded products and blow molded products, from
the viewpoints of transparency and heat resistance.
[0754] The propylene polymer of the present invention (3) is
appropriate in, for example, containers or non-woven fabrics. Such
container may be exemplified by food containers such as freeze
storage containers, and retort pouches, bottle containers and the
like. Examples thereof also include medical containers, and
infusion bags.
[0755] A composition comprising the propylene polymer (A) of the
present invention (3) is excellent in moldability and heat
resistance, and thus can also be used in the above-described
applications (applications of the propylene polymer (A)).
[0756] <Propylene-Based Polymer Composition (X1)>
[0757] Hereinafter, the present invention (4) will be described in
detail.
[0758] The propylene-based polymer composition (X1) of the present
invention (4) comprises a specific (AA) syndiotactic propylene
polymer and a specific (B2) propylene..alpha.-olefin copolymer.
[0759] (AA) Syndiotactic Propylene Polymer
[0760] The syndiotactic propylene polymer (AA) used in present the
invention (4) and in the present inventions (5) and (6) that will
be described later may be homopolypropylene or may be a random
copolymer of propylene..alpha.-olefin having 2 to 20 carbon atoms
(excluding propylene), or may be a propylene block copolymer, if
the polymer possesses the following properties, homopolypropylene
or a random copolymer of propylene..alpha.-olefin having 2 to 20
carbon atoms (excluding propylene) is preferred. The polymer is
particularly preferably homopolypropylene or a copolymer of
propylene with ethylene or an .alpha.-olefin having 4 to 10 carbon
atoms, and homopolypropylene is particularly preferred in view of
heat resistance.
[0761] Here, the .alpha.-olefin having 2 to 20 carbon atoms other
than propylene may be exemplified by ethylene, 1-butene,
3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
1-octadecene, 1-eicosene, or the like. Also, usually, constituent
units derived from propylene are contained in an amount of more
than 90 mol %, and preferably 91 mol % or more, based on 100 mol %
of the total amount of the constituent unit derived from the
.alpha.-olefin having 2 to 20 carbon atoms (including propylene).
In other words, the syndiotactic propylene polymer (AA) of the
present invention usually contains constituent units derived from
propylene in an amount of more than 90 mol % to 100 mol % or less,
and constituent units derived from an .alpha.-olefin having 2 to 20
carbon atoms (excluding propylene) in an amount of 0 mol % or more
to less than 10 mol % (provided that the sum of amounts of the
constituent unit derived from propylene and the constituent unit
derived from .alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene) is 100 mol %), and preferably constituent units derived
from propylene in an amount of 91 mol % or more and 100 mol % or
less, and constituent units derived from an .alpha.-olefin having 2
to 20 carbon atoms (excluding propylene) in an amount of 0 mol % or
more and 9 mol % or less.
[0762] When the syndiotactic propylene polymer (AA) is a
propylene..alpha.-olefin random copolymer, it preferably contains
the constituent unit derived from .alpha.-olefin having 2 to 20
carbon atoms (excluding propylene) in an amount of 0.3 to 7 mol %,
preferably 0.3 to 6 mol %, and more preferably 0.3 to 5 mol %.
[0763] The syndiotactic pentad fraction (rrrr fraction, pentad
syndiotacticity) of the above-described syndiotactic propylene
polymer (AA), as measured by NMR, is 85% or greater, preferably 90%
or greater, more preferably 93% or greater, and even more
preferably 94% or greater, and a syndiotactic propylene polymer
(AA) having an rrrr fraction in this range has excellent
moldability, heat resistance and transparency, and have good
properties as a crystalline polypropylene, which is preferable.
There is no particular limitation on the rrrr fraction, but it is
100% or less, and usually 99% or less, for example.
[0764] This syndiotactic pentad fraction (rrrr fraction) is
measured as follows.
[0765] The rrrr fraction is determined from the absorption
intensities of Prrrr (the absorption intensity resulting from the
methyl group in the third unit at a site wherein five propylene
units are sequentially syndiotactically bonded) and PW (the
absorption intensity originating from the entire methyl groups in
the propylene units) in the .sup.13C-NMR spectrum according to the
following equation (1):
rrrr fraction (%)=100.times.Prrrr/PW (1)
[0766] The NMR measurement is performed, for example, as follows.
Specifically, 0.35 g of a sample is dissolved under heating in 2.0
ml of hexachlorobutadiene. This solution is filtered through a
glass filter (G2), and then is introduced into an NMR tube having
an internal diameter of 10 mm after adding 0.5 ml of deuterated
benzene. Then, .sup.13C-NMR measurement is performed at 120.degree.
C. using a GX-500 NMR measuring apparatus manufactured JEOL, Ltd.
The accumulation times are 10,000 times or more.
[0767] The intrinsic viscosity [.eta.] of the syndiotactic
propylene polymer (AA) as measured in decalin at 135.degree. C. is
usually 0.1 to 10 dL/g, preferably 0.5 to 10 dL/g, more preferably
0.50 to 8.00 dL/g, even more preferably 0.95 to 8.00 dL/g,
particularly preferably in the range of 1.00 to 8.00, more
preferably in the range of 1.40 to 8.00 dL/g, and inter alia,
preferably in the range of 1.40 to 5.00 dL/g. A syndiotactic
propylene polymer (AA) having such intrinsic viscosity [.eta.]
value exhibits good flowability and good miscibility with other
components, and tends to yield molded products having excellent
mechanical strength from the resulting composition.
[0768] Furthermore, the melting point (Tm) of the syndiotactic
propylene polymer (AA) that can be measured by differential
scanning calorimetry (DSC) is 145.degree. C. or higher, preferably
150.degree. C. or higher, more preferably 155.degree. C. or higher,
and particularly 0.10 preferably 156.degree. C. or higher. Although
there is no particular upper limit of Tm, it is usually 170.degree.
C. or lower, for example. Moreover, the heat of fusion (.DELTA.H)
of the syndiotactic propylene polymer (AA) that can be measured by
differential scanning calorimetry (DSC) is preferably 40 mJ/mg or
higher, more preferably 45 mJ/mg, even more preferably 50 mJ/mg or
higher, even more preferably 52 mJ/mg or higher, and particularly
preferably 55 mJ/mg or higher.
[0769] The measurement of differential scanning calorimetry is
performed, for example, in the following manner. About 5.00 mg of a
sample is filled in an aluminum pan for exclusive use, and the
melting point (Tm) and the heat of fusion (.DELTA.H) is determined
from an endothermic curve obtained by heating the sample from
30.degree. C. to 200.degree. C. at a rate of 320.degree. C./min,
maintaining at 200.degree. C. for 5 minutes, cooling from
200.degree. C. to 30.degree. C. at a rate of 10.degree. C./min,
maintaining again at 30.degree. C. for 5 minutes, and heating again
at a rate of 10.degree. C./min, using DSCPyris1 or DSC7
manufactured by PerkinElmer, Inc. If a plurality of peaks are
detected during the DSC measurement, the peak detected on the
highest temperature side is defined as the melting point (Tm).
[0770] A syndiotactic propylene polymer (AA) having the melting
point (Tm) in this range has excellent moldability, heat resistance
and mechanical properties, and has good properties as a crystalline
polypropylene, which is preferable. By establishing the
polymerization conditions that will be described later using the
catalyst system that will be described later, a syndiotactic
propylene polymer (AA) having the melting point within this range
can be produced.
[0771] The syndiotactic propylene polymer (AA) satisfies, when the
isothermal crystallization temperature determined by differential
scanning calorimetry (DSC) is designated as T.sub.iso, and the
half-crystallization time at the isothermal crystallization
temperature T.sub.iso is designated as t.sub.1/2, the following
Equation (Eq-1) in the range of 110.ltoreq.T.sub.iso.ltoreq.150
(.degree. C.):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.5.-
56.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-1)
[0772] preferably satisfies the following equation (Eq-2):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.3.-
71.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-2)
[0773] and more preferably satisfies the following equation
(Eq-3):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.2.-
23.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-3)
[0774] The half-crystallization time (t.sub.1/2) determined by
isothermal crystallization measurement is, when the area between
the DSC caloric curve and the baseline during the isothermal
crystallization process is considered as the total calories, the
time taken to reach 50% of the calories [see New Lectures on
Polymer Experiments, 8. Properties of Polymers (KYORITSU SHUPPAN
CO., LTD.)].
[0775] Measurement of the half-crystallization time (t.sub.1/2) is
performed as follows. About 5 mg of a sample is filled in an
aluminum pan for exclusive use, and the half-crystallization time
is determined from a DSC curve obtained by heating the sample from
30.degree. C. to 200.degree. C. at a rate of 320.degree. C./min,
maintaining at 200.degree. C. for 5 minutes, cooling from that
temperature (200.degree. C.) to the respective isothermal
crystallization temperature at a rate of 320.degree. C./min, and
maintaining at that isothermal crystallization temperature, using
DSCPyris1 or DSC7 manufactured by PerkinElmer, Inc. Here, the
half-crystallization time (t.sub.1/2) is determined by setting the
initial time of the isothermal crystallization process (the time to
reach the isothermal crystallization temperature from 200.degree.
C.) as t=0. For the syndiotactic propylene polymer of the present
invention, t.sub.1/2 can be determined as described above, but when
crystallization does not occur at any isothermal crystallization
temperature, for example, at 110.degree. C., then measurement is
taken for convenience at several points at an isothermal
crystallization temperature at below 110.degree. C., and the half
crystallization time (t.sub.1/2) is determined from the
extrapolated value.
[0776] A syndiotactic propylene polymer (AA) satisfying the
equation (Eq-1) is remarkably excellent in moldability compared to
existing syndiotactic propylene polymers. Here, moldability being
excellent indicates that in the case of carrying out molding such
as injection molding, inflation molding, blow molding, extrusion or
press molding, the time taken from the molten state to the solid
state is short. Also, such syndiotactic propylene polymer is
excellent in molding cycle properties, shape stability, long-term
productivity and the like.
[0777] By establishing the polymerization conditions that will be
described later using the catalyst system that will be described
later, a syndiotactic propylene polymer (AA) satisfying the
equation (Eq-1) can be produced.
[0778] As a preferred embodiment of the syndiotactic propylene
polymer (AA) may be exemplified by an embodiment of simultaneously
satisfying the following requirement (n-decane-soluble part), in
addition to the above-described preferred embodiments (satisfying
.DELTA.H.gtoreq.40 mJ/mg, and satisfying the above equation
(Eq-1)).
[0779] The amount of the n-decane-soluble part of the syndiotactic
propylene polymer (AA) is preferably 1 (wt %) or less, more
preferably 0.8 (wt %) or less, and even more preferably 0.6 (wt %)
or less. This amount of n-decane-soluble part is an index closely
related to the blocking properties of the syndiotactic propylene
polymer (AA) or the molded products obtained therefrom, and a
smaller amount of n-decane-soluble part usually means a smaller
amount of low-crystalline components. That is, a syndiotactic
propylene polymer (AA) satisfying the present requirement
(n-decane-soluble part) as well has very good anti-blocking
properties.
[0780] Therefore, one of the most preferred embodiments of the
component (AA) is a syndiotactic propylene polymer containing
constituent units derived from propylene in an amount of more than
90 mol %, has a syndiotactic pentad fraction (rrrr fraction) of 85%
or more as measured by .sup.13C-NMR, a melting point (Tm) of
145.degree. C. or higher as measured by DSC, and a heat of fusion
(.DELTA.H) of 40 mJ/mg or more, satisfies the equation (Eq-1), and
has an n-decane-soluble part of 1 wt % or less.
[0781] In the production of the syndiotactic polypropylene polymer
(AA), the catalyst for polymerization (cat-1) comprising:
[0782] (a-3) a bridged metallocene compound represented by the
following General Formula [1-3], and
[0783] (b) at least one compound selected from:
[0784] (b-1) an organoaluminum oxy compound,
[0785] (b-2) a compound which reacts with the bridged metallocene
compound (a-3) to form an ion pair, and
[0786] (b-3) an organoaluminum compound,
[0787] or the catalyst for polymerization (cat-2) having the
catalyst (cat-1) supported on a particulate support, is suitably
used. However, as long as the produced polymer shows properties
that satisfy the requirements required from the syndiotactic
propylene polymer (AA), the catalyst used in the production of the
syndiotactic polypropylene polymer (AA) is not limited to such
catalysts.
[0788] Details of the component (a-3), component (b-1), component
(b-2) and component (b-3) are as described above.
[0789] The component (a-3), component (b-1), component (b-2) and
component (b-3) may be used after being supported on the
particulate support (c), if necessary.
[0790] Also, the catalyst for olefin polymerization (3) used in the
production of the syndiotactic propylene polymer (AA) may contain
the organic compound component (d) if necessary, along with the
respective components.
[0791] Details of the component (c) and component (d) are as
described above.
[0792] Method for Producing Syndiotactic Propylene Polymer (AA)
[0793] During the polymerization, the method of using each
component, and the order of addition are arbitrarily selected, but
the following methods may be mentioned as the methods of
polymerization.
[0794] (1) Method of adding the component (a-3) alone into the
polymerization vessel.
[0795] (2) Method of adding the component (a-3) and component (b)
into the polymerization vessel in an arbitrary order.
[0796] (3) Method of adding a catalyst component in which the
component (a-3) is supported on the support (c), and the component
(b) into the polymerization vessel in an arbitrary order.
[0797] (4) Method of adding a catalyst component in which the
component (b) is supported on the support (c), and the component
(a-3) into the polymerization vessel in an arbitrary order.
[0798] (5) Method of adding a catalyst component in which the
component (a-3) and the component (b) are supported on the support
(c) into the polymerization vessel.
[0799] According to the respective methods of (2) to (5) described
above, at least two or more of the catalyst components may be
brought into contact in advance.
[0800] In the respective methods of (4) and (5) described above
using supported component (b), unsupported component (b) may be
added in any order, as necessary. In this case, the component (b)
may be identical or different.
[0801] Furthermore, the solid catalyst component having the
component (a-3) supported on the component (c), and the solid
catalyst component having the component (a-3) and component (b)
supported on the component (c) may have the olefin prepolymerized,
or the prepolymerized solid catalyst component may further have the
catalyst component supported thereon.
[0802] The syndiotactic propylene polymer (AA) can be obtained by
polymerizing or copolymerizing propylene and at least one olefin
selected from .alpha.-olefins having 2 to 20 carbon atoms
(excluding propylene) in the presence of the catalyst for olefin
polymerization as described above.
[0803] Polymerization can be carried out by any of liquid phase
polymerization method such as a solution polymerization, suspension
polymerization or the like, and a gas phase polymerization method.
As the inert hydrocarbon medium used in the liquid phase
polymerization method, specifically aliphatic hydrocarbons such as
propane, butane, pentane, hexane, heptane, octane, decane,
dodecane, kerosene and the like; alicyclic hydrocarbons such as
cyclopentane, cyclohexane, methylcyclopentane and the like;
halogenated hydrocarbons such as ethylene chloride, chlorobenzene,
dichloromethane and the like, or mixtures thereof may be mentioned,
and the olefin to be polymerized may also be used per se as the
solvent.
[0804] When polymerization of propylene and at least one olefin
selected from .alpha.-olefins having 2 to 20 carbon atoms
(excluding propylene) is performed using the catalyst for olefin
polymerization as described above, the component (a-3) is usually
used in an amount of 10.sup.-9 to 10.sup.-1 moles, and preferably
10.sup.-8 to 10.sup.-2 moles, per liter of the reaction volume.
[0805] The component (b-1) is used in an amount such that the molar
ratio of the component (b-1) and the total transition metal atoms
(M) in the component (a-3) [(b-1)/M] is usually 0.01 to 5000, and
preferably 0.05 to 2000. The component (b-2) is used in an amount
such that the molar ratio of the component (b-2) and the transition
metal atoms (M) in the component (a-3) [(b-2)/M] is usually 1 to
10, and preferably 1 to 5. The component (b-3) is used in an amount
such that the molar ratio of the aluminum atoms in the component
(b-3) and the total transition metal (M) in the component (a-3) is
usually 10 to 5000, and preferably 20 to 2000.
[0806] The component (d) is used, in the case where the component
(b) is component (b-1), in an amount such that the molar ratio
[(d)/(b-1)] is usually 0.01 to 10, and preferably 0.1 to 5; in the
case where the component (b) is component (b-2), in an amount such
that the molar ratio [(d)/(b-2)] is usually 0.01 to 10, and
preferably 0.1 to 5; in the case where the component (b) is
component (b-3), the molar ratio [(d)/(b-3)] is usually 0.01 to 2,
and preferably 0.005 to 1.
[0807] The temperature for olefin polymerization using the catalyst
for olefin polymerization is generally within the range from -50 to
+200.degree. C., and preferably from 0 to 170.degree. C. The
polymerization pressure is under the condition of generally from
normal pressure to 10 MPa gauge pressure, and preferably from
normal pressure to 5 MPa gauge pressure, and the polymerization
reaction can be carried out either batchwise, semicontinuously or
continuously. The polymerization can be carried out by dividing the
process into two or more stages having different reaction
conditions. The molecular weight of the resulting propylene polymer
can be also regulated by allowing hydrogen to exist in the
polymerization system or by varying the polymerization temperature.
Moreover, the molecule weight can be regulated according to the
amount of the component (b) used. When adding hydrogen, the
suitable amount to be added is from about 0.001 to 100 NL per 1 kg
of olefin.
[0808] The olefin supplied to the polymerization reaction is one or
more olefins selected from .alpha.-olefins having 2 to 20 carbon
atoms (excluding propylene). The .alpha.-olefin having 4 to 20
carbon atoms is a straight-chained or branched .alpha.-olefin
having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and
for example, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene,
1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene,
l-eicosene and the like may be mentioned.
[0809] (B2) Propylene-.alpha.-Olefin Copolymer
[0810] The propylene..alpha.-olefin copolymer (B2) is a
propylene..alpha.-olefin copolymer containing constituent units
derived from propylene in an amount of 55 to 90 mol %, and
constituent units derived from at least one olefin selected from
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene)
in an amount of 10 to 45 mol %, has an MFR in the range of 0.01 to
100 g/min as measured according to JIS K-6721 at 230.degree. C.
under a load of 2.16 kg, and is characterized in satisfying at
least one of the following requirements (b-1) and (b-2):
[0811] (b-1): the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater, and
[0812] (b-2): the intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship.
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
[0813] The propylene..alpha.-olefin copolymer (B2) contains
constituent units derived from propylene in an amount of 50 to 95
mol %, and constituent units derived from an .alpha.-olefin having
2 to 20 carbon atoms (excluding propylene) in an amount of 10 to 45
mol %.
[0814] In the case of using in the present invention (4), when the
syndiotactic propylene polymer (AA) is used in an amount of 50
parts by weight based on 100 parts by weight of the sum of amounts
of (AA) and (B2), the polymer contains constituent units derived
from propylene in an amount of 55 to 90 mol %, preferably in an
amount of 55 to 85 mol %, and more preferably in an amount of 60 to
85 mol %, and constituent units derived from an .alpha.-olefin
having 2 to 20 carbon atoms (excluding propylene) in an amount of
10 to 45 mol %, preferably 15 to 45 mol %, and more preferably 15
to 40 mol %.
[0815] When used in the present invention (4), in the case where
the syndiotactic propylene polymer (AA) is present in an amount of
less than 50 parts by weight based on 100 parts by weight of the
sum of amounts of (AA) and (B2), the propylene..alpha.-olefin
copolymer (B2) contains a constituent derived from propylene in an
amount of 55 to 90 mol %, preferably in an amount of 65 to 85 mol
%, and more preferably in an amount of 70 to 85 mol %, and
constituent units derived from an .alpha.-olefin having 2 to 20
carbon atoms (excluding propylene) in an amount of 10 to 45 mol %,
preferably 15 to 35 mol %, and more preferably 15 to 30 mol %.
[0816] Here, the sum of amounts of the constituent unit derived
from propylene and the constituent unit derived from an
.alpha.-olefin having 2 to 20 carbon atoms (excluding propylene) is
100 mol %.
[0817] In addition, the .alpha.-olefin having 2 to 20 carbon atoms
(excluding propylene) may be exemplified by ethylene,
3-methyl-1-butene, 1-butene, 1-pentene, 1-hexene,
4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene or the like. In particular,
ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are
preferred.
[0818] Among the propylene..alpha.-olefin copolymers (B2) as
described above, a propylene-ethylene copolymer is one of preferred
embodiments.
[0819] Also, among the propylene..alpha.-olefin copolymers (B2) as
described above, a propylene.ethylene.HAO copolymer comprising
constituent units derived from propylene, constituent units derived
from ethylene, and constituent units derived from any one of
1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene (may be
referred to as HAO comonomer), wherein the proportion of the
constituent unit derived from ethylene is larger than the
proportion of the constituent unit derived from the HAO comonomer,
is one of preferred embodiments.
[0820] Furthermore, for the propylene ethylene copolymer or the
propylene.ethylene.HAO copolymer, which are polymers of the
preferred scope, those satisfying both (b-1) and (b-2) described
above.
[0821] The propylene..alpha.-olefin copolymer (B2) preferably has
an MFR in the range of 0.01 to 100 g/10 min, and more preferably in
the range of 0.02 to 100 g/10 min, as measured according to JIS
K-6721 at 230.degree. C. under a load of 2.16 kg.
[0822] The propylene..alpha.-olefin copolymer (B2) satisfies at
least one of (b-1) and (b-2) below;
[0823] (b-1): The syndiotactic triad fraction (rr fraction, triad
syndiotacticity) as measured by .sup.13C-NMR is 60% or greater;
and
[0824] (b-2): The intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
First, the requirement (b-1) will be explained.
[0825] (b-1): The syndiotactic triad fraction (rr fraction, triad
syndiotacticity) of the propylene..alpha.-olefin copolymer (B2) as
measured by .sup.13C-NMR is 60% or greater, preferably 70% or
greater, and more preferably 75% or greater, and a
propylene..alpha.-olefin copolymer (B2) having the rr fraction in
this range has good compatibility with the syndiotactic propylene
polymer (AA), which is preferable.
[0826] A polymer satisfying (b-1) can be obtained, for example, by
copolymerizing propylene and an .alpha.-olefin in the presence of a
catalyst capable of producing syndiotactic polypropylene, and may
also be produced using, for example, a catalyst as will be
described later.
[0827] The rr fraction is determined from the absorption
intensities of Prr (absorption intensity resulting from the methyl
group of the second unit at a site of 3 propylene units being
sequentially syndiotactically bound) and Pw (absorption intensity
resulting from the total methyl groups of propylene units) in the
.sup.13C-NMR spectrum, by the following formula (2).
rr fraction (%)=100.times.Prr/Pw (2)
[0828] Here, when the absorption resulting from mr (the absorption
resulting from at least both the syndiotactic bonding and isotactic
bonding among the 3 propylene units; used in the determination of
Pmr (absorption intensity)), the absorption resulting from rr (the
absorption resulting from the methyl group of the second unit at a
site of 3 propylene units being sequentially syndiotactically
bound; used in the determination of Prr (absorption intensity)), or
the absorption resulting from mm (the absorption resulting from the
methyl group of the second unit at a site of 3 propylene units
being sequentially isotactically bound; used in the determination
of Pmm (absorption intensity)) overlaps the absorption resulting
from the comonomer, the value is directly calculated without
subtracting the contribution of the comonomer component.
[0829] Specifically, in the description of the method for
determining the "syndiotacticity parameter (SP value)" described in
from [0018] to [0031] of JP-A No. 2002-097325, the procedure from
[0018] to [0023] is performed, and the value is determined by
calculating from the integrated intensities of the signals from the
first region, the second region and the third region, by the above
formula (2).
[0830] Also, in the present invention (4), particularly the
rr.sub.1 value, specifically, the value determined by the method
for determining the "syndiotacticity parameter (SP value)"
described in from [0018] to [0031] of JP-A No. 2002-097325, is
preferably 60% or greater, more preferably 65% or greater, and even
more preferably 70% or greater. In the calculation of the rr.sub.1
value, that is, of the rr value, when the absorption resulting from
mr (the absorption resulting from at least both the syndiotactic
bonding and isotactic bonding among the 3 propylene units; used in
the determination of Pmr (absorption intensity)), the absorption
resulting from rr (the absorption resulting from the methyl group
of the second unit at a site of 3 propylene units being
sequentially syndiotactically bound; used in the determination of
Prr (absorption intensity)), or the absorption resulting from mm
(the absorption resulting from the methyl group of the second unit
at a site of 3 propylene units being sequentially isotactically
bound; used in the determination of Pmm (absorption intensity))
overlaps the absorption resulting from the comonomer, subtraction
of the contribution of the comonomer component has been taken into
account.
[0831] The measurement of the rr value and rr.sub.1 value is, for
example, carried out in the following manner. Specifically, 0.35 g
of a sample is heated to melt in 2.0 ml of hexachlorobutadiene.
This solution is filtered through a glass filter (G2),
subsequently, 0.5 ml of deuterated benzene is added, and the
mixture is placed in an NMR tube having an internal diameter of 10
mm. Then, .sup.13C-NMR measurement is performed at 120.degree. C.
using a GX-500 type NMR measuring apparatus manufactured by JEOL,
Ltd. The accumulation times are 8,000 or greater.
[0832] Next, the requirement (b-2) will be explained.
[0833] (b-2): The propylene..alpha.-olefin copolymer (B2) is such
that the intrinsic viscosity [.eta.] (dL/g) as measured in decalin
at 135.degree. C. and the MFR (g/10 min, 230.degree. C., under a
load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
[0834] more preferably,
1.80.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.50.times.MFR.sup.(-0.-
19)
[0835] A propylene..alpha.-olefin copolymer (B2) satisfying these
relationships has good compatibility with the syndiotactic
propylene polymer (AA), and thus is preferable.
[0836] The propylene..alpha.-olefin copolymer (B2) satisfying the
above expressions can be obtained, for example, by copolymerizing
propylene with an .alpha.-olefin with a catalyst capable of
producing syndiotactic polypropylene, and may be produced, for
example, using a catalyst as will be described later. Such
materials are highly compatible with the syndiotactic propylene
polymer (AA), which is preferable.
[0837] A propylene..alpha.-olefin copolymer satisfying (b-2) has
the same [.eta.] and a larger MFR compared to conventionally
isotactic propylene-based copolymers.
[0838] It is conceived that as described in Macromolecules, 31,
1335-1340 (1998), this is attributable to the difference between
the entanglement molecular weight (reported as Me=6900 (g/mol) in
the article) of isotactic polypropylene and the entanglement
molecular weight of syndiotactic polypropylene (reported as Me=2170
(g/mol) in the article). That is, it is conceived that at the same
[.eta.], having a syndiotactic structure leads to a larger number
of entanglements and larger MFR compared to a material having an
isotactic structure.
[0839] As described above, the (B2) propylene..alpha.-olefin
copolymer satisfying at least one of (b-1) and (b-2) is a polymer
having different stereoreglarity from the propylene..alpha.-olefin
copolymer having an isotactic structure, and is thought to have a
syndiotactic structure. Therefore, the propylene..alpha.-olefin
copolymer (B2) is believed to have good compatibility with the
component (AA).
[0840] The intrinsic viscosity [.eta.] of the
propylene..alpha.-olefin copolymer (B2) as measured in decalin at
135.degree. C. is preferably 0.1 to 10 dL/g, more preferably 0.5 to
10 dL/g, and even more preferably 0.5 to 7.0 dL/g.
[0841] This propylene..alpha.-olefin copolymer (B2) preferably has
a degree of crystallization of 20% or less, and more preferably 0
to 15%, as measured by X-ray diffraction.
[0842] It is preferable that this propylene..alpha.-olefin
copolymer (B2) has a single glass transition temperature, and the
glass transition temperature (Tg) obtained by the measurement of
differential scanning calorimeter (DSC) is usually 0.degree. C. or
less. If the glass transition temperature (Tg) of the
propylene..alpha.-olefin copolymer (B2) is within the
above-described range, the cold resistance and low temperature
properties are excellent.
[0843] Differential scanning calorimetric measurement is performed,
for example, in the following manner. About 10.00 mg of a sample is
filled in an aluminum pan for exclusive use, and the glass
transition temperature (Tg) is determined from a endothermal curve
obtained by heating the sample from 30.degree. C. to 200.degree. C.
at a rate of 200.degree. C./min, maintaining at 200.degree. C. for
5 minutes, cooling 200.degree. C. to -100.degree. C. at a rate of
10.degree. C./min, maintaining at -100.degree. C. for 5 minutes,
and then heating at a rate 10.degree. C./min, using DSCRDC220
manufactured by Seiko Instruments, Inc.
[0844] Also, the molecular weight distribution of this
propylene..alpha.-olefin copolymer (B2) as measured by GPC (Mw/Mn,
relative to polystyrene, Mw: weight average molecular weight, Mn:
number average molecular weight) is preferably 3.5 or less, more
preferably 3.0 or less, and even more preferably 2.5 or less.
[0845] The propylene..alpha.-olefin copolymer (B2) can be produced
by polymerizing propylene, and at least one monomer selected from
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene),
in the presence of a catalyst for olefin polymerization
comprising:
[0846] (a-2) a bridged metallocene compound represented by the
following Formula [1-2],
[0847] (b) at least one compound selected from:
[0848] (b-1) an organoaluminum oxy compound,
[0849] (b-2) a compound which reacts with the bridged metallocene
compound (a-2) to form an ion pair, and
[0850] (b-3) an organoaluminum compound,
[0851] But as long as the polymer satisfies the requirements as the
propylene..alpha.-olefin copolymer (B2), the method for production
is not limited to this.
##STR00011##
wherein in Formula [1-2], R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.8, R.sup.9 and R.sup.12, which may be identical to
or different from each other, are each an atom or a group selected
from a hydrogen atom, a hydrocarbon group and a silicon-containing
group;
[0852] R.sup.6 and R.sup.11 are the same atoms or same groups
selected from a hydrogen atom, a hydrocarbon group and a
silicon-containing group;
[0853] R.sup.7 and R.sup.10 are the same atoms or same groups
selected from a hydrogen atom, a hydrocarbon group and a
silicon-containing group;
[0854] all of R.sup.6, R.sup.7, R.sup.10 and R.sup.11 cannot be
simultaneously hydrogen atoms;
[0855] R.sup.2 and R.sup.3 may be linked to each other to form a
ring;
[0856] among R.sup.5 to R.sup.12, adjacent groups may be linked to
each other to form a ring;
[0857] R.sup.13 and R.sup.14, which may be identical to and
different from each other, are each selected from an aryl group
having 6 to 18 carbon atoms, an alkyl group having 1 to 40 carbon
atoms, an alkylaryl group having 6 to 40 carbon atoms, a fluoroaryl
group having 6 to 20 carbon atoms, a fluoroalkylaryl group having 7
to 40 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms,
a chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl
group having 6 to 20 carbon atoms, a bromoalkylaryl group having 7
to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms,
and an iodoalkylaryl group having 7 to 40 carbon atoms;
[0858] at least one of R.sup.13 and R.sup.14 is selected from an
aryl group having 7 to 18 carbon atoms, a chloroaryl group having 6
to 20 carbon atoms, a chloroalkylaryl group having 7 to 40 carbon
atoms, a bromoaryl group having 6 to 20 carbon atoms, a
bromoalkylaryl group having 7 to 40 carbon atoms, an iodoaryl group
having 6 to 20 carbon atoms, an iodoalkylaryl group having 7 to 40
carbon atoms, and a fluoroalkylaryl group having 7 to carbon
atoms;
[0859] M is Ti, Zr or Hf;
[0860] Y is carbon or silicon;
[0861] Q is selected from a halogen, a hydrocarbon group, a
neutral, conjugated or non-conjugated diene having 10 or fewer
carbon atoms, an anion ligand, and a neutral ligand capable of
coordination with a lone electron pair, in identical or different
combinations; and
[0862] j is an integer from 1 to 4.
[0863] Hereinafter, specific examples of the bridged metallocene
compound represented by the General Formula [1-2] will be given,
but the scopes of the present invention (4) and the present
invention (5) that will be described later are not intended to be
particularly limited thereby. Herein,
octamethyloctahydrodibenzofluorene refers to a structure
represented by Formula [10],
octamethyltetrahydrodicyclopentafluorene refers to a structure
represented by Formula [11], and dibenzofluorene refers to a
structure represented by Formula [12].
##STR00012##
[0864] Specific examples of this bridged metallocene compound (a-2)
include the bridged metallocene compound (a-2a) elucidated in the
description of the present invention (2).
[0865] Furthermore, a compound resulting from replacing the
"zirconium" of the compound described above with "hafnium" or
"titanium", as well as a metallocene compound having "difluoride",
"dibromide" or "diiodide" instead of "dichloride", or having
"dimethyl" or "methylethyl" instead of "dichloride", and the like
are also likewise the metallocene compound represented by General
Formula [1-2].
[0866] The bridged metallocene compound (a-2) described above can
be produced by referring to known methods. As the known method for
production, for example, the method for production described in the
pamphlet of WO 04/029062 filed by the present Applicant may be
mentioned.
[0867] The metallocene compound as described above can be used
individually or in combination of two or more species.
[0868] As the organoaluminum oxy compound (b-1) used in the
production of the propylene..alpha.-olefin copolymer (B2), the same
compound as the organoaluminum oxy compound (b-1) used in the
production of the syndiotactic propylene polymer (AA) described
above, is used.
[0869] As the compound (b-2) reacting with the bridged metallocene
compound (a-2) to form an ion pair used in the production of the
propylene..alpha.-olefin copolymer (B2), the same compound as the
compound (b-2) reacting with the bridged metallocene compound (a-2)
to form an ion pair used in the production of the syndiotactic
propylene polymer (AA) described above, is used.
[0870] As the organoaluminum compound (b-3) used in the production
of the propylene..alpha.-olefin copolymer (B2), the same compound
as the organoaluminum compound (b-3) used in the production of the
syndiotactic propylene polymer (AA), is used.
[0871] The component (a-3), component (b-1), component (b-2) and
component (b-3) may be used after being supported on the
particulate support (c), if necessary.
[0872] Method for Producing Propylene..alpha.-Olefin Copolymer
(B2)
[0873] During polymerization of the propylene..alpha.-olefin
copolymer (B2), the method of using each component, and the order
of addition are arbitrarily selected, but the following method may
be mentioned.
[0874] Method of adding the component (a-2) and component (b) into
the polymerization vessel in an arbitrary order.
[0875] According to the method described above, at least two or
more of the catalyst components may be brought into contact in
advance.
[0876] When polymerization of olefin is performed using the
catalyst for olefin polymerization as described above, the
component (a-2) is usually used in an amount of 10.sup.-9 to
10.sup.-1 moles, and preferably 10.sup.-8 to 10.sup.-2 moles, per
liter of the reaction volume.
[0877] The component (b-1) is used in an amount such that the molar
ratio of the component (b-1) and the total transition metal atoms
(M) in the component (b-1) and the component (a-2) [(b-1)/M] is
usually 0.01 to 5000, and preferably 0.05 to 2000.
[0878] The component (b-2) is used in an amount such that the molar
ratio of the aluminum atoms in the component (b-2) and the total
transition metal (M) in the component (a-2) [(b-2)/M] is usually 1
to 1,000, and preferably 1 to 500. The component (b-3) is used in
an amount such that the molar ratio of the component (b-3) and the
transition metal atoms (M) in the component (b-3) and the component
(a-2) [(b-3)/M] is usually 1 to 10,000, and preferably 1 to
5,000.
[0879] For the propylene..alpha.-olefin copolymer (B2), propylene
and at least one olefin selected from .alpha.-olefins having 2 to
20 carbon atoms (excluding propylene) are usually copolymerized in
the liquid phase in the presence of the catalyst for olefin
polymerization as described above. Here, hydrocarbon solvents are
generally used, but .alpha.-olefins may also be used as the
solvent. As the hydrocarbon medium, the same compounds as those
described above may be specifically mentioned. Copolymerization can
be performed in any mode such as batch mode or continuous mode.
[0880] Examples of the .alpha.-olefin that can be used in
polymerization include ethylene, 1-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene and the like. The
.alpha.-olefin can be used alone, or in combination of two or more
species.
[0881] When performing copolymerization in batch mode using the
catalyst for olefin polymerization, the concentration of the
metallocene compound in the polymerization system used is usually
0.00005 to 1 millimoles, and preferably 0.0001 to 0.50 millimoles,
per 1 liter of the polymerization volume.
[0882] Furthermore, the reaction time (average residence time in
the case of performing copolymerization in the continuous mode) may
vary depending on the conditions such as catalyst concentration,
polymerization temperature and the like, but it is usually 5
minutes to 3 hours, and preferably 10 minutes to 1.5 hours.
[0883] The propylene and the at least one monomer selected
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene)
are respectively supplied in an amount such that a
propylene..alpha.-olefin copolymer (B2) of specific composition can
be obtained as described above. Upon copolymerization, a molecular
weight adjusting agent such as hydrogen can also be used.
[0884] When propylene and at least one olefin selected from
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene)
are copolymerized as described above, the propylene..alpha.-olefin
copolymer (B2) is usually obtained as a polymerization solution
containing the same. This polymerization solution is treated
according to conventional methods to obtain the
propylene..alpha.-olefin copolymer (B2).
[0885] The copolymerization reaction is usually performed under the
conditions of a temperature of 40.degree. C. to 200.degree. C.,
preferably 40.degree. C. to 180.degree. C., and more preferably
50.degree. C. to 150.degree. C., and of a pressure of greater than
0 to 10 MPa, preferably 0.5 to 10 MPa, and more preferably 0.5 to 7
MPa.
[0886] Propylene-Based Polymer Composition (X1)
[0887] The propylene-based polymer composition (X1) of the present
invention (4) contains:
[0888] (AA) 10 to 95 parts by weight, preferably 15 to 90 parts by
weight, of the syndiotactic propylene polymer, and
[0889] (B2) 90 to 5 parts by weight, preferably 85 to 10 parts by
weight, of the propylene..alpha.-olefin copolymer (provided that
the sum of amounts of (AA) and (B2) is 100 parts by weight).
[0890] Within this range, a propylene-based polymer composition
having excellent moldability and heat resistance, as well as
excellent transparency, flexibility and scratch resistance, is
obtained, which is preferable.
[0891] Also, if a material having high heat resistance, high
rigidity and excellent impact resistance is needed, the composition
preferably contains 50 parts by weight or more and 95 parts by
weight or less, more preferably 55 parts by weight or more and 90
parts by weight or less, of the syndiotactic propylene polymer
(AA), and 5 parts by weight or more and 50 parts by weight or less,
more preferably 10 parts by weight or more and 45 parts by weight
or less, of the propylene..alpha.-olefin copolymer (B2) (here, the
sum of amounts of (AA) and (B2) is 100 parts by eight) (composition
(X1i)).
[0892] When a material having excellent flexibility and rubber
elasticity is needed, the composition preferably contains 10 parts
by weight or more to less than 50 parts by weight, more preferably
10 parts by weight or more and 49 parts by weight or less, and even
more preferably 15 to 45 parts by weight, of the syndiotactic
propylene polymer (AA), and preferably more than 50 parts by weight
and 90 parts by weight or less, more preferably 51 parts by weight
or more and 90 parts by weight or less, and even more preferably 55
to 85 parts by weight, of the propylene..alpha.-olefin copolymer
(B2) (composition (X1ii)).
[0893] The composition of the present invention (4) has
particularly excellent moldability and heat resistance, and also
excellent transparency, flexibility and scratch resistance.
[0894] Here, moldability being excellent indicates that in the case
of carrying out molding such as injection molding, inflation
molding, blow molding, extrusion or press molding, the time taken
from the molten state to the solid state is short. Also, such
syndiotactic propylene polymer is excellent in molding cycle
properties, shape stability, long-term productivity and the
like.
[0895] Specifically, the time to solidification is such that the
half-crystallization time (t.sub.1/2) during the isothermal
crystallization measurement at 110.degree. C. as determined by
differential scanning calorimetry (DSC) is in the range of 1000 sec
or less, and more preferably 500 sec or less. Also, the
half-crystallization time (t.sub.1/2) determined from the
isothermal crystallization measurement at 110.degree. C. as
determined by differential scanning calorimetry (DSC) may be
referred to as property (1). The composition of the present
invention (4) has remarkably improved t.sub.1/2, compared to prior
art, by containing specific components (AA) and (B2), and for
example, can be molded without difficulties by generally used
molding methods for isotactic polypropylene.
[0896] The half-crystallization time (t.sub.1/2) determined by
isothermal crystallization measurement is, when the area between
the DSC caloric curve and the baseline during the isothermal
crystallization process is considered as the total calories, the
time taken to reach 50% of the calories [see New Lectures on
Polymer Experiments, 8. Properties of Polymers (KYORITSU SHUPPAN
CO., LTD.)]. Measurement of the half-crystallization time
(t.sub.1/2) is performed as follows. About 5.00 mg of a sample is
filled in an aluminum pan for exclusive use, and the
half-crystallization time is determined from a DSC curve obtained
by heating the sample from 30.degree. C. to 200.degree. C. at a
rate of 320.degree. C./min, maintaining at 200.degree. C. for 5
minutes, cooling from that temperature (200.degree. C.) to the
isothermal crystallization temperature of 110.degree. C. at a rate
of 320.degree. C./min, and maintaining the temperature at
110.degree. C., using DSCPyris1 or DSC7 manufactured by
PerkinElmer, Inc. Here, the half-crystallization time (t.sub.1/2)
is determined by setting the initial time of the isothermal
crystallization process (the time to reach the isothermal
crystallization temperature of 110.degree. C. from 200.degree. C.)
as t=0. For the composition of the present invention (4), t.sub.1/2
can be determined as described above, but when crystallization does
not occur at any isothermal crystallization temperature, for
example, at 110.degree. C., then measurement is taken for
convenience at several points at an isothermal crystallization
temperature at or below 110.degree. C., and the half
crystallization time (t.sub.1/2) is determined from the
extrapolated value.
[0897] The needle penetration temperature (hereinafter, may also be
referred to as property (2)) measured for the propylene-based
polymer composition (X1) described above is 145.degree. C. or
higher, more preferably 147.degree. C. or higher, and particularly
preferably 150.degree. C. or higher.
[0898] The needle penetration temperature (may be referred to as
softening temperature which is determined by TMA) can be measured
as follows.
[0899] Using SS-120 manufactured by Seiko Co., Ltd. or Q-400
manufactured by TA Instrument, and using a specimen of press sheet
having a thickness of 1 mm, a pressure of 2 kgf/cm.sup.2 is applied
with a planar indentor of 1.8 mm.phi. at a rate of temperature
increase of 5.degree. C./min, and the needle penetration
temperature (.degree. C.) is determined from the TMA curve.
[0900] Furthermore, methods for measurement of the Izod impact
strength (may also be referred to as property (3)), tensile modulus
(may also be referred to as property (4)), and haze (may also be
referred to as property (5)) will be described below.
[0901] For the Izod impact strength, a specimen of 12.7 mm
(width).times.3.2 mm (thickness).times.64 mm (length) is punched
from a press sheet having a thickness of 3 mm, a notch is inserted
by machine processing, and the Izod impact strength is measured at
0.degree. C. An average of three measurements was taken as the
value.
[0902] For the tensile modulus, a press sheet having a thickness of
1 mm was punched for No. JIS3 dumbbell according to JIS K6301, and
the specimen was provided as evaluation sample. The measurement was
performed, for example, by measuring the tensile modulus using a
tensile tester Inston 1123 manufactured by Instron, Inc. at a span
interval of 30 mm and a tensile rate of 30 mm/min at 23.degree. C.,
and an average value of 3 measurements was taken as the value.
[0903] Using a specimen from a press sheet having a thickness of 1
mm, the internal haze was measured with a digital turbidimeter
"NDH-2OD" manufactured by Nippon Denshoku Industries Co., Ltd., and
an average of 2 measurements was taken as the value.
[0904] Also, for the description above, in the respective tests,
specimens were obtained by producing a sheet having a predetermined
thickness by residual pre-heating the sample at 200.degree. C. for
5 minutes to 10 minutes in a press molding machine, subsequently
molding the sheet for 1 to 2 minutes under a pressure of 10 MPa,
and then cooling the sheet at 20.degree. C. under a pressure of 10
MPa.
[0905] In the case of the composition (X1i), as the .alpha.-olefin
having 2 to 20 carbon atoms (excluding propylene) of the
propylene..alpha.-olefin copolymer (B2), ethylene, or a combination
of ethylene and a HAO comonomer is preferred, and ethylene is
particularly preferred. Also, the constituent unit derived from an
.alpha.-olefin is more preferably contained in an amount of mol %
to 45 mol %, and particularly preferably 15 to 40 mol %. Within
this range, a composition having particularly excellent heat
resistance, transparency and impact resistance is obtained.
[0906] In the case of the composition (X1i), the
half-crystallization time (1) is preferably 1000 sec or less, and
more preferably 500 sec or less; the needle penetration temperature
(2) is preferably 145.degree. C. or higher, and more preferably
147.degree. C. or higher; the Izod impact strength (3) is
preferably 50 J/m or greater, and more preferably 100 J/m; the
tensile modulus (4) is preferably in the range of 100 MPa to 2000
MPa, more preferably in the range of 200 MPa to 1500 MPa, and even
more preferably in the range of 400 MPa to 1000 MPa; and the
internal haze (5) is preferably 50% or less, and more preferably
40% or less.
[0907] In the case of the composition (X1i), it is preferable that
at least one or more of the properties among (1) to (5) satisfy the
preferred ranges; it is more preferable that the composition
satisfies (1) or (2); it is even more preferable that the
composition either simultaneously satisfies (1), (3) and (4), or
simultaneously satisfies (2), (3) and (4), or simultaneously
satisfies (3), (4) and (5); and it is even more preferable that the
composition simultaneously satisfies (2), (3), (4) and (5); and it
is particularly preferable that the composition satisfies all of
(1), (2), (3), (4) and (5).
[0908] Furthermore, in the case of the composition (X1ii), the
syndiotactic propylene polymer (AA) is preferably contained in an
amount of 10 parts by weight or more to less than 50 parts by
weight, more preferably 10 parts by weight or more and 49 parts by
weight or less, and even more preferably 15 parts by weight or more
and 45 parts by weight or less; while the propylene..alpha.-olefin
copolymer (B2) is preferably contained in an amount of more than 50
parts by weight to 90 parts by weight or less, more preferably 51
to 90 parts by weight, and even more preferably 55 to 85 parts by
weight.
[0909] In this case, as the .alpha.-olefin having 2 to 20 carbon
atoms (excluding propylene) of the propylene..alpha.-olefin
copolymer (B2), ethylene, or a combination of ethylene and a HAO
comonomer is preferred, and ethylene is particularly preferred.
Also, the constituent unit derived from an .alpha.-olefin is more
preferably contained in an amount of 10 mol % to 45 mol %, even
more preferably to 35 mol %, and particularly preferably 15 to 30
mol %. Within this range, a composition having particularly
excellent heat resistance, transparency and impact resistance is
obtained.
[0910] In the case of the composition (X1ii), the
half-crystallization time (1) is preferably 1000 sec or less, and
more preferably 500 sec or less; the needle penetration temperature
(2) is 145.degree. C. or higher, and more preferably 147.degree. C.
or higher; the Izod impact strength (3) is preferably 100 J/m or
greater, and more preferably 200 J/m; the tensile modulus (4) is in
the range of 1 MPa to 400 MPa, more preferably in the range of 1
MPa to 200 MPa, and even more preferably 1 MPa to 100 MPa; and the
internal haze (5) is 30 or less, and more preferably 25 or
less.
[0911] In the case of the composition (X1ii), it is preferable that
at least one or more properties among (1), (2), (4) and (5); it is
more preferable that (1) or (2) satisfies the preferred range; it
is even more preferable that the composition either simultaneously
satisfies (1) and (4), or simultaneously satisfies (2) and (4), or
simultaneously satisfies (4) and (5); it is even more preferable
that the composition either simultaneously satisfies (1), (4) and
(5), or simultaneously satisfies (2), (4) and (5); and it is
particularly preferable that the composition satisfies all of (1),
(2), (4) and (5).
[0912] Also, in the case of the composition (X1ii), the residual
deformation after 200% stretching is preferably 50(%) or less, and
more preferably 40(%) or less. The gross rate of change before and
after the Japan Society for the Promotion of Science type abrasion
test is preferably 40(%) or less, and more preferably 30(%) or
less. Within this range, a composition having heat resistance,
transparency, flexibility, scratch resistance and rubber elasticity
is obtained.
[0913] The propylene-based polymer composition (Y) of the present
invention (4) comprises:
[0914] 99.7 to 70 mol % of constituent units derived from
propylene, and 0.3 to 30 mol % of constituent units derived from an
.alpha.-olefin having 2 to 20 carbon atoms (excluding propylene)
(here, the constituent unit derived from an .alpha.-olefin having 2
to 20 carbon atoms (including propylene) is 100 ml %), and has:
[0915] (2) a needle penetration temperature of 145.degree. C. or
higher, and preferably 147.degree. C. or higher;
[0916] (3) an Izod impact strength of 50 J/m or larger, and
preferably 100 J/m;
[0917] (4) a tensile modulus of in the range of 100 MPa to 2,000
MPa, and preferably in the range of 200 MPa to 1,500 MPa; and
[0918] (5) an internal haze value of 50% or less, and preferably
40% or less.
[0919] The term "composition" with regard to this propylene-based
polymer composition (Y) refers to a composition having at least a
23.degree. C. decane-soluble part and a 23.degree. C.
decane-insoluble part, and 2 parts by weight or more and 98 parts
by weight or less of the 23.degree. C. decane-soluble part, and 2
parts by weight or more and 98 parts by weight or less of the
23.degree. C. decane-insoluble part.
[0920] Here, in the case of the composition (Y), the decane-soluble
part is in the range of 5 to 55 parts by weight, and preferably in
the range of 5 to 50 parts by weight. Also, the syndiotactic pentad
fraction (rrrr fraction) of the decane-insoluble part is 85% or
greater, and the melting point (Tm) determined by DSC is
145.degree. C. or higher.
[0921] The measurement of the amount of n-decane-soluble component
is performed by adding and dissolving about 3 g of the composition
in 450 ml of n-decane at 145.degree. C., subsequently cooling the
solution to room temperature, removing the n-decane-insoluble part
by filtration, and recovering the n-decane-soluble part from the
filtrate.
[0922] The constituent unit derived from propylene is more
preferably contained in an amount of 99.7 to 75 mol %, and the
constituent unit derived from .alpha.-olefin is more preferably
contained in an amount of 0.3 to 25 mol %.
[0923] As the .alpha.-olefin, it is more preferable that at least
ethylene is contained, and it is even more preferable that only
ethylene is contained.
[0924] This composition can be produced, for example, by blending
the components that can constitute the composition (X1i) in the
propylene-based polymer composition (X1) described above.
[0925] Another propylene-based polymer composition (Z) of the
present invention (4) comprises 95 to 55 mol %, preferably 95 to 60
mol %, of constituent units derived from propylene, and to 45 mol
%, and preferably 5 to 40 mol %, of constituent units derived from
an .alpha.-olefin having 2 to 20 carbon atoms (excluding propylene)
(here, the constituent unit derived from an .alpha.-olefin having 2
to 20 carbon atoms (including propylene) is 100 ml %), and has:
[0926] (2) a needle penetration temperature of 145.degree. C. or
higher, and preferably 147.degree. C. or higher;
[0927] (3) a tensile modulus of in the range of 1 to 400 MPa, and
preferably 1 to 200 MPa; and
[0928] (5) an internal haze value of 40% or less, and preferably
30% or less. Here, the term "composition" with regard to the
propylene-based polymer composition (Z) refers to a composition
having at least a 23.degree. C. decane-soluble part and a
23.degree. C. decane-insoluble part, and 2 parts by weight or more
and98 parts by weight or less of the 23.degree. C. decane-soluble
part, and 2 parts by weight or more and 98 parts by weight or less
of the 23.degree. C. decane-insoluble part.
[0929] Here, in the case of the composition (Z), the decane-soluble
part is in the range of 50 to 95 parts by weight, and preferably in
the range of 50 to 90 parts by weight. Also, the syndiotactic
pentad fraction (rrrr fraction) of the decane-insoluble part is 85%
or greater, and the melting point (Tm) determined by DSC is
145.degree. C. or higher.
[0930] This composition can be produced, for example, by blending
the components that can constitute the composition (X1ii) in the
propylene-based polymer composition (X1) described above.
[0931] Graft Modification
[0932] With regard to any of the propylene-based polymer
composition (X1), propylene-based polymer composition (Y) and
propylene-based polymer composition (Z) of the present invention
(4), at least a part or the entirety of the propylene-based polymer
composition as described above may be graft modified with a polar
monomer.
[0933] In the case of the propylene-based polymer composition (X1),
for example, a part or all of the component (AA) may be graft
modified, a part or all of the component (B2) may be graft
modified, and a part or all of each of the component (AA) and
component (B2) may be graft modified.
[0934] This polar monomer may be exemplified by a hydroxyl
group-containing ethylenic unsaturated compound, an amino
group-containing ethylenic unsaturated compound, an epoxy
group-containing ethylenic unsaturated compound, an aromatic vinyl
compound, an unsaturated carboxylic acid or a derivative thereof, a
vinyl ester compound, vinyl chloride, a carbodiimide compound, or
the like.
[0935] As the polar monomer, in particular, the unsaturated
carboxylic acid or its derivatives are particularly preferred. As
the unsaturated carboxylic acid or its derivatives, an unsaturated
compound having at least one carboxylic acid group, an ester of a
compound having a carboxylic acid group and an alkyl alcohol, an
unsaturated compound having at least one anhydrous carboxylic acid
group, or the like, and as the unsaturated group, a vinyl group, a
vinylene group, an unsaturated cyclic hydrocarbon group, or the
like.
[0936] Specific examples of the compound include unsaturated
carboxylic acids such as acrylic acid, maleic acid, fumaric acid,
tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic
acid, isocrotonic acid, Nadic acid [trade
name](endocis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid) and
the like; or derivatives thereof, for example, acid halides,
amides, imides, anhydrides, esters and the like. Specific examples
of these derivatives include, for example, malenyl chloride,
maleimide, maleic anhydride, citraconic anhydride, monomethyl
maleate, dimethyl maleate, glycidyl maleate and the like.
[0937] These unsaturated carboxylic acids and/or derivatives
thereof may be used individually or in combination of two or more
species. Among these, an unsaturated dicarboxylic acid or an acid
anhydride thereof is suitable, and particularly maleic acid, Nadic
acid or acid anhydrides thereof are preferably used.
[0938] Modification can be obtained by graft polymerizing a polar
monomer to a product to be modified. When graft polymerizing such
polar monomer to the product to be modified, the polar monomer is
usually used in an amount of 1 to 100 parts by weight, and
preferably 5 to 80 parts by weight, based on 100 parts by weight of
the product to be modified. This graft polymerization is generally
performed in the presence of a radical initiator.
[0939] As the radical initiator, an organic peroxide, an azo
compound or the like may be used.
[0940] The radical initiator can be used after directly mixing with
the product to be modified and the polar monomer, but may be used
after dissolving the initiator in a small amount of an organic
solvent. This organic solvent is not particularly limited for use,
as long as it is an organic solvent which can dissolve the radical
initiator.
[0941] Also, upon graft polymerizing a polar monomer to the product
to be modified, a reducing substance can be used. If a reducing
substance is used, the amount of the polar monomer to be grafted
can be enhanced.
[0942] Graft modification of the product to be modified with a
polar monomer can be performed by a conventionally known method,
and for example, can be performed by dissolving the product to be
modified in an organic solvent, subsequently adding a polar
monomer, a radical initiator and the like to the solution, and
allowing the mixture to react at a temperature of 70 to 200.degree.
C., and preferably 80 to 190.degree. C., for 0.5 to 15 hours, and
preferably 1 to 10 hours.
[0943] Also, a modified propylene-based polymer composition can be
produced by reacting the product to be modified with a polar
monomer in the absence of solvent, using an extruder or the like.
This reaction is preferably performed at a temperature usually
above the melting point the product to be modified, specifically in
the case of modifying the component (B2), at a temperature of 120
to 300.degree. C., and preferably 120 to 250.degree. C., usually
for 0.5 to 10 minutes. Also, in the case of modifying a product to
be modified containing the component (AA), for example, the
reaction is preferably performed at a temperature of 160 to
300.degree. C., and preferably 180.degree. C. to 250.degree. C.,
usually for 0.5 to 10 minutes.
[0944] The amount of modification of the modified product thus
obtained (amount of the polar monomer to be grafted) is usually 0.1
to 50 wt %, preferably 0.2 to 30 wt %, and more preferably 0.2 to
10 wt %, when the modified product is taken as 100 wt %.
[0945] In the present invention (4), a propylene-based polymer
composition (X1), a propylene-based polymer composition (Y), or a
propylene-based polymer composition (Z) of the present invention
(4), which is at least partially graft modified, can be obtained by
using these modified products, and kneading, if necessary, the
products with one or more unmodified products selected from the
component (AA) and component (B2).
[0946] For example, the propylene-based polymer composition (W) of
the present invention (4), or pellets of the propylene-based
polymer composition (W) are modified, and this modified product may
be further melt kneaded with a necessary amount of unmodified
polymer (one or more selected from the component (AA) and component
(B2)), to produce the propylene-based polymer (X1), (Y) or (Z).
[0947] Furthermore, in any of the propylene-based polymer
composition (X1), (Y), and (Z), the content of the polar monomer
relative to 100 wt % of the propylene-based polymer composition
having at least partially graft modified by the polar monomer is
usually 0.001 to 50 wt %, preferably 0.001 to 10 wt %, more
preferably 0.001 to 5 wt %, and even more preferably 0.01 to 3 wt
%. Control of the content of the polar monomer can be easily
performed, for example, by appropriately selecting the grafting
conditions.
[0948] When the propylene-based polymer composition of the present
invention (4) is at least partially graft modified by a polar
monomer, the composition has excellent adhesiveness to other resins
and excellent compatibility, and also, the surface wettability of
the molded product obtained from the propylene-based polymer
composition may be improved.
[0949] Also, by at least partially graft modifying the composition,
compatibility with other materials or adhesiveness may be added,
while maintaining the performance of the propylene-based polymer
composition of the present invention (4), such as transparency, low
temperature impact resistance, mechanical properties (rigidity or
flexibility), heat resistance, and the like.
[0950] When the content of the polar monomer, for example, an
unsaturated carboxylic acid and/or a derivative thereof, is within
in the mentioned range, the propylene-based polymer composition of
the present invention (4) shows high adhesive strength to polar
group-containing resins (for example, polyesters, polyvinyl
alcohols, ethylene-vinyl alcohol copolymers, polyamides, PMMA,
polycarbonates, etc.).
[0951] The at least partially graft modified propylene-based
polymer composition of the present invention (4) may have added
other polymers, for example, thermoplastic resins or elastomers,
within the scope of not impairing the properties possessed by the
modified product. Such addition may be carried out by mixing during
the graft modification step, or after modification.
[0952] The propylene-based polymer composition of the present
invention (4) may have incorporated, if necessary, within the scope
of not impairing the purpose of the present invention, additives
such as a weather resistant stabilizer, a heat resistant
stabilizer, an antistatic agent, an anti-slipping agent, an
anti-blocking agent, an anti-fogging agent, a nucleating agent, a
lubricating agent, a dye, a pigment, a plasticizer, an anti-aging
agent, a hydrochloric acid absorbent, an antioxidant, and the
like.
[0953] The propylene-based polymer composition of the present
invention (4) may contain other polymers such as elastomers, resins
and the like, within the scope of not impairing the purpose of the
present invention (4).
[0954] Also, the propylene-based polymer composition of the present
invention (4) may contain a nucleating agent, which is a specific
arbitrary component, in order to improve the moldability, that is,
to increase the crystallization temperature and increase the rate
of crystallization. In this case, for example, the nucleating agent
is a dibenzylidene sorbitol-based nucleating agent, phosphoric acid
ester-based nucleating agent, a rosin-based nucleating agent, a
benzoic acid metal salt-based nucleating agent, a fluorinated
polyethylene, sodium
2,2-methylenebis(4,6-di-tert-butylphenyl)phosphate, pimellic acid
or a salt thereof, 2,6-naphthalenic acid dicarboxylic acid
dicyclohexylamide, or the like. The amount of mixing is not
particularly limited, but the amount is preferably about 0.1 to 1
part by weight based on 100 parts by weight of the propylene based
polymer composition. The timing for mixing is not particularly
limited, and addition is possible during or after polymerization,
or during the molding process.
[0955] Method for Production of Propylene-Based Polymer Composition
(X1)
[0956] The propylene-based polymer composition as described above
can be produced by various methods that are known in the scope
described above, for example, by multi-stage polymerizing the
respective components in the continuous mode or batch mode in a
slurry phase, solution phase or gas phase, by mixing the respective
components in a Henschel mixer, a V-blender, a ribbon blender, a
tumbler blender or the like, or by melt kneading the respective
components in a single screw extruder, a twin screw extruder, a
kneader, a Bunbury mixer or the like, and then granulating or
grinding.
[0957] The pellets of the present invention (4) comprises a
propylene-based polymer composition (W) comprising 1 to 65 parts by
weight of the syndiotactic propylene polymer (AA1) and 99 to 35
parts by weight of the propylene..alpha.-olefin copolymer (B21)
(provided that the sum of amounts of (AA1) and (B21) is 100 parts
by weight), wherein the polymer (AA1) satisfies the following
requirement (a1) and the copolymer (B21) satisfies the following
requirement (b1):
[0958] (a1): the syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or greater, the melting point (Tm)
as determined by DSC is 145.degree. C. or higher, and constituent
units derived from propylene is contained in an amount of more than
90 mol % (provided that the total amount of the constituent unit in
the polymer (AA1) is 100 mol %);
[0959] (b1): constituent units derived from propylene are contained
in an amount of 55 to 90 mol % (provided that the sum of amounts of
the constituent units in the copolymer (B21) is 100 mol %),
constituent units derived from at least one olefin selected from
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene)
are contained in an amount of 10 to 45 mol %, the MFR measured
according to JIS K-6721 at 230.degree. C. under a load of 2.16 kg
is in the range of 0.01 to 100 g/10 min, and at least one of the
following requirements (b1-1) and (b1-2) is satisfied;
[0960] (b1-1) The syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater; and
[0961] (b1-2) The intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
[0962] The syndiotactic propylene polymer (AA1) used in the pellets
of the present invention (4) may be exemplified by the same ones as
the propylene-based polymer used in the propylene-based polymer
composition (X1) described above. Preferred embodiments of the
bonding mode, the type of the constituent unit derived from
.alpha.-olefin other than the constituent unit derived from
propylene, the amount present, syndiotactic pentad fraction, Tm,
.DELTA.H, [.eta.] and the like, and the method for production are
all the same as those concerning the syndiotactic propylene polymer
(AA) used in the propylene polymer composition (X1).
[0963] The (B21) propylene..alpha.-olefin copolymer used in the
pellets of the present invention (4) may be exemplified by the same
copolymer as the propylene..alpha.-olefin copolymer (B2) used in
the propylene-based polymer composition (X1).
[0964] According to the present invention (4), preferred
embodiments of the type of the constituent units of the copolymer,
proportions, rr value, rr1 value, [.eta.], degree of
crystallization, Tg, Mw/Mn and the like, and the method for
production are all the same as those concerning the
propylene..alpha.-olefin copolymer (B2) used in the propylene-based
polymer composition (X1).
[0965] The pellets of the present invention (4) comprises a
propylene-based polymer composition (W) containing 1 to 65 parts by
weight, preferably 1 to 40 parts by weight, of the component (AA1),
and 99 to 35 parts by weight, preferably 99 to 60 parts by weight,
of the component (B21) (herein, the sum of amounts of the component
(AA1) and the component (B21) is 100 parts by weight).
[0966] The shape of the pellets of the propylene-based polymer
composition (W) may be exemplified by spherical shape, cylindrical
shape, lens shape, or cubic shape. These can be produced by
existing method for pelletization, and for example, spherical,
cylindrical or lens-shaped pellets can be obtained by homogeneously
melt mixing the component (AA1) and the component (B21), extruding
the mixture through an extruder, and then subjecting the extrudate
to hot cutting or strand cutting. In this case, cutting may be
performed either in the water, or under a gas stream such as air.
Also, by cutting an extruder having an apparatus which can
constitute the outer layer and the inner layer of the strand with
different polymers, a strand having a dual structure having the
component (AA1) disposed in the outer layer and the component (B21)
disposed in the inner layer, inter-adhesiveness can be further
suppressed, which is effective. Cubic-shaped pellets can be
obtained, for example, by homogeneously mixing, molding into a
sheet shape with rollers or the like, and using a sheet pelletizer.
A preferred size is that the length of the longest part of a pellet
is 3 cm or less. In the case of a pellet having a size exceeding
this length, the metering error may be increased.
[0967] The pellets of the propylene-based polymer composition (W)
may have the pellet surface powdered with one or two or more
powders of calcium carbonate, barium sulfate, silica, talc, stearic
acid and polyolefin. This is preferable in view of further
suppressing inter-adhesion, or suppressing the bridge phenomenon of
pellets when taken out of silo. The amount of powdering is such
that a necessary amount may be added depending on the size and
shape of the pellet, but usually 0.05 to 3 parts by weight is added
to resin composition pellets.
[0968] Within the scope of not impairing the purpose of the present
invention (4), the propylene-based polymer composition of the
present invention (4) may have incorporated, if necessary, within
the scope of not impairing the purpose of the present invention,
additives such as a weather resistant stabilizer, a heat resistant
stabilizer, an antistatic agent, an anti-slipping agent, an
anti-blocking agent, an expanding agent, a crystallization aid, an
anti-fogging agent, a nucleating agent, a lubricating agent, a dye,
a pigment, a plasticizer, an anti-aging agent, a hydrochloric acid
absorbent, an antioxidant, and the like. The propylene-based
polymer composition of the present invention (4) may contain other
polymers (excluding propylene polymer (AA1) and
propylene..alpha.-olefin copolymer (B21)) within the scope of not
impairing the purpose of the present invention (4).
[0969] As a preferred method of obtaining pellets of the
propylene-based polymer composition (W), a method may be mentioned
in which the component (AA1) and the component (B21) are kneaded at
a temperature above the maximum peak temperature (Tm) of the
component (AA1) in differential scanning calorimetry (DSC), and for
example, a temperature of 280.degree. C. or lower.
[0970] The pellets of the propylene-based polymer composition (W)
of the present invention (4) can be used as a modifier for
thermoplastic polymers, and preferably as a modifier for polyolefin
polymers.
[0971] The polymer to be modified is not particularly limited, but
polyolefin polymers are preferred. Examples of the polyolefin resin
include high density polyethylene, medium density polyethylene, low
density polyethylene, LLDPE (linear low density polyethylene),
polypropylene-based polymer, poly-4-methyl-pentene-1, and the like.
Preferred are polypropylene-based resins. The polypropylene-based
polymer in this case is a crystalline polypropylene-based polymer,
and is a homopolymer of propylene, or a random or block copolymer
of propylene and a small amount of .alpha.-olefin and/or
ethylene.
[0972] It is preferable that Tm of the polypropylene-based polymer
in this case, as measured by DSC, is 120.degree. C. or higher and
170.degree. C. or lower. Also, the polypropylene-based polymer may
be exemplified by the same ones as the component (AA). Preferred
embodiments of the bonding mode, the type of the constituent unit
derived from .alpha.-olefin other than the constituent unit derived
from propylene, the amount present, syndiotactic pentad fraction,
Tm, .DELTA.H, MFR and the like, and the method for production are
all the same as those concerning the propylene-based polymer (AA)
used in the propylene-based polymer composition (X1).
[0973] The component (AA1) contained in the pellets of the present
invention (4) and the polymer to be modified may be of the same
properties.
[0974] To obtain a modified polymer composition, the polymer to be
modified, for example, a polyolefin-based polymer, the
polyolefin-based modifier of the present invention (4), and if
necessary, the additives described in the section for the
propylene-based polymer composition (X1) may be kneaded in. As the
method for kneading, it is preferable to melt knead the pellets of
the present invention (4) and the polymer to be modified. The
amount of addition of the modifier is 3 to 95 wt %, preferably 10
to 80 wt %, and more preferably 30 to 70 wt %. If the amount is
within this range, a modified polymer composition having sufficient
modification effect, good flowability, excellent molding
processability and strength, and excellent heat resistance, can be
obtained.
[0975] The pellets of the present invention (4) have excellent
anti-blocking properties, and thus can modify other polymers with
good productivity, but are useful as a modifier for polymers
because a polymer composition having excellent transparency, low
temperature impact resistance, mechanical properties (flexibility
or rigidity, etc.), as well as excellent heat resistance can be
obtained. The effect of modification is particularly great for the
propylene-based polymer (AA) used in the propylene-based polymer
composition (X1).
[0976] Therefore, the composition (X1) of the present invention (4)
can be obtained by melt kneading the pellets of the present
invention (4) (modifier for thermoplastic polymers), a necessary
amount of the component (AA), and if necessary, other polymers
(excluding the propylene-based polymer (AA) and
propylene..alpha.-olefin copolymer (B2)) and additives.
[0977] <Propylene-Based Polymer Composition (X2)>
[0978] Hereinafter, the present invention (5) which is one of
preferred embodiments of the composition containing the
syndiotactic propylene polymer (AA) will be described in
detail.
[0979] The propylene-based polymer composition (X2) of the present
invention (5) comprises the specific (AA) syndiotactic propylene
polymer, a specific (B2) propylene..alpha.-olefin copolymer, and a
(C0) ethylene..alpha.-olefin copolymer.
[0980] Details of the syndiotactic propylene polymer (AA) and
propylene..alpha.-olefin copolymer (B2) are as described above.
[0981] Ethylene..alpha.-Olefin Random Copolymer (C0)
[0982] The ethylene..alpha.-olefin random copolymer (C0) used in
the present invention (5) is preferably an ethylene..alpha.-olefin
copolymer containing 50 to 99 mol % of constituent units derived
from ethylene, and 1 to 50 mol % of constituent units derived from
an .alpha.-olefin having 3 to 20 carbon atoms other than ethylene
(the sum of amounts of ethylene and .alpha.-olefin is 100 mol
%).
[0983] Preferably, the polymer contains constituent units derived
from ethylene in an amount of 60 to 95 mol %, and constituent units
derived from an .alpha.-olefin having 3 to 20 carbon atoms other
than ethylene in an amount of 5 to 40 mol % (the sum of amounts of
ethylene and .alpha.-olefin is 100 mol %), has a density of 910 to
850 kg/m.sup.3, and has an MFR in the range of 0.01 to 100 g/10
min, as measured according to JIS K-6721 at 190.degree. C. under a
load of 2.16 kg.
[0984] More preferably, the polymer contains constituent units
derived from ethylene in an amount of 80 to 95 mol %, and
constituent units derived from an .alpha.-olefin having 3 to 20
carbon atoms other than ethylene in an amount of 5 to 20 mol % (the
sum of amounts of ethylene and .alpha.-olefin is 100 mol %), has a
density of 900 to 860 kg/m.sup.3, and has an MFR in the range of
0.05 to 50 g/10 min, as measured according to JIS K-6721 at
190.degree. C. under a load of 2.16 kg.
[0985] The .alpha.-olefin to be copolymerized with ethylene is an
.alpha.-olefin having 3 to 20 carbon atoms, and specific examples
thereof include propylene, 1-butene, 1-pentene, 1-hexene,
1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,
1-hexadodecene, 1-octadecene, 1-nonadecene, 1-eicosene,
4-methyl-1-pentene, and the like. Among these, an .alpha.-olefin
having 3 to 10 carbon atoms is preferred. In particular, propylene,
1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferred.
These .alpha.-olefins are used individually or in combination of
two or more species.
[0986] Also, the ethylene..alpha.-olefin random copolymer (C0) may
contain a unit derived from other polymerizable monomers, within
the scope of not impairing the purpose of the present
invention.
[0987] Examples of these other polymerizable monomers include vinyl
compounds such as styrene, vinylcyclopentene, vinylcyclohexane,
vinylnorbornane and the like; vinyl esters such as vinyl acetate
and the like; unsaturated organic acids or derivatives thereof,
such as maleic anhydride and the like; conjugated dienes such as
butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene and the
like; non-conjugated polyenes such as 1,4-hexadiene, 1,
6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene,
7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene,
dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene,
5-ethylidene-2-norbornene, 5-methylene-2-norbornene,
5-isopropylidene-2-norbornene,
6-chloromethyl-5-isopropene-2-norbornene,
2,3-diisopropylidene-5-norbornene,
2-ethylidene-3-isopropylidene-5-norbornene,
2-propenyl-2,2-norbornadiene and the like. Furthermore, one of
preferred embodiments does not contain non-conjugated dienes and
non-conjugated polyenes.
[0988] The ethylene..alpha.-olefin random copolymer (C0) may
contain such unit derived from other polymerizable monomers in an
amount of 10 mol % or less, preferably 5 mol % or less, and more
preferably 3 mol % or less.
[0989] Specific examples of the ethylene..alpha.-olefin random
copolymer (C0) include ethylene-propylene random copolymer,
ethylene.1-butene random copolymer, ethylene.propylene.1-butene
random copolymer, ethylene.propylene.ethylidenenorbornene random
copolymer, ethylene.1-butene.1-octene random copolymer,
ethylene.4-methyl-1-pentene random copolymer, ethylene.1-hexene
random copolymer, ethylene.1-octene random copolymer, and the like.
Among these, ethylene-propylene random copolymer, ethylene.1-butene
random copolymer, ethylene.1-butene.1-octene random copolymer,
ethylene.1-hexene random copolymer, ethylene.1-octene random
copolymer, and the like are particularly preferably used. These
copolymers may be used in combination of two or more species.
[0990] Also, the ethylene..alpha.-olefin random copolymer (C0) used
in the present invention (5) has a degree of crystallization, as
measured by X-ray diffraction, of usually 40% or less, preferably 0
to 39%, and more preferably 0 to 35%. Also, the
ethylene..alpha.-olefin random copolymer (C0) of the present
invention (5) has an intrinsic viscosity [.eta.], as measured in
decalin at 135.degree. C., of usually 0.1 to 10 dL/g, and more
preferably 0.5 to 5 dL/g.
[0991] According to the present invention (5), by using the
component (C0), particularly the balance between impact resistance
and transparency is improved.
[0992] The ethylene..alpha.-olefin random copolymer as described
above can be produced by conventionally known methods of using a
vanadium-based catalyst, a titanium-based catalyst, or a
metallocene-based polymer. As the ethylene..alpha.-olefin random
copolymer (C0), for example, commercial products may be used, and
trade name "TAFMER.TM." manufactured by Mitsui Co., Ltd. and the
like may be used.
[0993] Propylene-Based Polymer Composition (X2)
[0994] The propylene-based polymer composition (X2) of the present
invention (5) is characterized in comprising:
[0995] (AA) 100 to 25 parts by weight of the syndiotactic propylene
polymer,
[0996] (B2) 0 to 75 parts by weight of the propylene..alpha.-olefin
copolymer (provided that the sum of amounts of (AA) and (B2) is 100
parts by weight), and
[0997] (C0) 1 to 100 parts by weight of the ethylene..alpha.-olefin
copolymer, based on 100 parts by weight of the sum of amounts of
(AA) and (B2).
[0998] Within this range, a propylene-based polymer composition
having particularly excellent moldability and heat resistance, and
excellent transparency, flexibility, and low temperature impact
resistance, is obtained, which is preferable.
[0999] Also, in the case of needing a material having good
flexibility and excellent low temperature impact resistance, a
composition comprising:
[1000] (AA) 98 to 40 parts by weight of the syndiotactic propylene
polymer,
[1001] (B2) 2 to 60 parts by weight of the propylene..alpha.-olefin
copolymer (provided that the sum of amounts of (AA) and (B2) is 100
parts by weight), and
[1002] (C0) 1 to 100 parts by weight of the ethylene..alpha.-olefin
copolymer, based on 100 parts by weight of the sum of amounts of
(AA) and (B2) (may be referred to as composition (X2i)), is
preferred.
[1003] In the case of needing a material having excellent heat
resistance, relatively high rigidity and good low temperature
impact resistance, a composition comprising:
[1004] (AA) 100 parts by weight of the syndiotactic propylene
polymer,
[1005] (B2) 0 part by weight of the propylene..alpha.-olefin
copolymer, and (C0) 1 to 100 parts by weight of the
ethylene..alpha.-olefin copolymer (may be referred to as
composition (X2ii)), is preferred.
[1006] The composition of the present invention (5) is excellent in
moldability and heat resistance, as well as in the balance between
transparency, flexibility and low temperature impact resistance.
Here, the low temperature impact resistance being excellent
indicates that, for example, when a comparison is made with
materials having the same elastic moduli, a material having higher
low temperature impact strength, or having, for example, the same
low temperature impact strength, the tensile modulus is higher.
[1007] Also, moldability being excellent indicates herein that in
the case of carrying out molding such as injection molding,
inflation molding, blow molding, extrusion or press molding, the
time taken from the molten state to the solid state is short. Also,
good moldability means being excellent in molding cycle properties,
shape stability, long-term productivity and the like.
[1008] Specifically, the time to solidification is such that the
half-crystallization time (t.sub.1/2) during the isothermal
crystallization measurement at 110.degree. C. as determined by
differential scanning calorimetry (DSC) is in the range of 1000 sec
or less, and more preferably 500 sec or less. Also, the
half-crystallization time (t.sub.1/2) determined from the
isothermal crystallization measurement at 110.degree. C. as
determined by differential scanning calorimetry (DSC) may be
referred to as property (1). The composition of the present
invention (5) has remarkably improved t.sub.1/2, compared to prior
art, by containing specific components (AA) and (B2), and for
example, can be molded without difficulties by generally used
molding methods for isotactic polypropylene.
[1009] The half-crystallization time (t.sub.1/2) determined by
isothermal crystallization measurement is, when the area between
the DSC caloric curve and the baseline during the isothermal
crystallization process is considered as the total calories, the
time taken to reach 50% of the calories [see New Lectures on
Polymer Experiments, 8. Properties of Polymers
(Shin-koubunsizikkenkouza 8 Koubunsi no Bussei) (KYORITSU SHUPPAN
CO., LTD.)]. Measurement of the half-crystallization time
(t.sub.1/2) is performed as follows. About 5.00 mg of a sample is
filled in an aluminum pan for exclusive use, and the
half-crystallization time is determined from a DSC curve obtained
by heating the sample from 30.degree. C. to 200.degree. C. at a
rate of 320.degree. C./min, maintaining at 200.degree. C. for 5
minutes, cooling from that temperature (200.degree. C.) to the
isothermal crystallization temperature of 110.degree. C. at a rate
of 320.degree. C./min, and maintaining the temperature at
110.degree. C., using DSCPyris1 or DSC7 manufactured by
PerkinElmer, Inc. Here, the half-crystallization time (t.sub.1/2)
is determined by setting the initial time of the isothermal
crystallization process (the time to reach the isothermal
crystallization temperature of 110.degree. C. from 200.degree. C.)
as t=0. For composition of the present invention (5), t.sub.1/2 can
be determined as described above, but when crystallization does not
occur at any isothermal crystallization temperature, for example,
at 110.degree. C., then measurement is taken for convenience at
several points at an isothermal crystallization temperature at or
below 110.degree. C., and the half crystallization time (t.sub.1/2)
is determined from the extrapolated value.
[1010] The needle penetration temperature (softening temperature
determined by TMA measurement; hereinafter, may also be referred to
as property (2)) measured for the propylene-based polymer
composition (X2) described above is 145.degree. C. or higher, more
preferably 150.degree. C. or higher.
[1011] The needle penetration temperature (may be referred to as
softening temperature which is determined by TMA) can be measured
as follows.
[1012] Using SS-120 manufactured by Seiko Co., Ltd. or Q-400
manufactured by TA Instrument, and using a specimen of press sheet
having a thickness of 1 mm, a pressure of 2 kgf/cm.sup.2 is applied
with a planar indentor of 1.8 mm.phi. at a rate of temperature
increase of 5.degree. C./min, and the needle penetration
temperature (.degree. C.) is determined from the TMA curve.
[1013] Furthermore, methods for measurement of the Izod impact
strength (may also be referred to as property (3)), tensile modulus
(may also be referred to as property (4)), and haze (may also be
referred to as property (5)) will be described below.
[1014] For the Izod impact strength, a specimen of 12.7 mm
(width).times.3.2 mm (thickness).times.64 mm (length) is punched
from a press sheet having a thickness of 3 mm, a notch is inserted
by machine processing, and the Izod impact strength is measured at
0.degree. C. An average of three measurements is employed.
[1015] For the tensile modulus, a press sheet having a thickness of
1 mm is punched for No. JIS3 dumbbell according to JIS K6301, and
the specimen is provided as evaluation sample. The measurement was
performed, for example, by measuring the tensile modulus using a
tensile tester Inston 1123 manufactured by Instron, Inc. at a span
interval of 30 mm and a tensile rate of 30 mm/min at 23.degree. C.,
and an average value of 3 measurements is employed.
[1016] Using a specimen from a press sheet having a thickness of 1
mm, the internal haze is measured with a digital turbidimeter
"NDH-20D" manufactured by Nippon Denshoku Industries Co., Ltd., and
an average of 2 measurements is employed.
[1017] Also, in the respective tests, a specimen is obtained by
producing a sheet having a predetermined thickness by pre-heating
the sample at 200.degree. C. for 5 minutes to 10 minutes in a press
molding machine, subsequently molding the sheet for 1 to 2 minutes
under a pressure of 10 MPa, and then cooling the sheet at
20.degree. C. under a pressure of 10 MPa.
[1018] The propylene-based polymer composition (X2) of the present
invention (5) preferably satisfies:
[1019] (2) the needle penetration temperature is 145.degree. C. or
higher, and preferably 147.degree. C. or higher;
[1020] (3) the Izod impact strength is 50 J/m or larger, and
preferably 100 J/m;
[1021] (4) the tensile modulus is in the range of 1 MPa to 2000
MPa, and preferably in the range of 1 MPa to 1500 MPa; and
[1022] (5) the internal haze value is 50% or less, and preferably
40% or less.
[1023] In the case of the composition (X2i), as the .alpha.-olefin
propylene..alpha.-olefin copolymer (B2), ethylene, or a combination
of ethylene and a HAO comonomer is preferred, and ethylene is
particularly preferred. Also, the constituent unit derived from an
.alpha.-olefin is more preferably contained in an amount of mol %
to 40 mol %, and particularly preferably 15 to 35 mol %. Within
this range, a composition having particularly excellent heat
resistance, transparency and impact resistance is obtained.
[1024] In the case of the composition (X2i), the
half-crystallization time (1) is preferably 1000 sec or less, and
more preferably 500 sec or less;
[1025] the needle penetration temperature (2) is preferably
145.degree. C. or higher, and more preferably 147.degree. C. or
higher;
[1026] the Izod impact strength (3) is preferably 50 J/m or
greater, and more preferably 100 J/m or greater;
[1027] the tensile modulus (4) is preferably in the range of 1 MPa
to 2000 MPa, more preferably in the range of 1 MPa to 1000 MPa, and
even more preferably in the range of 1 MPa to 800 MPa; and
[1028] the internal haze (5) is preferably 50% or less, and more
preferably 40% or less.
[1029] In the case of the composition (X2i), it is preferable that
at least one or more of the properties among (1) to (5) satisfy the
preferred ranges; it is more preferable that the composition either
simultaneously satisfies (1), (3) and (4), or simultaneously
satisfies (2), (3) and (4), or simultaneously satisfies (3), (4)
and (5); it is even more preferable that the composition
simultaneously satisfies (2), (3), (4) and (5); and it is
particularly preferable that the composition satisfies all of (1),
(2), (3), (4) and (5).
[1030] In the case of the composition (X2ii), as the .alpha.-olefin
of the ethylene..alpha.-olefin copolymer (C0), 1-butene and
1-octene are particularly preferred. Also, the constituent derived
from .alpha.-olefin is preferably 5 mol % to 40 mol %, more
preferably 5 to 30 mol %, and particularly preferably 5 to 20 mol
%. Within this range, a composition having particularly excellent
heat resistance, transparency, low temperature impact resistance
and rigidity is obtained.
[1031] In the case of the composition (X2ii), the
half-crystallization time (1) is preferably 1000 sec or less, and
more preferably 500 sec or less;
[1032] the needle penetration temperature (2) is preferably
145.degree. C. or higher, more preferably 147.degree. C. or higher,
and even more preferably 150.degree. C. or higher;
[1033] the Izod impact strength (3) is preferably 100 J/m or
greater, and more preferably 200 J/m;
[1034] the tensile modulus (4) is in the range of 100 MPa to 2000
MPa, more preferably in the range of 100 MPa to 1000 MPa, and even
more preferably 100 MPa to 800 MPa; and
[1035] the internal haze (5) is 50% or less, and more preferably
40% or less.
[1036] In the case of the composition (X2ii), it is preferable that
at least one or more of the properties among (1), (2), (3), (4) and
(5) satisfy the preferred ranges; it is even more preferable that
the composition either simultaneously satisfies (1), (3) and (4),
or simultaneously satisfies (2), (3) and (4), or simultaneously
satisfies (3), (4) and (5); it is even more preferable that the
composition either simultaneously satisfies (1), (3), (4) and (5),
or simultaneously satisfies (2), (3), (4) and (5); and it is
particularly preferable that the composition satisfies all of (1),
(2), (3), (4) and (5).
[1037] The propylene-based polymer composition (X2) of the present
invention (5) preferably contains 99.0 to 35.0 mol % of constituent
units derived from propylene, and 1.0 to 65 mol % of constituent
units derived from an .alpha.-olefin having 2 to 20 carbon atoms
(excluding propylene) (herein the amount of the constituent unit
derived from .alpha.-olefin having 2 to 20 carbon atoms (including
propylene) is 100 mol %). It is more preferable that the
composition contains ethylene as the .alpha.-olefin having 2 to 20
carbon atoms (excluding propylene).
[1038] The propylene-based polymer composition (X2) of the present
invention (5) may have incorporated, if necessary, within the scope
of not impairing the purpose of the present invention, additives
such as a weather resistant stabilizer, a heat resistant
stabilizer, an antistatic agent, an anti-slipping agent, an
anti-blocking agent, an anti-fogging agent, a nucleating agent, a
lubricating agent, a dye, a pigment, a plasticizer, an anti-aging
agent, a hydrochloric acid absorbent, an antioxidant, and the
like.
[1039] The propylene-based polymer composition (X2) of the present
invention (5) may contain other polymers such as elastomers, resins
and the like, within the scope of not impairing the purpose of the
present invention (5).
[1040] Graft Modification
[1041] In the propylene-based polymer composition (X2) of the
present invention (5), at least a part or the entirety of the
propylene polymer composition as described above may be graft
modified with a polar monomer.
[1042] For example, a part or all of the component (AA) may be
graft modified; a part or all of the component (B2) may be graft
modified; a part or all of the component (C0) may be graft
modified; a part or all of each of the component (AA) and component
(B2) may be graft modified; a part or all of each of the component
(B2) and component (C0) may be graft modified; a part or all of
each of the component (AA) and component (C0) may be graft
modified; and a part or all of each of the component (AA),
component (B2) and component (C0) may be graft modified.
[1043] This polar monomer may be exemplified by a hydroxyl
group-containing ethylenic unsaturated compound, an amino
group-containing ethylenic unsaturated compound, an epoxy
group-containing ethylenic unsaturated compound, an aromatic vinyl
compound, an unsaturated carboxylic acid or a derivative thereof, a
vinyl ester compound, vinyl chloride, a carbodiimide compound, or
the like.
[1044] As the polar monomer, in particular, the unsaturated
carboxylic acid or its derivatives are particularly preferred. As
the unsaturated carboxylic acid or its derivatives, an unsaturated
compound having at least one carboxylic acid group, an ester of a
compound having a carboxylic acid group and an alkyl alcohol, an
unsaturated compound having at least one anhydrous carboxylic acid
group, or the like, and as the unsaturated group, a vinyl group, a
vinylene group, an unsaturated cyclic hydrocarbon group, or the
like.
[1045] Specific examples of the compound include unsaturated
carboxylic acids such as acrylic acid, maleic acid, fumaric acid,
tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic
acid, isocrotonic acid, Nadic acid [trade
name](endocis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid) and
the like; or derivatives thereof, for example, acid halides,
amides, imides, anhydrides, esters and the like. Specific examples
of these derivatives include, for example, malenyl chloride,
maleimide, maleic anhydride, citraconic anhydride, monomethyl
maleate, dimethyl maleate, glycidyl maleate and the like.
[1046] These unsaturated carboxylic acids and/or derivatives
thereof may be used individually or in combination of two or more
species. Among these, an unsaturated dicarboxylic acid or an acid
anhydride thereof is suitable, and particularly maleic acid, Nadic
acid or acid anhydrides thereof are preferably used.
[1047] Modification can be obtained by graft polymerizing a polar
monomer to a product to be modified. When graft polymerizing such
polar monomer to the product to be modified, the polar monomer is
usually used in an amount of 1 to 100 parts by weight, and
preferably 5 to 80 parts by weight, based on 100 parts by weight of
the product to be modified. This graft polymerization is generally
performed in the presence of a radical initiator.
[1048] As the radical initiator, an organic peroxide, an azo
compound or the like may be used.
[1049] The radical initiator can be used after directly mixing with
the product to be modified and the polar monomer, but may be used
after dissolving the initiator in a small amount of an organic
solvent. This organic solvent is not particularly limited for use,
as long as it is an organic solvent which can dissolve the radical
initiator.
[1050] Also, upon graft polymerizing a polar monomer to the product
to be modified, a reducing substance can be used. If a reducing
substance is used, the amount of the polar monomer to be grafted
can be enhanced.
[1051] Graft modification of the product to be modified with a
polar monomer can be performed by a conventionally known method,
and for example, can be performed by dissolving the product to be
modified in an organic solvent, subsequently adding a polar
monomer, a radical initiator and the like to the solution, and
allowing the mixture to react at a temperature of 70 to 200.degree.
C., and preferably 80 to 190.degree. C., for 0.5 to 15 hours, and
preferably 1 to 10 hours.
[1052] Also, a modified propylene-based polymer composition can be
produced by reacting the product to be modified with a polar
monomer, using an extruder or the like. This reaction is preferably
performed at a temperature usually above the melting point of a
product to be modified, specifically in the case of modifying the
component (B2), at a temperature of 120 to 300.degree. C., and
preferably 120 to 250.degree. C., usually for 0.5 to 10 minutes.
Also, in the case of modifying a product to be modified containing
the component (AA), for example, the reaction is preferably
performed at a temperature of 160 to 300.degree. C., and preferably
180.degree. C. to 250.degree. C., usually for 0.5 to 10
minutes.
[1053] The amount of modification of the modified product thus
obtained (amount of the polar monomer to be grafted) is usually 0.1
to 50 wt %, preferably 0.2 to 30 wt %, and more preferably 0.2 to
10 wt %, when the modified product is taken as 100 wt %.
[1054] In the present invention (5), the propylene-based polymer
composition (X2) of the present invention (5) can be obtained by
using these modified products, and kneading, if necessary, the
products with one or more unmodified products selected from the
component (AA), component (B2) and component (C0).
[1055] For example, the propylene-based polymer composition (V) of
the present invention (5) that will be described later, or pellets
of the propylene-based polymer composition (V) are modified, and
this modified product may be further melt kneaded with a necessary
amount of unmodified polymer (one or more selected from the
component (AA), component (B2) and component (C0)), to produce the
propylene-based polymer (X2).
[1056] Furthermore, the content of the polar monomer relative to
100 wt % of the propylene-based polymer composition (X2) having at
least partially graft modified by the polar monomer is usually
0.001 to 50 wt %, preferably 0.001 to 10 wt %, more preferably
0.001 to 5 wt %, and even more preferably 0.01 to 3 wt %. Control
of the content of the polar monomer can be easily performed, for
example, by appropriately selecting the grafting conditions.
[1057] When the propylene-based polymer composition of the present
invention (5) is at least partially graft modified by a polar
monomer, the composition has excellent adhesiveness to other resins
and excellent compatibility, and also, the surface wettability of
the molded product obtained from the propylene-based polymer
composition may be improved.
[1058] Also, by at least partially graft modifying the composition,
compatibility with other materials or adhesiveness may be added,
while maintaining the performance of the propylene polymer
composition of the present invention (5), such as transparency, low
temperature impact resistance, mechanical properties (rigidity or
flexibility), heat resistance, and the like.
[1059] When the content of the polar monomer, for example, an
unsaturated carboxylic acid and/or a derivative thereof, is within
in the mentioned range, the polyolefin composition of the present
invention (5) shows high adhesive strength to polar
group-containing resins (for example, polyesters, polyvinyl
alcohols, ethylene-vinyl alcohol copolymers, polyamides, PMMA,
polycarbonates, etc.).
[1060] The at least partially graft modified propylene-based
polymer composition of the present invention (5) may have added
other polymers, for example, thermoplastic resins or elastomers,
within the scope of not impairing the properties possessed by the
modified product. Such addition may be carried out by mixing during
the graft modification step, or after modification.
[1061] Also, the propylene polymer composition of the present
invention (5) may contain a nucleating agent, which is a specific
arbitrary component, in order to improve the moldability, that is,
to increase the crystallization temperature and increase the rate
of crystallization. In this case, for example, the nucleating agent
is a dibenzylidene sorbitol-based nucleating agent, phosphoric acid
ester-based nucleating agent, a rosin-based nucleating agent, a
benzoic acid metal salt-based nucleating agent, a fluorinated
polyethylene, sodium
2,2-methylenebis(4,6-di-tert-butylphenyl)phosphate, pimellic acid
or a salt thereof, 2,6-naphthalenic acid dicarboxylic acid
dicyclohexylamide, or the like. The amount of mixing is not
particularly limited, but the amount is preferably about 0.1 to 1
part by weight based on 100 parts by weight of the propylene based
polymer composition. The timing for mixing is not particularly
limited, and addition is possible during or after polymerization,
or during the molding process.
[1062] Method for Producing Propylene-Based Polymer Composition
(X2)
[1063] The propylene-based polymer composition as described above
can be produced by various methods that are known in the scope
described above, for example, by multi-stage polymerizing the
respective components in the continuous mode or batch mode in a
slurry phase, solution phase or gas phase, by mixing the respective
components in a Henschel mixer, a V-blender, a ribbon blender, a
tumbler blender or the like, or by melt kneading the respective
components in a single screw extruder, a twin screw extruder, a
kneader, a Bunbury mixer or the like, and then granulating or
grinding.
[1064] Upon producing the propylene-based polymer composition (X2)
of the present invention (5), for example, pellets comprising the
propylene-based polymer composition (V) as described later can be
used as the raw material. The propylene-based polymer composition
(V) comprises:
[1065] 1 to 65 parts by weight of a syndiotactic propylene-based
polymer (AA1), and
[1066] 99 to 35 parts by weight of a propylene..alpha.-olefin
copolymer (B21) (provided that the sum of amounts of (AA1) and
(B21) is 100 parts by weight),
[1067] wherein the polymer (AA1) satisfies the following
requirement (a1), and the copolymer (B21) satisfies the following
requirement (b'):
[1068] (a1) the syndiotactic pentad fraction (rrrr fraction) as
measured by .sup.13C-NMR is 85% or greater, the melting point (Tm)
as determined by DSC is 145.degree. C. or higher, and constituent
units derived from propylene are contained in an amount of more
than 90 mol % (provided that the total amount of the constituent
units in the polymer (AA1) is 100 mol %),
[1069] (b1) constituent units derived from propylene are contained
in an amount of 55 to 90 mol %, constituent units derived from at
least one olefin selected from .alpha.-olefins having 2 to 20
carbon atoms (excluding propylene) are contained in an amount of 10
to 45 mol % (provided that the sum of amounts of the constituent
unit derived from propylene and the constituent units derived from
the .alpha.-olefin having 2 to 20 carbon atoms (provided that
propylene is excluded) is 100 mol %), the MFR measured according to
JIS K-6721 at 230.degree. C. under a load of 2.16 kg is in the
range of 0.01 to 100 g/10 min, and at least one of the following
requirements (b1-1) and (b1-2) is satisfied:
[1070] (b1-1): the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater.
[1071] (b1-2) the intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
[1072] As the syndiotactic propylene polymer (AA1) used in the
pellets, the same one as the propylene-based polymer used in the
propylene-based polymer composition (X2) can be mentioned. The
bonding mode. Preferred embodiments of the bonding mode, the type
of the constituent unit derived from .alpha.-olefin other than the
constituent unit derived from propylene, the amount present,
syndiotactic pentad fraction, Tm, .DELTA.H, [.eta.] and the like,
and the method for production are all the same as those concerning
the syndiotactic propylene polymer (AA) used in the propylene-based
polymer composition (X1).
[1073] The (B21) propylene..alpha.-olefin copolymer used in the
pellets of the present invention (5) may be exemplified by the same
as the propylene..alpha.-olefin copolymer (B2) used in the
propylene-based polymer composition (X2).
[1074] According to the present invention (5), preferred
embodiments of the type of the constituent units of the copolymer,
proportions, rr value, rr1 value, [.eta.], degree of
crystallization, Tg, Mw/Mn and the like, and the method for
production are all the same as those concerning the
propylene..alpha.-olefin copolymer (B2) used in the propylene-based
polymer composition (X2).
[1075] The pellets comprise propylene based polymer composition (V)
which includes 1 to 65 parts by weight, preferably 1 to 40 parts by
weight, of the (AA1) component; 99 to 35 parts by weight,
preferably 99 to 60 parts by weight, of (B21) component (herein,
the sum of amounts of (AA1) component and (B21) component is 100
mol).
[1076] The shape of the pellets of the propylene-based polymer
composition (V) may be exemplified by spherical shape, cylindrical
shape, lens shape, or cubic shape. These can be produced by
existing method for pelletization, and for example, spherical,
cylindrical or lens-shaped pellets can be obtained by homogeneously
melt mixing the component (AA1) and the component (B21), extruding
the mixture through an extruder, and then subjecting the extrudate
to hot cutting or strand cutting. In this case, cutting may be
performed either in the water, or under a gas stream such as air.
Also, by cutting an extruder having an apparatus which can
constitute the outer layer and the inner layer of the strand with
different polymers, a strand having a dual structure having the
component (AA1) disposed in the outer layer and the component (B21)
disposed in the inner layer, inter-adhesiveness can be further
suppressed, which is effective. Cubic-shaped pellets can be
obtained, for example, by homogeneously mixing, molding into a
sheet shape with rollers or the like, and using a sheet pelletizer.
A preferred size is that the length of the longest part of a pellet
is 3 cm or less. In the case of a pellet having a size exceeding
this length, the metering error may be increased.
[1077] The pellets comprising the propylene-based polymer
composition (V) may have the pellet surface powdered with one or
two or more powders of calcium carbonate, barium sulfate, silica,
talc, stearic acid and polyolefin. This is preferable in view of
further suppressing inter-adhesion, or suppressing the bridge
phenomenon of pellets when taken out of silo. The amount of
powdering is such that a necessary amount may be added depending on
the size and shape of the pellet, but usually 0.05 to 3 parts by
weight is added to resin composition pellets.
[1078] Within the scope of not impairing the purpose of the present
invention (5), the propylene-based polymer composition of the
present invention (5) may have incorporated, if necessary, within
the scope of not impairing the purpose of the present invention,
additives such as a weather resistant stabilizer, a heat resistant
stabilizer, an antistatic agent, an anti-slipping agent, an
anti-blocking agent, an expanding agent, a crystallization aid, an
anti-fogging agent, a nucleating agent, a lubricating agent, a dye,
a pigment, a plasticizer, an anti-aging agent, a hydrochloric acid
absorbent, an antioxidant, and the like. The propylene-based
polymer composition of the present invention (5) may contain other
polymers (excluding propylene polymer (AA1),
propylene..alpha.-olefin copolymer (B21), and
ethylene..alpha.-olefin copolymer (C0)) within the scope of not
impairing the purpose of the present invention (5).
[1079] As a preferred method of obtaining pellets of the
propylene-based polymer composition (V), a method may be mentioned
in which the component (AA1) and the component (B21) are kneaded at
a temperature above the maximum peak temperature (Tm) of the
component (AA1) in differential scanning calorimetry (DSC), and for
example, a temperature of 28.degree. C. or lower.
[1080] To obtain a modified polymer composition (X2) from the
propylene-based polymer composition (V), the polymer to be
modified, for example, a polyolefin polymer, the polyolefin
modifier of the present invention (5), and if necessary, the
additives described in the section for the propylene-based polymer
composition (X2) may be kneaded in. As the method for kneading, it
is preferable to melt knead the pellets of the present invention
(5) and the polymer to be modified. The amount of addition of the
modifier is 3 to 95 wt %, preferably to 80 wt %, and more
preferably 30 to 70 wt %. If the amount is within this range, a
modified polymer composition having sufficient modification effect,
good flowability, excellent molding processability and strength,
and excellent heat resistance, can be obtained.
[1081] The pellets have excellent anti-blocking properties, and
thus can modify other polymers with good productivity.
[1082] Therefore, the composition (X2) of the present invention (5)
can be obtained by melt kneading the pellets of the present
invention (5) (modifier for thermoplastic polymers), a necessary
amount of component (AA), and if necessary, a necessary amount of
(C0) ethylene..alpha.-olefin copolymer, other polymers (excluding
the syndiotactic propylene polymer (AA) and
propylene..alpha.-olefin copolymer (B2) having 2 to 20 carbon atoms
(excluding propylene), ethylene..alpha.-olefin copolymer (C0)
having 3 to 20 carbon atoms) and additives.
[1083] <Propylene-Based Polymer Composition (X3)>
[1084] Hereinafter, the present invention (6) will be described in
detail.
[1085] The propylene-based polymer composition (X3) of the present
invention (6) comprises a specific (AA) syndiotactic propylene
polymer, and a specific (B3) propylene..alpha.-olefin
copolymer.
[1086] Details of the syndiotactic propylene polymer (AA) are as
described above.
[1087] Propylene..alpha.-Olefin Copolymer (B3)
[1088] The propylene..alpha.-olefin copolymer (B3) contains
constituent units derived from propylene in an amount of 30 to 90
mol %, and constituent units derived from at least one olefin
selected from .alpha.-olefins having 2 to 20 carbon atoms
(excluding propylene) in an amount of 10 to 70 mol % (provided that
the sum of amounts of the constituent unit derived from propylene
and the constituent unit derived from the .alpha.-olefin having 2
to 20 carbon atom (excluding propylene) is 100 mol %), has an MFR
in the range of 0.01 to 100 g/10 min as measured according to JIS
K-6721 at 230.degree. C. under a load of 2.16 kg, and is
characterized in satisfying at least one of the following
requirements (b-1) and (b-2):
[1089] (b-1): the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater, and
[1090] (b-2): the intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship.
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
[1091] According to the present invention (6), a
propylene..alpha.-olefin copolymer (B3) having various properties
within the above-described ranges is used without any particularly
limitation, but this propylene..alpha.-olefin copolymer (B3) is a
copolymer containing 30 to 90 mol %, preferably 40 to 90 mol %,
more preferably 50 to 90 mol %, and even more preferably 51 to 90
mol % of constituent units derived from propylene; and 10 to 70 mol
% (herein the sum of amounts of the constituent units derived from
propylene and a constituent unit derived from ethylene, and
constituent units derived from .alpha.-olefin is 100 mol %),
preferably 10 to 60 mol %, more preferably 10 to 50 mol %, and even
more preferably 10 to 49 mol %, in a total amount of constituent
units derived from ethylene and constituent units derived from an
.alpha.-olefin having 4 to 20 carbon atoms. This is one of
preferred embodiments in view of damping properties, scratch
resistance and abrasion resistance.
[1092] The propylene..alpha.-olefin copolymer (B3) is a copolymer
of propylene, ethylene and an .alpha.-olefin having 4 to 20 carbon
atoms, and when the molar fraction of the constituent unit derived
from ethylene is designated as PE, and the molar fraction of an
.alpha.-olefin having 4 to 20 carbon atoms is designated as
P.sub.HAO, a copolymer having P.sub.E.ltoreq.P.sub.HAO is more
preferred. More specifically, the value of P.sub.E/P.sub.HAO is
0.01 to 1.00, preferably 0.05 to 0.80, more preferably 0.06 to
0.60, and even more preferably 0.10 to 0.50.
[1093] The propylene-based polymer composition (X3) of the present
invention (6) is a composition (composition (X3i) further
containing 0.1 to 100 parts by weight of a hydrocarbon resin (C1)
that will be described later, based on 100 parts by weight of the
sum of amounts of the syndiotactic propylene polymer (AA) and
propylene..alpha.-olefin copolymer (B3)), and the
propylene..alpha.-olefin copolymer (B3) is a copolymer of
propylene.ethylene..alpha.-olefin containing 4 to 20 carbon atoms,
containing constituent units derived from propylene in an amount of
30 to 90 mol %, preferably 40 to 90 mol %, more preferably 50 to 90
mol %, and even more preferably 51 to 90 mol %, and constituent
units derived from ethylene and constituent units derived from an
.alpha.-olefin having 4 to 20 carbon atoms in a total amount of 10
to 70 mol % (herein, the sum of amounts of the constituent unit
derived from propylene, the constituent unit derived from ethylene,
and the constituent unit derived from an .alpha.-olefin having 4 to
20 is 100 mol %), preferably 10 to 60 mol %, more preferably 10 to
50 mol %, and even more preferably to 49 mol %, wherein
.alpha.-olefin copolymer is preferably an copolymer of
propylene.ethylene..alpha.-olefin having 4 to 20 carbon atoms which
satisfies P.sub.E.ltoreq.P.sub.HAO when the proportion of the
constituent unit derived from ethylene being designated as P.sub.E
(mol %), and the proportion of an .alpha.-olefin having 4 to 20
carbon atoms being designated as P.sub.HAO (mol %).
[1094] More specifically, the value of P.sub.E/P.sub.HAO is
preferably 0.01 to 1.00, more preferably 0.05 to 0.80, even more
preferably 0.06 to 0.60, and particularly preferably 0.10 to
0.50.
[1095] When the propylene-based polymer composition (X3) of the
present invention (6) is a composition ("composition (X3ii)")
further containing 0.1 to 500 parts by weight of a non-crosslinked
or crosslinked olefinic thermoplastic elastomer (C2), based on 100
parts by weight of the sum of amounts of the syndiotactic propylene
polymer (AA) and propylene..alpha.-olefin copolymer (B3), the
propylene..alpha.-olefin copolymer (B3) more preferably contains
constituent units derived from propylene in an amount of 30 to 90
mol %, preferably 50 to 90 mol %, more preferably 55 to 90 mol %,
and even more preferably 60 to 90 mol %, and the sum of amounts of
constituent units derived from ethylene and constituent units
derived from an .alpha.-olefin having 4 to 20 carbon atoms is 10 to
70 mol % (herein, the sum of amounts of the constituent unit
derived from propylene, the constituent unit derived from ethylene,
and the constituent unit derived from an .alpha.-olefin having 4 to
20 is 100 mol %), preferably 10 to 50 mol %, and more preferably 10
to 45 mol %.
[1096] Preferred examples of the .alpha.-olefin having 2 to 20
carbon atoms (excluding propylene) include ethylene, 1-butene,
1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,
1-octadecene, 1-eicosene and the like.
[1097] It is preferable that the MFR of the
propylene..alpha.-olefin copolymer (B3) as measured according to
JIS K-6721 at 230.degree. C. under a load of 2.16 kg, is within the
range of 0.01 to 100 g/10 min.
[1098] The propylene..alpha.-olefin copolymer (B3) used in the
present invention (6) satisfies at least one of the following (b-1)
and (b-2).
[1099] (b-1) The syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or greater; and
[1100] (b-2) The intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
[1101] These requirements (b-1) and (b-2) are the same as the
requirements (b-1) and (b-2) for the propylene..alpha.-olefin
copolymer (B2) used in the present inventions (4) and (5) described
above, and details of the requirements are as described above.
[1102] The propylene..alpha.-olefin copolymer (B3) is, like the
propylene..alpha.-olefin copolymer (B2), can be produced by
polymerizing propylene, and at least one olefin selected from
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene),
in the presence of a catalyst for olefin polymerization
comprising:
[1103] (a-2) a bridged metallocene compound represented by the
following Formula [1-2],
[1104] (b) at least one compound selected from:
[1105] (b-1) an organoaluminum oxy compound,
[1106] (b-2) a compound which reacts with the bridged metallocene
compound (a-2) to form an ion pair, and
[1107] (b-3) an organoaluminum compound,
[1108] but as long as the requirements as the
propylene..alpha.olefin copolymer (B3) are satisfied, the method
for production is not limited thereto.
##STR00013##
wherein in Formula [1-2], R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.8, R.sup.9 and R.sup.12, which may be identical to
or different from each other, are each an atom or a group selected
from a hydrogen atom, a hydrocarbon group and a silicon-containing
group;
[1109] R.sup.6 and R.sup.11 are the same atoms or same groups
selected from a hydrogen atom, a hydrocarbon group and a
silicon-containing group;
[1110] R.sup.7 and R.sup.10 are the same atoms or same groups
selected from a hydrogen atom, a hydrocarbon group and a
silicon-containing group;
[1111] all of R.sup.6, R.sup.7, R.sup.10 and R.sup.11 cannot be
simultaneously hydrogen atoms;
[1112] R.sup.2 and R.sup.3 may be linked to each other to form a
ring;
[1113] among R.sup.5 to R.sup.12, adjacent groups may be linked to
each other to form a ring;
[1114] R.sup.13 and R.sup.14, which may be identical to and
different from each other, are each selected from an aryl group
having 6 to 18 carbon atoms, an alkyl group having 1 to 40 carbon
atoms, an alkylaryl group having 6 to 40 carbon atoms, a fluoroaryl
group having 6 to 20 carbon atoms, a fluoroalkylaryl group having 7
to 40 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms,
a chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl
group having 6 to 20 carbon atoms, a bromoalkylaryl group having 7
to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms,
and an iodoalkylaryl group having 7 to 40 carbon atoms;
[1115] at least one of R.sup.13 and R.sup.14 is selected from an
aryl group having 7 to 18 carbon atoms, a chloroaryl group having 6
to 20 carbon atoms, a chloroalkylaryl group having 7 to 40 carbon
atoms, a bromoaryl group having 6 to 20 carbon atoms, a
bromoalkylaryl group having 7 to 40 carbon atoms, an iodoaryl group
having 6 to 20 carbon atoms, an iodoalkylaryl group having 7 to 40
carbon atoms, and a fluoroalkylaryl group having 7 to 40 carbon
atoms;
[1116] M is Ti, Zr or Hf;
[1117] Y is carbon or silicon;
[1118] Q is selected from a halogen, a hydrocarbon group, a
neutral, conjugated or non-conjugated diene having 10 or fewer
carbon atoms, an anion ligand, and a neutral ligand capable of
coordination with a lone electron pair, in identical or different
combinations; and
[1119] j is an integer from 1 to 4.
[1120] Specific examples of this bridged metallocene compound (a-2)
include the bridged metallocene compound (a-2a) described in the
explanation of the present invention (4).
[1121] Furthermore, a compound resulting from replacing the
"zirconium" of the compound described above (bridged metallocene
compound (a-2a)) with "hafnium" or "titanium", as well as a
metallocene compound having "difluoride", "dibromide" or "diiodide"
instead of "dichloride", or having "dimethyl" or "methylethyl"
instead of "dichloride", and the like are also likewise the
metallocene compound represented by the General Formula [1-2].
[1122] The bridged metallocene compound (a-2) described above can
be produced by a known method. As the known method for production,
for example, the method for production described in the pamphlet of
WO 2004/029062 filed by the present Applicant may be mentioned.
[1123] The metallocene compound as described above can be used
alone or in combination of two or more species.
[1124] As the organoaluminum oxy compound (b-1) used in the
production of the propylene..alpha.-olefin copolymer (B3), the same
compound as the organoaluminum oxy compound (b-1) used in the
production of the syndiotactic propylene polymer (AA) is used.
[1125] As the compound (b-2) reacting with the bridged metallocene
compound (a-2) to form an ion pair, used in the production of
propylene..alpha.-olefin copolymer (B3), the same compound as the
compound (b-2) reacting with the bridged metallocene compound (a-2)
to form an ion pair, used in the production of the syndiotactic
propylene polymer (AA), is used.
[1126] As the organoaluminum compound (b-3) used in the production
of the propylene..alpha.-olefin copolymer (B3), the same compound
as the organoaluminum compound (b-3) used in the production of the
syndiotactic propylene polymer (AA) is used.
[1127] The respective components (a-2, b-1, b-2 and b-3) may be
used, if necessary, after being supported on the particulate
support (c).
[1128] Method for Producing Propylene..alpha.-Olefin Copolymer
(B3)
[1129] During polymerization of the propylene..alpha.-olefin
copolymer (B3), the method of using each component, and the order
of addition are arbitrarily selected, but the following method may
be mentioned.
[1130] Method of adding the component (a-2) and component (b) into
the polymerization vessel in an arbitrary order.
[1131] According to the method described above, at least two or
more of the catalyst components may be brought into contact in
advance.
[1132] When polymerization of olefin is performed using the
catalyst for olefin polymerization as described above, the
component (a-2) is usually used in an amount of 10.sup.-9 to
10.sup.-1 moles, and preferably 10.sup.-8 to 10.sup.-2 moles, per
liter of the reaction volume.
[1133] The component (b-1) is used in an amount such that the molar
ratio of the component (b-1) and the total transition metal atoms
(M) in the component (b-1) and the component (a-2) [(b-1)/M] is
usually 0.01 to 5000, and preferably 0.05 to 2000. The component
(b-2) is used in an amount such that the molar ratio of the
aluminum atoms in the component (b-2) and the total transition
metal (M) in the component (a-2) [(b-2)/M] is usually 1 to 1,000,
and preferably 1 to 500. The component (b-3) is used in an amount
such that the molar ratio of the component (b-3) and the transition
metal atoms (M) in the component (b-3) and the component (a-2)
[(b-3)/M] is usually 1 to 10,000, and preferably 1 to 5,000.
[1134] For the propylene..alpha.-olefin copolymer (B3), propylene
and at least one olefin selected from .alpha.-olefins having 2 to
20 carbon atoms (excluding propylene) are usually copolymerized in
the liquid phase in the presence of the catalyst for olefin
polymerization as described above. Here, hydrocarbon solvents are
generally used, but .alpha.-olefins may also be used as the
solvent. As the hydrocarbon medium, the same compounds as those
described above may be specifically mentioned. Copolymerization can
be performed in any mode such as batch mode or continuous mode.
[1135] Examples of the .alpha.-olefin that can be used in
polymerization include ethylene, 1-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene and the like. The
.alpha.-olefin can be used alone, or in combination of two or more
species.
[1136] When performing copolymerization in batch mode using the
catalyst for olefin polymerization, the concentration of the
metallocene compound in the polymerization system used is usually
0.00005 to 1 millimoles, and preferably 0.0001 to 0.50 millimoles,
per 1 liter of the polymerization volume.
[1137] Furthermore, the reaction time (average residence time in
the case of performing copolymerization in the continuous mode) may
vary depending on the conditions such as catalyst concentration,
polymerization temperature and the like, but it is usually 5
minutes to 3 hours, and preferably 10 minutes to 1.5 hours.
[1138] The propylene and the at least one monomer selected
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene)
are respectively supplied in an amount such that a
propylene..alpha.-olefin copolymer (B3) of specific composition can
be obtained as described above. Upon copolymerization, a molecular
weight adjusting agent such as hydrogen can also be used.
[1139] When propylene and at least one olefin selected from
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene)
are copolymerized as described above, the propylene..alpha.-olefin
copolymer (B3) is usually obtained as a polymerization solution
containing the same. This polymerization solution is treated
according to conventional methods to obtain the
propylene..alpha.-olefin copolymer (B3).
[1140] The copolymerization reaction is usually performed under the
conditions of a temperature of 40.degree. C. to 200.degree. C.,
preferably 40.degree. C. to 180.degree. C., and more preferably
50.degree. C. to 150.degree. C., and of a pressure of greater than
0 to 10 MPa, preferably 0.5 to 10 MPa, and more preferably 0.5 to 7
MPa.
[1141] [(C1) One or More Resins Selected from the Group Consisting
of Rosin-Based Resins, Terpene-Based Resins and Petroleum
Resins]
[1142] Among one or more resins (C1) selected from the group
consisting of rosin-based resins, terpene-based resins and
petroleum resins used in the present invention (6), examples of the
rosin-based resin include natural rosins, polymerized rosins,
rosins modified with maleic acid, fumaric acid, (meth)acrylic acid
and the like, and rosin derivatives. These rosin derivatives
include esterification products of the above-described natural
rosins, polymerized rosins or modified rosins, phenol modified
products and esterification products thereof, and the like.
Hydrogenation products thereof are also included.
[1143] Also, examples of terpene-based resins include resins such
as .alpha.-pinene, .beta.-pinene, limonene, dipentene, terpene
phenol, terpene alcohol, terpene aldehyde and the like, and
aromatic-modified terpene-based resins obtained by polymerizing an
aromatic monomer such as styrene to .alpha.-pinene, .beta.-pinene,
limonene, dipentene and the like, may also be mentioned.
Hydrogenation products thereof are also included.
[1144] Furthermore, examples of petroleum resin include aliphatic
petroleum resins having the C5 distillate fraction of tar-naphtha
as the main ingredient, aromatic petroleum resins having the C9
distillate fraction as the main ingredient, and copolymerization
petroleum resins thereof. That is, C5-based petroleum resins
(resins polymerized with the C5 distillate fraction of
naphtha-cracked oil), C9-based petroleum resins (resins polymerized
with the C9 distillate fraction of naphtha-cracked oil), and
C5C9-copolymerized petroleum resins (resins copolymerized with the
C5 distillate fraction and C9 distillate fraction of
naphtha-cracked oil), as well as styrenes, indenes in the
tar-naphtha distillate fraction, coumarone, coumarone-indene-based
resins containing dicyclopentadiene and the like, alkylphenol
resins represented by a condensation product of p-tertiary
butylphenol and acetylene, xylene-based resins formed by reacting
o-xylene, p-xylene or m-xylene with formalin, and the like.
[1145] Also, the one or more resins (C1) selected from the group
consisting of rosin-based resins, terpene-based resins and
petroleum resins, which may be used in the present invention (6),
are preferably in the form of hydrogenated derivatives since the
derivatives have excellent weather resistance and discoloration
resistance. The softening temperature of the resin (C1) determined
by the ring and ball method is preferably in the range of 40 to
180.degree. C. The number average molecular weight (Mn) molecular
weight of the resin (C1) determined by GPC is preferably in the
range of about 100 to 10,000.
[1146] As the one or more resins (C1) selected from the group
comprising rosin-based resins, terpene-based resins and petroleum
resins, which may be used in the present invention (6),
commercially available products can be used.
[1147] [Non-Crosslinked or Partially Crosslinked Olefinic
Thermoplastic Elastomer (C2)]
[1148] Hereinafter, the component (C2) used in the present
invention (6) will be described in detail.
[1149] The non-crosslinked or partially crosslinked olefinic
thermoplastic elastomer (C2) which may be used in the present
invention (6) preferably contains polypropylene and an
ethylene..alpha.-olefin random copolymer containing a
non-conjugated diene, but is not limited thereto. For example, a
non-crosslinked or partially crosslinked olefinic thermoplastic
elastomer containing polypropylene and an ethylene..alpha.-olefin
random copolymer may be used, and the .alpha.-olefin is preferably
propylene or butene.
[1150] The MFR of the non-crosslinked or partially crosslinked
olefinic thermoplastic elastomer (C2), as measured at 230.degree.
C. under a load of 10 kg, is preferably 0.001 to 100, and more
preferably 0.01 to 80.
[1151] The melting point (Tm) of the non-crosslinked or partially
crosslinked olefinic thermoplastic elastomer (C2), as measured from
an endothermic curve of DSC, is preferably in the range of 120 to
165.degree. C., and more preferably 130 to 160.degree. C. The
non-crosslinked or partially crosslinked olefinic thermoplastic
elastomer (C2) is a non-crosslinked thermoplastic elastomer
composition or a partially crosslinked thermoplastic elastomer
composition, and is preferably composed of a crystalline polyolefin
resin (C2-1) and an .alpha.-olefin copolymer rubber (C2-2).
[1152] [Crystalline Polyolefin Resin (C2-1)]
[1153] The crystalline polyolefin resin (C2-1) which may be used in
the present invention (6) is a crystalline high molecular weight
solid product obtainable by polymerizing one or two or more
monoolefins by a high pressure method or a lower pressure method.
Examples of such resin include isotactic and syndiotactic
monoolefin polymer resins, but representative resins thereof are
commercially available.
[1154] Specific examples of suitable raw material olefin for the
crystalline polyolefin resin (C2-1) include ethylene, propylene,
1-butene, 1-pentene, 1-hexene, 2-methyl-1-propene,
3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene,
1-octene, 1-decene, and olefin mixture having two or more of these
olefin mixed.
[1155] As the crystalline polyolefin resin (C2-1), particularly an
isotactic polypropylene having a propylene content of 70 mol % or
greater, and preferably having a propylene content of 80 mol % or
greater, is suitably used.
[1156] The polymerization mode may be any of random type or block
type, and any polymerization mode can be employed without any
problem, as long as a resin-like product can be obtained. The MFR
of the crystalline polyolefin resin (C2-1) (A-1STM A-4 1238-65 T,
230.degree. C.) is usually in the range of 0.01 to 100 g/10 min,
and particularly preferably 0.05 to 50 g/10 min.
[1157] The melting point (Tm) of the crystalline polyolefin resin
(C2-1) used in the thermoplastic elastomer (C2), as determined by
an endothermic curve of DSC, is preferably in the range of 120 to
165.degree. C., and more preferably 130.degree. C. to 160.degree.
C. Also, the crystalline polyolefin resin (C2-1) may be the
polypropylene exemplified as the syndiotactic polypropylene (AA),
or may be a crystalline polyolefin other than the (AA).
[1158] The crystalline polyolefin resin (C2-1) plays a role in
enhancing the flowability and heat resistance of the composition.
According to the present invention (6), the crystalline polyolefin
resin (C2-1) is used in a proportion of to 60 parts by weight, and
preferably 20 to 55 parts by weight, based on 100 parts by weight
of the sum of amounts of the crystalline polyolefin resin (C2-1)
and the .alpha.-olefin copolymer rubber (C2-2).
[1159] When the crystalline polyolefin resin (C2-1) is used in the
proportion as described above, an olefinic thermoplastic elastomer
composition having excellent rubber elasticity and excellent
molding processability can be obtained.
[1160] [.alpha.-Olefin Copolymer Rubber (C2-2)]
[1161] The .alpha.-olefin polymer rubber (C2-2) used in the present
invention (6) is a rubber obtained by copolymerizing an
.alpha.-olefin having 2 to 20 carbon atoms, and preferably 2 to 12
carbon atoms, and if necessary, a non-conjugated polyene, for
example, a non-conjugated diene.
[1162] Specific examples of the .alpha.-olefin include ethylene,
propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene,
1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,
1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,
1-nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene,
12-ethyl-1-tetradecene and the like.
[1163] According to the present invention (6), the .alpha.-olefins
as described above may be used alone or as a mixture of two or more
species. In the case of using 4-methyl-1-pentene and another
.alpha.-olefin as a mixture, the molar ratio of the another
.alpha.-olefin to 4-methyl-1-pentene (another
.alpha.-olefin/4-methyl-1-pentene) is preferably in the range of
10/90 to 95/5.
[1164] Among the .alpha.-olefins, particularly ethylene, propylene
and 1-butene are preferably used.
[1165] Examples of the .alpha.-olefin copolymer rubber (C2-2)
include a copolymer containing constituent units derived from
ethylene and constituent units derived from an .alpha.-olefin
having 3 or more carbon atoms, wherein the ratio of the constituent
units derived from ethylene and the constituent units derived from
an .alpha.-olefin having 3 or more carbon atoms, ethylene/a-olefin
having 3 or more carbon atoms (molar ratio), is 40/60 to 95/5.
[1166] Furthermore, specific examples of the non-conjugated polyene
used in the present invention (6) as necessary, include
dicyclopentadiene, 1,4-hexadiene, cyclooctadiene,
methylenenorbornene, ethylidenenorbornene 4-methyl-1,4-hexadiene,
5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene,
5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene,
5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene,
5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene,
5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene,
5-ethyl-1,4-octadiene, 5-methyl-1,5-octadiene,
6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene,
6-ethyl-1,5-octadiene, 6-methyl-1,6-octadiene,
7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene,
4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene,
4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene,
5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene,
5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene,
6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene,
6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene,
7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene,
7-ethyl-1,7-nonadiene, 5-methyl-1,4-decadiene,
5-ethyl-1,4-decadiene, 5-methyl-1,5-decadiene,
6-methyl-1,5-decadiene, 5-ethyl-1,5-decadiene,
6-ethyl-1,5-decadiene, 6-methyl-1,6-decadiene,
7-methyl-1,6-decadiene, 6-ethyl-1,6-decadiene,
7-ethyl-1,6-decadiene, 7-methyl-1,7-decadiene,
8-methyl-1,7-decadiene, 7-ethyl-1,7-decadiene,
8-ethyl-1,7-decadiene, 8-methyl-1,8-decadiene,
9-methyl-1,8-decadiene, 8-ethyl-1,8-decadiene,
9-methyl-1,8-undecadiene and the like. Among these,
5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene,
4,8-dimethyl-1,4,8-decatriene (DMDT), and
4-ethylidene-8-methyl-1,7-nonadiene (EMND) in particular are
preferred.
[1167] According to the present invention (6), in the case of using
non-conjugated polyenes as described above, for example,
non-conjugated dienes, they may be used alone or as a mixture of
two or more species. Furthermore, in addition to the non-conjugated
polyenes as described above, other copolymerizable monomers may be
used within the scope of not impairing the purpose of the present
invention (6).
[1168] For the .alpha.-olefin polymer rubber (C2-2), when the
non-conjugated polyene is copolymerized, the content of the
constituent unit derived from the non-conjugated polyene in the
copolymer is in the range of 0.01 to 30 mol %, preferably 0.1 to 20
mol %, and particularly preferably 0.1 to 10 mol % (provided that
the total amount of the constituent unit in this .alpha.-olefin
copolymer rubber (C2-2) is 100 mol %).
[1169] As the .alpha.-olefin copolymer rubber (C2-2), a copolymer
of an .alpha.-olefin and a non-conjugated polyene is preferred. In
particular, there may be preferably mentioned an
ethylene..alpha.-olefin having 3 or more carbon atoms
non-conjugated polyene copolymer, wherein the ratio of ethylene and
the .alpha.-olefin having 3 or more carbon atoms, ethylene/a-olefin
having 3 or more carbon atoms (molar ratio), is 40/60 to 95/5, and
constituent units derived from the non-conjugated polyene is
contained in an amount of 0.01 to 30 mol %.
[1170] The intrinsic viscosity [.eta.] of the .alpha.-olefin
copolymer rubber (C2-2), as measured in a decalin solvent at
135.degree. C., is in the range of 1.0 to 10.0 dl/g, and preferably
1.5 to 7 dl/g. Also, without any particularly limitation, the
melting point of the .alpha.-olefin copolymer rubber (C2-2), as
determined from an endothermic curve of DSC, is preferably either
absent, or present at a temperature below 120.degree. C.
[1171] According to the present invention (6), the .alpha.-olefin
copolymer rubber (C2-2) is used in a proportion of 90 to 40 parts
by weight, and preferably 80 to 45 parts by weight, based on 100
parts by weight of the sum of amounts of the crystalline polyolefin
resin (C2-1) and the .alpha.-olefin copolymer rubber (C2-2).
[1172] The .alpha.-olefin copolymer rubber (C2-2) as described
above can be produced by the following method. The .alpha.-olefin
copolymer rubber (C2-2) can be produced but copolymerizing an
.alpha.-olefin having 2 to 20 carbon atoms, and if necessary, a
non-conjugated diene, in the presence of a catalyst for olefin
polymerization.
[1173] The non-crosslinked or partially crosslinked olefinic
thermoplastic elastomer composition (C2) may contain, in addition
to the crystalline polyolefin resin (C2-1) and the .alpha.-olefin
copolymer rubber (C2-2), a softening agent (C2-3) and/or an
inorganic filler (C2-4) as optional components.
[1174] As the softening agent (C2-3), those softening agents that
are usually used for rubber can be used, and specific examples
thereof include petroleum-based materials such as process oils,
lubricant oils, paraffin, liquid paraffin, petroleum asphalt,
petrolatum and the like; coal tar such as coal tar, coal tar pitch
and the like; fatty oils such as castor oil, linseed oil, rapeseed
oil, soybean oil, palm oil and the like; waxes such as tall oil,
beeswax, carnauba wax, lanoline and the like; fatty acids or metal
salts thereof, such as ricinolic acid, palmitic acid, stearic acid,
barium stearate, calcium stearate and the like; synthetic polymeric
materials such as petroleum resins, coumarone-indene resins,
atactic polypropylene and the like; ester-based plasticizers such
as dioctyl phthalate, dioctyl adipate, dioctyl sebacate and the
like; and microcrystalline waxes, sabu (factice), liquid
polybutadiene, modified liquid polybutadiene, liquid thiocole, and
the like.
[1175] According to the present invention (6), the softening agent
(C2-3) is used in a proportion of usually 200 parts by weight or
less, and preferably 2 to 100 parts by weight, based on 100 parts
by weight of the sum of amounts of the crystalline polyolefin resin
(C2-1) and the .alpha.-olefin copolymer rubber (C2-2).
[1176] As the inorganic filler (C2-4), specifically calcium
carbonate, calcium silicate, clay, kaolin, talc, silica,
diatomaceous earth, mica powder, asbestos, alumina, barium sulfate,
aluminum sulfate, calcium sulfate, basic magnesium carbonate,
molybdenum disulfide, graphite, glass fiber, glass bead, Shirasu
balloon, and the like may be mentioned.
[1177] According to the present invention (6), the inorganic filler
(C2-4) is used in a proportion of usually 100 parts by weight or
less, and preferably 2 to 50 parts by weight, based on 100 parts by
weight of the sum of amounts of the crystalline polyolefin resin
(C2-1) and the .alpha.-olefin copolymer rubber (C2-2). According to
the present invention (6), when the amount of use of the inorganic
filler (C2-4) exceeds 100 parts by weight, rubber elasticity and
molding processability of the resulting thermoplastic elastomer
composition tend to be deteriorated.
[1178] Furthermore, the partially crosslinked olefinic
thermoplastic elastomer composition can be obtained under the
presence of organic peroxide compounds described-below by
dynamically heat treating a mixture of the above-described
crystalline polyolefin resin (C2-1), the .alpha.-olefin copolymer
rubber (C2-2), and the softening agent (C2-3) and/or inorganic
filler (C2-4) which are added as necessary, thus to perform partial
crosslinking.
[1179] The term "dynamically heat treating" as used herein refers
to kneading in a molten state. Specific examples of the organic
peroxide include dicumyl peroxide, di-tert-butyl peroxide,
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3,1,3-bis(tert-butylperoxyis-
opropyl)benzene,
1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,
4-bis(tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl
peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate,
tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl
peroxide, tert-butylcumyl peroxide and the like.
[1180] Such organic peroxide is used in an amount of 0.02 to 3
parts by weight, and preferably 0.05 to 1 parts by weight, based on
100 parts by weight of the entire material to be treated, that is,
the sum of amounts of the crystalline polyolefin resin (C2-1) and
the .alpha.-olefin copolymer rubber (C2-2). When this amount of
mixing is smaller than the above range, the degree of crosslinking
of the resulting thermoplastic elastomer composition is low, and
thus heat resistance, tensile properties, elastic recovery and
rebound resilience and the like are insufficient. Also, when this
amount of mixing is larger than the above range, the resulting
thermoplastic elastomer composition has a degree of crosslinking so
high that moldability may be deteriorated.
[1181] According to the present invention (6), during the partial
crosslinking treatment by the organic peroxide, a peroxy
crosslinking aid such as sulfur, p-quinonedioxime,
p,p'-dibenzoylquinonedioxime, N-methyl-N,N'-m-phenylenedimaleimide
or the like; a polyfunctional methacrylate monomer of
divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate,
polyethylene glycol dimethacrylate, trimethylolpropane
trimethacrylate, acryl methacrylate or the like; or a
polyfunctional vinyl monomer such as vinyl butyrate or vinyl
stearate may be added therein.
[1182] By using a compound as described above, such as a
crosslinking aid, a uniform and mild crosslinking reaction can be
expected. Such compound as crosslinking aid or polyfunctional vinyl
monomer is used in an amount of usually 2 parts by weight or less,
and more preferably 0.3 to 1 parts by weight, based on 100 parts by
weight of the entire material to be treated.
[1183] Furthermore, to promote degradation of the organic peroxide,
a degradation promoting agent such as a tertiary amine such as
triethylamine, tributylamine, 2,4,6-tri(dimethylamino)phenol or the
like, or a naphthenate salt of aluminum, cobalt, vanadium, copper,
calcium, zirconium, manganese, magnesium, lead, mercury or the like
may also be used.
[1184] The dynamic heat treatment in the present invention (6) is
preferably performed in a non-open type apparatus, and preferably
in an atmosphere of inert gas such as nitrogen, carbon dioxide gas
or the like. The temperature is in the range of from the melting
point of the crystalline polyolefin resin (C2-1) to 300.degree. C.,
and usually 150 to 250.degree. C., and preferably 170 to
225.degree. C. The kneading time is usually 1 to 20 minutes, and
preferably 1 to 10 minutes. The applied shear force is, in terms of
the shear rate, 10 to 100,000 sec-1, and preferably 100 to 50,000
sec.sup.-1.
[1185] As the kneading apparatus, a mixing roll, an intensive mixer
(for example, a Banbury mixer, a kneader), a single screw or twin
screw extruder and the like can be used, but a non-open type
apparatus is preferred.
[1186] An olefinic thermoplastic elastomer composition which
comprises the crystalline polyolefin resin (C2-1) and the
.alpha.-olefin copolymer rubber (C2-2), or which is partially
crosslinked, can be obtained by the above-described dynamic heat
treatment.
[1187] According to the present invention (6), the thermoplastic
elastomer composition being partially crosslinked indicates that
the gel content as measured by the method that will be described
later is 20% or greater, preferably in the range of to 99.5%, and
particularly preferably 45 to 98%. Measurement of the gel content
can be performed by weighing 100 mg of a sample of the
thermoplastic elastomer composition, cutting this to small pieces
of 0.5 mm.times.0.5 mm.times.0.5 mm, immersing the sample pieces in
30 ml of cyclohexane in a sealed vessel at 23.degree. C. for 48
hours, subsequently removing the sample pieces on a filter paper,
and drying at room temperature for 72 hours or more until a
constant weight is obtained.
[1188] From this dried residual weight, the weight of all
cyclohexane-insoluble components other than the polymer components
(fiber-shaped filler, filler, pigment, etc.) and the weight of the
crystalline polyolefin resin (C2-1) in the sample prior to
immersion in cyclohexane are subtracted, and the result is
designated as "corrected final weight [y]".
[1189] Meanwhile, the weight of the .alpha.-olefin copolymer (C2-2)
in the sample is designated as "corrected initial weight [x]".
Herein, the gel content is determined by the following
equation.
Gel content [wt %]=(corrected final weight [y]/corrected initial
weight [x]).times.100.
[1190] Propylene-Based Polymer Composition (X3)
[1191] The propylene-based polymer composition (X3) of the present
invention (6) comprises:
[1192] (AA) 10 to 95 parts by weight, preferably 15 to 90 parts by
weight, of the syndiotactic propylene polymer, and
[1193] (B3) 90 to 5 parts by weight, preferably 85 to 10 parts by
weight, of the propylene..alpha.-olefin copolymer (provided that
the sum of amounts of (AA) and (B3) is 100 parts by weight).
[1194] A composition (X3) having the mixing ratio of the
syndiotactic propylene polymer (AA) and the
propylene..alpha.-olefin copolymer within this range has excellent
moldability and heat resistance, as well as excellent flexibility,
scratch resistance and abrasion resistance, which is
preferable.
[1195] As a material having high heat resistance, and excellent
flexibility, abrasion resistance, scratch resistance, damping
properties and tackiness, a propylene polymer composition (X3)
(composition (X3i) comprising:
[1196] (AA) 10 to 95 parts by weight, preferably 15 to 90 parts by
weight, of the syndiotactic propylene polymer,
[1197] (B3) 90 to 5 parts by weight, preferably 85 to 10 parts by
weight, of the propylene..alpha.-olefin copolymer (provided that
the sum of amounts of (AA) and (B3) is 100 parts by weight),
and
[1198] 0.1 to 100 parts by weight in total of one or more resins
(C1) selected from the group consisting of rosin-based resins,
terpene-based resins and petroleum resins) may be preferably
mentioned.
[1199] The one or more resins (C1) selected from the group
consisting of rosin-based resins, terpene-based resins and
petroleum resins is used in an amount of preferably 1 to 90 parts
by weight, more preferably 1 to 80 parts by weight, and even more
preferably 2 to 70 parts by weight. When (C1) is contained within
the above range, the propylene-based polymer composition (X3) has
excellent tackiness. Also, the composition (X3i) can be provided as
a composition having excellent transparency.
[1200] As a material having high heat resistance, as well as
excellent abrasion resistance, scratch resistance and low
temperature impact resistance, a propylene-based polymer
composition (X3) (composition (X3ii) comprising:
[1201] (AA) 10 to 95 parts by weight, preferably 15 to 90 parts by
weight, of the syndiotactic propylene polymer,
[1202] (B3) 90 to 5 parts by weight, preferably 85 to 10 parts by
weight, of the propylene..alpha.-olefin copolymer (provided that
the sum of amounts of (AA) and (B3) is 100 parts by weight),
and
[1203] 0.1 to 500 parts by weight of the non-crosslinked or
crosslinked olefinic thermoplastic elastomer (C2)) may be
preferably mentioned. The content of the elastomer (C2) is more
preferably 1 to 500 parts by weight, and even more preferably 50 to
400 parts by weight.
[1204] The composition of the present invention (6) can be provided
as a material having particularly excellent moldability and heat
resistance, as well as excellent flexibility, scratch resistance
and abrasion resistance.
[1205] Herein, moldability being excellent indicates that in the
case of carrying out molding such as injection molding, inflation
molding, blow molding, extrusion, foam or press molding, the time
taken from the molten state to the solid state is short. In the
case of moldability being excellent, molding cycle properties,
shape stability, long-term productivity and the like are also
excellent.
[1206] Specifically, the time to solidification is such that the
half-crystallization time (t.sub.1/2) during the isothermal
crystallization measurement at 110.degree. C. as determined by
differential scanning calorimetry (DSC) is in the range of 1000 sec
or less, and more preferably 500 sec or less. Also, the
half-crystallization time (t.sub.1/2) determined from the
isothermal crystallization measurement at 110.degree. C. as
determined by differential scanning calorimetry (DSC) may be
referred to as property (1). The composition of the present
invention (6) has remarkably improved t.sub.1/2, compared to prior
art, by containing specific components (AA) and (B3), and for
example, can be molded without difficulties by generally used
molding methods for isotactic polypropylene.
[1207] The half-crystallization time (t.sub.1/2) determined by
isothermal crystallization measurement is, when the area between
the DSC caloric curve and the baseline during the isothermal
crystallization process is considered as the total calories, the
time taken to reach 50% of the calories. For details, refer to
technical literatures such as New Lectures on Polymer Experiments,
8. Properties of Polymers (Shin-koubunsizikkenkouza 8 Koubunsi no
Bussei) (KYORITSU SHUPPAN CO., LTD.)].
[1208] Measurement of the half-crystallization time (t.sub.1/2) is
performed as follows. About 5.00 mg of a sample is filled in an
aluminum pan for exclusive use, and the half-crystallization time
is determined from a DSC curve obtained by heating the sample from
30.degree. C. to 200.degree. C. at a rate of 320.degree. C./min,
maintaining at 200.degree. C. for 5 minutes, cooling from that
temperature (200.degree. C.) to the isothermal crystallization
temperature of 110.degree. C. at a rate of 320.degree. C./min, and
maintaining the temperature at 110.degree. C., using DSCPyris1 or
DSC7 manufactured by PerkinElmer, Inc. Here, the
half-crystallization time (t.sub.1/2) is determined by setting the
initial time of the isothermal crystallization process (the time to
reach the isothermal crystallization temperature of 110.degree. C.
from 200.degree. C.) as t=0. For the composition of the present
invention (6), t.sub.1/2 can be determined as described above, but
when crystallization does not occur at any isothermal
crystallization temperature, for example, at 110.degree. C., then
measurement is taken for convenience at several points at an
isothermal crystallization temperature at or below 110.degree. C.,
and the half crystallization time (t.sub.1/2) is determined from
the extrapolated value.
[1209] The propylene polymer composition (X3) of the present
invention (6) preferably satisfies any one of the following (1) and
(2), and it is more preferable that (1) and (2) are respectively in
their preferred ranges.
[1210] (1) The half-crystallization time (t.sub.1/2) is preferably
1000 sec or shorter, and more preferably 500 sec or shorter.
[1211] (2) The softening temperature measured by TMA is preferably
110.degree. C. or higher, more preferably 120.degree. C. or higher,
and particularly preferably 130.degree. C. or higher.
[1212] The composition (X3i) which is a preferred embodiment of the
present invention (6), preferably satisfies at least one of the
following (i-1) to (i-3); more preferably either satisfies (i-1)
and (i-3), or satisfies (i-2) and (i-3); and even more preferably
satisfies all of (i-1) to (i-3).
[1213] (i-1) The half-crystallization time (t.sub.1/2) is
preferably 1000 sec or shorter, and more preferably 500 sec or
shorter.
[1214] (i-2) The softening temperature measured by TMA is
preferably 110.degree. C. or higher, more preferably 120.degree. C.
or higher, and particularly preferably 130.degree. C. or
higher.
[1215] (i-3) The modulus of rebound resilience measured according
to JIS K6255 is preferably 40% or less, more preferably 35% or
less, and even more preferably 30% or less.
[1216] The composition (X3i) more preferably also satisfies the
following (i-7).
[1217] (i-7) The internal haze is preferably 50% or less, and more
preferably 30% or less.
[1218] The composition (X3i) particularly preferably satisfies the
following (i-6).
[1219] (i-6) The tensile modulus is in the range of 1 MPa to 1000
MPa, preferably 1 to 800 MPa, more preferably 10 MPa to 500
MPa.
[1220] The composition (X3ii), which is a preferred embodiment of
the present invention (6), preferably satisfies one or more of the
following (ii-1), (ii-2), (ii-4) and (ii-5); more preferably either
satisfies (ii-1) and (ii-5), or satisfies (ii-2) and (ii-5); even
more preferably either satisfies (ii-1), (ii-5) and (ii-4), or
satisfies (ii-2), (ii-5) and (ii-4); and still more preferably
satisfies all of (ii-1), (ii-2), (ii-4) and (ii-5).
[1221] (ii-1) The half-crystallization time (t.sub.1/2) is
preferably 1000 sec or shorter, and more preferably 500 sec or
shorter.
[1222] (ii-2) The softening temperature measured by TMA is
preferably 145.degree. C. or higher, and more preferably
147.degree. C.
[1223] (ii-4) The Izod impact strength is preferably 50 J/m or
greater, and more preferably 100 J/m.
[1224] (ii-5) The gross rate of change before and after Gakushin
abrasion test is preferably 40(%) or less, and more preferably (%)
or less.
[1225] Also, the composition (X3ii) of the present invention (6)
more preferably satisfies the following (ii-6).
[1226] (ii-6) The tensile modulus is in the range of preferably 1
MPa to 1000 MPa, more preferably in the range of 1 MPa to 500 MPa,
and even more preferably in the range of 1 MPa to 200 MPa.
[1227] The softening temperature (property (2), or may also be
referred to as the needle penetration temperature) measured by TMA
can be measured as follows.
[1228] Using SS-120 manufactured by Seiko Co., Ltd. or Q-400
manufactured by TA Instrument, and using a specimen of press sheet
having a thickness of 1 mm, a pressure of 2 kgf/cm.sup.2 is applied
with a planar indentor of 1.8 mm.phi. at a rate of temperature
increase of 5.degree. C./min, and the needle penetration
temperature (.degree. C.) is determined from the TMA curve.
[1229] Furthermore, measurement methods for the modulus of rebound
resilience (may be referred to as property (3)), the Izod impact
strength (may be referred to as property (4)), the gross rate of
change (may be referred to as property (5)), the tensile modulus
(may be referred to as property (6)), and the haze (may be referred
to as property (7)) will be described below.
[1230] (3) Modulus of Rebound Resilience
[1231] The modulus of rebound resilience measured according to JIS
K6255 is preferably 40% or less, more preferably 35% or less, and
particularly preferably 30% or less.
[1232] (4) Izod Impact Strength
[1233] A specimen of 12.7 mm (width).times.3.2 mm
(thickness).times.64 mm (length) is punched from a press sheet
having a thickness of 3 mm, a notch is inserted by machine
processing, and the Izod impact strength is measured at 0.degree.
C. An average of three measurements was taken as the value.
[1234] (5) Gross Rate of Change
[1235] The gross rate of change before and after a JSPS type
abrasion test is preferably 40(%) or less, and more preferably (%)
or less.
[1236] (6) Tensile Modulus
[1237] A press sheet having a thickness of 1 mm is punched for No.
JIS3 dumbbell according to JIS K6301, and the specimen is provided
as evaluation sample. The measurement is performed, for example, by
measuring the tensile modulus using a tensile tester Inston 1123
manufactured by Instron, Inc. at a span interval of 30 mm and a
tensile rate of 30 mm/min at 23.degree. C., and an average value of
three measurements is determined.
[1238] (7) Haze
[1239] The internal haze is measured using a press sheet specimen
having a thickness of 1 mm, and using a digital hazemeter "NDH-20D"
manufactured by Nippon Denshoku Industries Co., Ltd. An average
value of two measurements is determined.
[1240] Also, for the description above, in the respective tests,
specimens were obtained by producing a sheet having a predetermined
thickness by pre-heating the sample at 200.degree. C. for 5 minutes
to 10 minutes in a press molding machine, subsequently molding the
sheet for 1 to 2 minutes under a pressure of 10 MPa, and then
cooling the sheet at 20.degree. C. under a pressure of 10 MPa.
[1241] Graft Modification
[1242] In the propylene-based polymer composition (X3) of the
present invention (6), at least a part or the entirety may be graft
modified with a polar monomer.
[1243] For example, a part or all of the component (AA) may be
graft modified, a part or all of the component (B3) may be graft
modified, and a part or all of each of the component (AA) and
component (B3) may be graft modified.
[1244] This polar monomer may be exemplified by a hydroxyl
group-containing ethylenic unsaturated compound, an amino
group-containing ethylenic unsaturated compound, an epoxy
group-containing ethylenic unsaturated compound, an aromatic vinyl
compound, an unsaturated carboxylic acid or a derivative thereof, a
vinyl ester compound, vinyl chloride, a carbodiimide compound, or
the like.
[1245] As the polar monomer, in particular, the unsaturated
carboxylic acid or its derivatives are particularly preferred. As
the unsaturated carboxylic acid or its derivatives, an unsaturated
compound having at least one carboxylic acid group, an ester of a
compound having a carboxylic acid group and an alkyl alcohol, an
unsaturated compound having at least one anhydrous carboxylic acid
group, or the like, and as the unsaturated group, a vinyl group, a
vinylene group, an unsaturated cyclic hydrocarbon group, or the
like.
[1246] Specific examples of the compound include unsaturated
carboxylic acids such as acrylic acid, maleic acid, fumaric acid,
tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic
acid, isocrotonic acid, Nadic acid [trade
name](endocis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid) and
the like; or derivatives thereof, for example, acid halides,
amides, imides, anhydrides, esters and the like. Specific examples
of these derivatives include, for example, malenyl chloride,
maleimide, maleic anhydride, citraconic anhydride, monomethyl
maleate, dimethyl maleate, glycidyl maleate and the like.
[1247] These unsaturated carboxylic acids and/or derivatives
thereof may be used individually or in combination of two or more
species. Among these, an unsaturated dicarboxylic acid or an acid
anhydride thereof is suitable, and particularly maleic acid, Nadic
acid or acid anhydrides thereof are preferably used.
[1248] Modification can be obtained by graft polymerizing a polar
monomer to a product to be modified. When graft polymerizing such
polar monomer to the product to be modified, the polar monomer is
usually used in an amount of 1 to 100 parts by weight, preferably 5
to 80 parts by weight, based on 100 parts by weight of the product
to be modified. This graft polymerization is generally performed in
the presence of a radical initiator.
[1249] As the radical initiator, an organic peroxide, an azo
compound or the like may be used.
[1250] The radical initiator can be used after directly mixing with
the product to be modified and the polar monomer, but may be used
after dissolving the initiator in a small amount of an organic
solvent. This organic solvent is not particularly limited for use,
as long as it is an organic solvent which can dissolve the radical
initiator.
[1251] Also, upon graft polymerizing a polar monomer to the product
to be modified, a reducing substance can be used. If a reducing
substance is used, the amount of the polar monomer to be grafted
can be enhanced.
[1252] Graft modification of the product to be modified with a
polar monomer can be performed by a conventionally known method,
and for example, can be performed by dissolving the product to be
modified in an organic solvent, subsequently adding a polar
monomer, a radical initiator and the like to the solution, and
allowing the mixture to react at a temperature of 70 to 200.degree.
C., and preferably 80 to 190.degree. C., for 0.5 to 15 hours, and
preferably 1 to 10 hours.
[1253] Also, a modified propylene-based polymer composition can be
produced by reacting the product to be modified with a polar
monomer, using an extruder or the like. This reaction is preferably
performed at a temperature usually above the melting point of the
product to be modified, specifically in the case of modifying the
component (B3), at a temperature of 120 to 300.degree. C., and
preferably 120 to 250.degree. C., usually for 0.5 to 10 minutes.
Also, in the case of modifying a product to be modified containing
the component (AA), for example, the reaction is preferably
performed at a temperature of 160 to 300.degree. C., and preferably
180.degree. C. to 250.degree. C., usually for 0.5 to 10
minutes.
[1254] The amount of modification of the modified product thus
obtained (amount of the polar monomer to be grafted) is usually 0.1
to 50 wt %, preferably 0.2 to 30 wt %, and more preferably 0.2 to
10 wt %, when the modified product is taken as 100 wt %.
[1255] In the present invention (6), a propylene-based polymer
composition (X3) of the present invention (6), which is at least
partially graft modified, can be obtained by using these modified
products, and kneading, if necessary, the products with one or more
unmodified products selected from the component (AA) and component
(B3).
[1256] Furthermore, the content of the polar monomer relative to
100 wt % of the propylene-based polymer composition (X3) having at
least partially graft modified by the polar monomer is usually
0.001 to 50 wt %, preferably 0.001 to 10 wt %, more preferably
0.001 to 5 wt %, and even more preferably 0.01 to 3 wt %. Control
of the content of the polar monomer can be easily performed, for
example, by appropriately selecting the grafting conditions.
[1257] When the propylene-based polymer composition (X3) of the
present invention (6) is at least partially graft modified by a
polar monomer, the composition has excellent adhesiveness to other
resins and excellent compatibility, and also, the surface
wettability of the molded product obtained from the propylene-based
polymer composition may be improved.
[1258] Also, by at least partially graft modifying the composition,
compatibility with other materials or adhesiveness may be added,
while maintaining the performance of the propylene-based polymer
composition (X3) of the present invention (6), such as low
temperature impact resistance, mechanical properties (rigidity or
flexibility), heat resistance, and the like.
[1259] When the content of the polar monomer, for example, an
unsaturated carboxylic acid and/or a derivative thereof, is within
in the mentioned range, the polyolefine composition (X3) of the
present invention (6) shows high adhesive strength to polar
group-containing resins (for example, polyesters, polyvinyl
alcohols, ethylene-vinyl alcohol copolymers, polyamides, PMMA,
polycarbonates, etc.).
[1260] The at least partially graft modified propylene-based
polymer composition (X3) of the present invention (6) may have
added other polymers, for example, thermoplastic resins or
elastomers, within the scope of not impairing the properties
possessed by the modified product. Such addition may be carried out
by mixing during the graft modification step, or after
modification.
[1261] The propylene-based polymer composition (X3) of the present
invention (6) may have incorporated, within the scope of not
impairing the purpose of the present invention, additives such as a
weather resistant stabilizer, a heat resistant stabilizer, an
antistatic agent, an anti-slipping agent, an anti-blocking agent,
an anti-fogging agent, a nucleating agent, a lubricating agent, a
dye, a pigment, a plasticizer, an anti-aging agent, a hydrochloric
acid absorbent, an antioxidant, and the like.
[1262] The propylene-based polymer composition (X3) of the present
invention (6) may contain polyethylene, isotactic polypropylene or
styrene-based elastomers, but a composition not containing
polyethylene, isotactic polypropylene or styrene-based elastomers
is also an embodiment.
[1263] Also, the propylene-based polymer composition (X3) of the
present invention (6) may contain a nucleating agent, which is a
specific arbitrary component, in order to improve the moldability,
that is, to increase the crystallization temperature and increase
the rate of crystallization. In this case, for example, the
nucleating agent is a dibenzylidene sorbitol-based nucleating
agent, phosphoric acid ester-based nucleating agent, a rosin-based
nucleating agent, a benzoic acid metal salt-based nucleating agent,
a fluorinated polyethylene, sodium
2,2-methylenebis(4,6-di-tert-butylphenyl)phosphate, pimellic acid
or a salt thereof, 2,6-naphthalenic acid dicarboxylic acid
dicyclohexylamide, or the like. The amount of mixing is not
particularly limited, but the amount is preferably about 0.1 to 1
part by weight based on 100 parts by weight of the propylene based
polymer composition. The timing for mixing is not particularly
limited, and addition is possible during or after polymerization,
or during the molding process.
[1264] Method for Producing Propylene-Based Polymer Composition
(X3)
[1265] The propylene-based polymer composition (X3) as described
above can be produced by various methods that are known in the
scope described above, for example, by multi-stage polymerizing the
respective components in the continuous mode or batch mode in a
slurry phase, solution phase or gas phase, by mixing the respective
components in a Henschel mixer, a V-blender, a ribbon blender, a
tumbler blender or the like, or by melt kneading the respective
components in a single screw extruder, a twin screw extruder, a
kneader, a Bunbury mixer or the like, and then granulating or
grinding.
[1266] Molded Products Formed Using Propylene-Based Polymer
Composition of the Present Inventions (4), (5) or (6)
[1267] The propylene-based polymer composition of the present
invention (4) as described above, and the propylene-based polymer
composition of the invention present (5) as described above have
excellent moldability and heat resistance, and molded products
having excellent flexibility, transparency and scratch resistance
can be obtained. On the other hand, the propylene-based polymer
composition of the present invention (6) as described above has
excellent moldability and heat resistance, and molded products
having excellent flexibility, scratch resistance, damping
properties and low temperature impact properties can be obtained.
Thus, it was practically difficult to use conventional syndiotactic
polypropylene. Being widely used in polyolefin applications,
particularly, the propylene-based polymer composition of the
present invention (4), the propylene-based polymer composition of
the invention present (5) or the propylene-based polymer
composition of the present invention (6) (hereinafter, they may be
collectively referred to as "propylene-based polymer composition
(X)") in particular can be molded into, for example, sheets,
unstretched or stretched films, filaments, and other molded
products of various shapes. Furthermore, the molded products formed
using the propylene-based polymer composition (X) may have the
propylene-based polymer composition (X) partially contained in the
molded products, that is, the propylene-based polymer composition
(X) may be used in parts of the molded products, and also the
propylene-based polymer composition (X) may be used in the entirety
of the molded products. As an example of using the propylene-based
polymer composition (X) in parts of a molded product, a multilayer
laminate may be mentioned. The multilayer laminate may be
specifically a laminate in which at least one layer is a layer
comprising the propylene-based polymer composition (X), and
multilayer films and sheets, multilayer containers, multilayer
tubes, multilayer film laminate contained in aqueous coating
materials as one constituent component, and the like may be
mentioned.
[1268] As the molded products, specifically those molded products
can be obtained by known thermal molding methods such as extrusion
molding, injection molding, inflation molding, blow molding,
extrusion blow molding, injection blow molding, press molding,
vacuum molding, calender molding, expansion molding, powder slash
molding, and the like. Hereinafter, various examples of molded
products will be described.
[1269] In the case where the molded product of the present
invention is, for example, an extrusion molded product, the shape
and the product type are not particularly limited, but for example,
sheets, films (unstretched), pipes, hoses, wire coatings, tubes and
the like may be mentioned, and particularly sheets (skin
materials), films, tubes, catheters, monofilaments (non-woven
fabrics) and the like are preferable.
[1270] Upon extrusion molding the propylene-based polymer
composition (X), conventionally known extrusion apparatuses and
molding conditions may be employed, and for example, using a single
screw extruder, a kneading extruder, a ram extruder, a gear
extruder and the like, a desired shape can be molded by extruding a
molten propylene-based composition through a certain die or the
like.
[1271] A stretched film can be obtained by stretching an extruded
sheet or extruded film (unstretched) as described above by a known
stretching method such as, for example, a tentering method
(longitudinal transverse stretching, transverse longitudinal
stretching), a simultaneous biaxial stretching method, a uniaxial
stretching method or the like.
[1272] The draw ratio employed during stretching a sheet or an
unstretched film is typically about 20 to 70 times in the case of
biaxial stretching, and typically about 2 to 10 times in the case
of uniaxial stretching. It is preferable to obtain a stretched film
having a thickness of about 5 to 200 .mu.m by stretching.
[1273] An inflation film can be also produced as a film-shaped
molded product. Drawdown is unlikely to occur during the process of
inflation molding.
[1274] The sheet and film molded products formed using the
propylene-based polymer composition (X) are not likely to be
statically charged, and are excellent in mechanical properties,
heat resistance, resilience, impact resistance, aging resistance,
transparency, visibility, gloss, rigidity, moisture-proof
properties and gas barrier properties. The products can be widely
used as packaging films and the like.
[1275] In this case, the sheet and film molded products formed
using the propylene-based polymer composition (X) may be multilayer
molded products, and may be used as multilayer laminates containing
the propylene-based polymer composition (X) in at least one
layer.
[1276] A filament molded product can be produced by, for example,
extruding the molten propylene based polymer composition (X)
through a spinneret. Specifically, a spun-bonding method or a melt
blown method is suitably used. A filament thus obtained may be
further stretched. This stretching may be performed so that the
molecules become oriented in at least one axial direction of the
filament, and it is usually desirable to perform stretching at a
draw ratio of about 5 to 10 times. The filament obtained from the
propylene based polymer composition (X) according to the present
invention is hardly charged, and is excellent in transparency,
rigidity, thermal resistance, impact resistance and resilience.
[1277] An injection molded product can be produced by injection
molding the propylene-based polymer composition (X) into various
shapes using conventionally known injection molding apparatuses and
employing known conditions. The injection molded product obtained
using the propylene-based polymer composition (X) is not likely to
be statically charged, is excellent in transparency, rigidity,
thermal resistance, impact resistance, surface gloss, chemical
resistance, abrasion resistance and the like, and can be used
widely as a trimming material for automobile interior decoration, a
material for automobile exterior decoration, housing for household
electric appliances, containers, and the like.
[1278] A blow molded product can be produced by blow molding the
propylene-based polymer composition (X) by using conventionally
known blow molding apparatuses and employing known conditions. In
this case, the blow molded product formed from the propylene-based
polymer composition (X) may be a multilayer molded product, and
contains the propylene-based polymer composition (X) in at least
one layer.
[1279] For example, in extrusion blow molding, the propylene-based
polymer composition (X) is extruded from a die in a molten state at
a resin temperature of 100 to 300.degree. C. to form a tube-shaped
parison. Then, after retaining the parison in a mold of a desired
shape, air is blown in to make the parison fit the mold at a resin
temperature of 130 to 300.degree. C., and thereby a hollow molded
product can be produced. It is desirable that the draw (blow) ratio
is about 1.5 to 5 times in the transverse direction.
[1280] In injection blow molding, the propylene-based polymer
composition (X) is injected into a parison-mold at a resin
temperature of 100.degree. C. to 300.degree. C. After retaining the
parison in a mold of the desired shape, air is blown in to make the
parison fit the mold at a resin temperature of 120.degree. C. to
300.degree. C., and thereby a hollow molded product can be
produced. In obtaining the hollow molded product, it is desirable
that the draw (blow) ratio is 1.1 to 1.8 times in the longitudinal
direction and 1.3 to 2.5 times in the transverse direction.
[1281] Blow molded products obtained from the propylene-based
polymer composition (X) has excellent transparency, rigidity,
flexibility, thermal resistance and impact resistance, and is also
excellent in moisture-proof properties.
[1282] As a press molded product, mold stamping molded products may
be mentioned. For example, when a base material and a skin material
are simultaneously press molded to perform composite integration
molding (mold stamping molding) of the two materials, the base
material can be formed from the propylene-based polymer composition
(X).
[1283] Specific examples of such mold stamping molded product
include the materials for automobile interior decoration, such as
door trims, rear package trims, seat back garnishes, instrument
panels, and the like.
[1284] Press molded products formed using the propylene-based
polymer composition (X) are not likely to be statically charged,
and are excellent in flexibility, thermal resistance, transparency,
impact resistance, aging resistance, surface gloss, chemical
resistance, abrasion resistance and the like.
[1285] Expanded molded products formed using the propylene-based
polymer composition (X) can be obtained at high expansion ratios,
and also have good injection moldability, as well as high rigidity
and material strength.
[1286] The propylene-based polymer composition (X) can be produced
into vacuum molded products such as interior decoration skin
materials for automobile instrument panels, door trims and the
like. The molded products are not likely to be statically charged,
and are excellent in flexibility, heat resistance, impact
resistance, aging resistance, surface gloss, chemical resistance,
abrasion resistance and the like.
[1287] The propylene-based polymer composition (X) can be produced
into powder slash molded products such as automobile parts,
electric appliance parts, toys, miscellaneous goods and the like
can be produced. The molded products are not likely to be
statically charged, and are excellent in flexibility, heat
resistance, impact resistance, aging resistance, surface gloss,
chemical resistance, abrasion resistance and the like.
[1288] Also, as the molded product of the present invention, a
laminate having at least one layer of a layer comprising the
propylene-based polymer composition (X) may be mentioned.
[1289] The propylene-based polymer composition (X) of the present
invention is appropriate in, for example, containers or non-woven
fabrics. Such container may be exemplified by food containers such
as freeze storage containers, retort pouches and the like, bottle
containers and the like. Also, medical containers, infusion bags
and the like may also be mentioned.
[1290] As described above, the propylene-based polymer composition
(X) can be widely used in applications such as, for example,
infusion bags, medical containers, automobile interior and exterior
decorating materials, beverage bottles, apparel cases, food
packaging materials, retort containers, PET replacements, pipes,
transparent substrates, transparent sealants, porous films, masking
films, films for condenser, laminates (including glass), expanded
products, reflective films, dicing films, wire cables,
soundproofing materials, damping materials, expanded materials,
construction materials, automobile skin materials, solar cell
sealing materials, radiation resistant films, .gamma.-ray resistant
films, flowmark modifiers, non-woven fabrics, modified materials,
shape memory materials, films for composite glass, bulletproof
materials, bulletproof glass films, protective films, adhesives,
compatibilized materials (for example, may be graft modified),
shrinkable films and the like.
[1291] The polypropylene-based resin film of the present invention
(7) (usually refers to a polypropylene-based resin monolayer film;
the term `monolayer` does not exclude the case where a layer other
than the polypropylene film is laminated) is a polypropylene-based
resin film simultaneously satisfying the following requirements (1)
to (3), preferably at least one requirement selected from the
requirements (4) to (7) in addition to the requirements (1) to (3),
and more preferably all of the requirements (4) to (7) in addition
to the requirements (1) to (3).
[1292] The thickness of the polypropylene-based resin film of the
present invention (7) is in the range of 10 to 500 .mu.m,
preferably 100 to 400 .mu.m, and more preferably-100 to 300 .mu.m.
Within the above range, the polypropylene-based resin film
simultaneously satisfying the requirements (1) to (3) can be stably
molded.
[1293] <Requirement (1)>
[1294] Young's modulus of the polypropylene-based resin film of the
present invention (7) is in the range of 10 to 500 MPa, preferably
50 to 400 MPa, as measured according to JIS K6781. When the Young's
modulus falls outside this range, flexibility may not be maintained
after the retort treatment (hot water sterilization treatment under
pressure).
[1295] <Requirement (2)>
[1296] Tensile impact strength of the polypropylene-based resin
film of the present invention (7) measured at 0.degree. C. is in
the range of 50 to 1,000 kJ/m.sup.2, preferably 100 to 1,000
kJ/m.sup.2. When the tensile impact strength is less than 50
kJ/m.sup.2, leak of contents from a container made from the
polypropylene-based resin film filled with food or medicine may be
caused when the container stored at low temperature is dropped.
[1297] <Requirement (3)>
[1298] Light transmittance of the polypropylene-based resin film of
the present invention (7) is in the range of 85 to 99%, preferably
85 to 95%, and the rate of decrease in light transmittance after
hot water treatment at 120.degree. C. for 30 minutes is less than
15%, preferably less than 10%. When the light transmittance is less
than 80%, visual identification of the content from outside the
container may be difficult depending on the content. Meanwhile,
when the light transmittance is more than 95%, it is practically
difficult to produce the polypropylene-based resin film of the
present invention which simultaneously satisfies all of the
requirements other than the present requirement. When the rate of
decrease in light transmittance after the hot water treatment is
15% or more, transparency significantly deteriorates by a
sterilization treatment at high temperature of 121.degree. C.
Herein, `light transmittance` can be measured according to the
method described in Examples that will be described later. Also,
`rate of decrease in light transmittance` is a value calculated
from the following equation.
( Rate of decrease in Light Transmittance ) = ( light transmittance
before hot water treatment ) - ( light transmittance after hot
water treatment ) ( light transmittance before hot water treatment
) .times. 100 ##EQU00001##
[1299] <Requirement (4)>
[1300] Tm of the polypropylene-based resin film of the present
invention (7) as measured by differential scanning calorimetry
(DSC) is preferably 145.degree. C. or higher, more preferably 145
to 170.degree. C., even more preferably 150 to 170.degree. C., and
particularly preferably 154 to 170.degree. C. Within this range,
excellent heat resistance can be exhibited.
[1301] <Requirement (5)>
[1302] The polypropylene-based resin constituting the
polypropylene-based resin film of the present invention (7) is
preferably a polypropylene-based resin composition formed from a
syndiotactic polypropylene polymer (7A), a propylene..alpha.-olefin
copolymer (7B), and if necessary, an ethylene..alpha.-olefin
copolymer (7C). Hereinbelow, each component will be described in
detail.
[1303] <Syndiotactic Propylene Polymer (7A)>
[1304] The syndiotactic propylene polymer (7A) of the present
invention (7) may be a homopolypropylene or may be a random
copolymer of propylene and an .alpha.-olefin having 2 to 20 carbon
atoms (excluding propylene), or may be a propylene block copolymer,
as long as it is a propylene polymer having the properties
described below. However, the polymer is preferably a
homopolypropylene or a random copolymer of propylene and an
.alpha.-olefin having 2 to 20 carbon atoms, and particularly
preferably a copolymer of propylene with ethylene or an
.alpha.-olefin having 4 to 10 carbon atoms, or a copolymer of
propylene with ethylene and an .alpha.-olefin having 4 to 10 carbon
atoms, while homopolypropylene is particularly preferable from the
viewpoint of heat resistance or the like.
[1305] Herein, the .alpha.-olefins having 2 to 20 carbon atoms
other than propylene include ethylene, 1-butene, 1-pentene,
1-hexene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene,
1-eicosene, and the like. The propylene units are generally
contained in an amount of more than 90 mol %, preferably 91 mol %
or more, based on 100 mol % of the sum of amounts of units of the
.alpha.-olefins having 2 to 20 carbon atoms (including propylene).
That is, the syndiotactic propylene polymer (7A) of the present
invention generally contains propylene units in an amount of more
than 90 mol % to 100 mol %, and units of .alpha.-olefin having 2 to
20 carbon atoms (excluding propylene) in an amount of 0 to less
than 10 mol % (provided that the sum of amounts of the propylene
units and the units of .alpha.-olefin having 2 to 20 carbon atoms
(excluding propylene) is 100 mol %), and particularly preferably
contains propylene units in an amount of 91 mol % to 100 mol % and
units of .alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene) in an amount of 0 to 9 mol %.
[1306] When the syndiotactic propylene polymer (7A) is a
propylene..alpha.-olefin random copolymer, units of .alpha.-olefin
having 2 to 20 carbon atoms (excluding propylene) are contained in
an amount of 0.3 to 7 mol %, preferably 0.3 to 6 mol %, and more
preferably 0.3 to 5 mol %.
[1307] The syndiotactic pentad fraction (rrrr fraction, pentad
syndiotacticity) of the syndiotactic propylene polymer (7A) used in
the present invention (7), as measured by NMR, is 85% or more,
preferably 90% or more, more preferably 93% or more, and even more
preferably 94% or more. The syndiotactic propylene polymer (7A)
having an rrrr fraction in this range is preferable from the
viewpoint of having excellent moldability, heat resistance, and
transparency, and having good properties as crystalline
polypropylene. There is no particular upper limit of the rrrr
fraction, but it is 100% or less, and usually 99% or less, for
example.
[1308] This syndiotactic pentad fraction (rrrr fraction) is
measured as follows.
[1309] The rrrr fraction is determined from the absorption
intensities of Prrrr (the absorption intensity resulting from the
methyl group of the third unit at a site where five propylene units
are sequentially syndiotactically bonded) and Pw (the absorption
intensity resulting from all the methyl groups of propylene units)
in the .sup.13C-NMR spectrum according to the following equation
(1):
rrrr fraction (%)=100.times.Prrrr/Pw (1)
[1310] The NMR measurement is performed, for example, as follows.
Specifically, 0.35 g of a sample is dissolved under heating in 2.0
ml of hexachlorobutadiene. This solution is filtered through a
glass filter (G2), and then is introduced into an NMR tube having
an internal diameter of 10 mm after addition of 0.5 ml of
deuterated benzene. Then, .sup.13C-NMR measurement is performed at
120.degree. C. using a GX-500 NMR measuring apparatus manufactured
by JEOL, Ltd. The number of scans is 10,000 or more.
[1311] The intrinsic viscosity [.eta.] of the syndiotactic
propylene polymer (7A) as measured in decalin at 135.degree. C. is
0.1 to 10 dL/g, preferably 0.5 to 10 dL/g, more preferably 0.50 to
8.00 dL/g, even more preferably 0.95 to 8.00 dL/g, particularly
preferably in the range of 1.00 to 8.00, more preferably in the
range of 1.40 to 8.00 dL/g, and particularly preferably in the
range of 1.40 to 5.00 dL/g. The syndiotactic propylene polymer (7A)
having such intrinsic viscosity ([.eta.] value exhibits good
flowability and good miscibility with other components, and the
obtainable composition tends to yield molded products having
excellent mechanical strength.
[1312] Furthermore, the melting point (Tm) of the syndiotactic
propylene polymer (7A) that is measured by differential scanning
calorimetry (DSC) is 145.degree. C. or higher, preferably
147.degree. C. or higher, more preferably 150.degree. C. or higher,
even more preferably 155.degree. C. or higher, and particularly
preferably 156.degree. C. or higher. Although there is no
particular upper limit of Tm, it is usually 170.degree. C. or
lower, for example.
[1313] Moreover, the heat of fusion (.DELTA.H) of the syndiotactic
propylene polymer (7A) is 40 mJ/mg or higher, preferably 45 mJ/mg
or higher, more preferably 50 mJ/mg or higher, even more preferably
52 mJ/mg or higher, and particularly preferably 55 mJ/mg or
higher.
[1314] The differential scanning calorimetry is performed, for
example, in the following manner. About 5.00 mg of a sample is
placed in an aluminum pan for exclusive use, and the melting point
(Tin) and the heat of fusion (.DELTA.H) are determined from an
endothermic curve obtained by heating the sample from 30.degree. C.
to 200.degree. C. at a rate of 320.degree. C./min, holding the
sample at 200.degree. C. for 5 minutes, cooling the sample from
200.degree. C. to 30.degree. C. at a rate of 10.degree. C./min,
allowing the sample to stand at 30.degree. C. for 5 minutes, and
heating the sample again at a rate of 10.degree. C./min, using DSC
Pyris 1 or DSC7 manufactured by PerkinElmer, Inc. If a plurality of
peaks is detected during the DSC measurement, the peak detected at
the highest temperature is defined as the melting point (Tm).
[1315] The syndiotactic propylene polymer (7A) having the melting
point (Tm) in this range has excellent moldability, heat
resistance, and mechanical properties, and has good properties as a
crystalline polypropylene. By controlling the polymerization
conditions as will be described later and by using the catalyst
system that will be described later, the syndiotactic propylene
polymer (7A) having the melting point (Tm) within this range can be
produced.
[1316] The syndiotactic propylene polymer (7A) satisfies, when the
isothermal crystallization temperature determined by differential
scanning calorimetry (DSC) is designated as T.sub.iso and the
half-crystallization time at the isothermal crystallization
temperature T.sub.iso is designated as t.sub.1/2, the following
Equation (Eq-1) in the range of 110.ltoreq.T.sub.iso.ltoreq.150
(.degree. C.):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.5.-
56.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-1)
[1317] preferably satisfies the following equation (Eq-2):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.3.-
71.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-2)
[1318] and more preferably satisfies the following equation
(Eq-3):
1.67.times.10.sup.-4exp(0.10.times.T.sub.iso).ltoreq.t.sub.1/2.ltoreq.2.-
23.times.10.sup.-4exp(0.12.times.T.sub.iso) (Eq-3)
[1319] The half-crystallization time (t.sub.1/2) determined by
isothermal crystallization measurement is, when the area between
the DSC caloric curve and the baseline in the course of the
isothermal crystallization process is considered as the total
calories, the time taken to reach 50% of the calories [see New
Lectures on Polymer Experiments, 8. Properties of Polymers
(KYORITSU SHUPPAN CO., LTD.)].
[1320] Measurement of the half-crystallization time (t.sub.1/2) is
performed as follows. About 5 mg of a sample is placed in an
aluminum pan for exclusive use, and the half-crystallization time
(t.sub.1/2) is determined from a DSC curve obtained by heating the
sample from 30.degree. C. to 200.degree. C. at a rate of
320.degree. C./min, holding the sample at 200.degree. C. for 5
minutes, cooling the sample from that temperature (200.degree. C.)
to the isothermal crystallization temperature at a rate of
320.degree. C./min, and allowing the sample to stand at that
isothermal crystallization temperature, using DSC Pyris 1 or DSC7
manufactured by PerkinElmer, Inc. Here, the half-crystallization
time (t.sub.1/2) is determined by zero-setting the time when the
isothermal crystallization process starts (t=0) (the time when the
isothermal crystallization temperature is reached from 200.degree.
C.). For the syndiotactic propylene polymer (7A) of the present
invention (7), t.sub.1/2 can be determined as described above. When
crystallization does not occur at any isothermal crystallization
temperature, for example, at 110.degree. C., then the degree of
crystallization is measured at an isothermal crystallization
temperature below 110.degree. C. several times, and the half
crystallization time (t.sub.1/2) is determined by
extrapolation.
[1321] The syndiotactic propylene polymer (7A) satisfying the
equation (Eq-1) is remarkably excellent in moldability compared to
existing syndiotactic propylene polymers. Here, the words excellent
in moldability indicate that in the case of molding processes such
as injection molding, inflation molding, blow molding, extrusion
and press molding, the time taken from the molten state to the
solid state is short. Also, such syndiotactic propylene polymer (A)
is excellent in molding cycle properties, shape stability,
long-term productivity, and the like.
[1322] By controlling the polymerization conditions as will be
described later and by using the catalyst system that will be
described later, the syndiotactic propylene polymer (7A) satisfying
the equation (Eq-1) can be produced.
[1323] In a preferred embodiment of the syndiotactic propylene
polymer (7A) of the present invention (7), the following
requirement (n-decane-soluble content) is satisfied in addition to
the above-described preferred embodiments (satisfying
.DELTA.H.gtoreq.40 mJ/mg, and satisfying the above equation
(Eq-1)).
[1324] The amount of the n-decane-soluble content of the
syndiotactic propylene polymer (7A) is preferably 1 (wt %) or less,
preferably 0.8 (wt %) or less, and more preferably 0.6 (wt %) or
less. This amount of n-decane-soluble content is an index closely
related to the blocking properties of the syndiotactic propylene
polymer (A) and the molded products obtained therefrom, and a
smaller amount of n-decane-soluble content usually means a smaller
amount of low-crystalline components. That is, the syndiotactic
propylene polymer (A) further satisfying the present requirement
(n-decane-soluble content) has very good anti-blocking
properties.
[1325] Therefore, one of the most preferred embodiments of the
component (7A) is a syndiotactic propylene polymer that contains
constituent units derived from propylene in an amount of more than
90 mol %, has a syndiotactic pentad fraction (rrrr fraction) of 85%
or more as measured by .sup.13C-NMR, a melting point (Tm) of
145.degree. C. or higher as measured by DSC, and a heat of fusion
(.DELTA.H) of 40 mJ/mg or more, satisfies the equation (Eq-1), and
has an n-decane-soluble content of 1 wt % or less.
[1326] In the production of the syndiotactic propylene polymer (7A)
used in the present invention (7), the catalyst for polymerization
(cat-1) comprising:
[1327] (I) a bridged metallocene compound represented by General
Formula [1], and
[1328] (II) at least one compound selected from:
[1329] (II-1) an organoaluminum oxy compound,
[1330] (II-2) a compound which reacts with the bridged metallocene
compound (7A) to form an ion pair, and
[1331] (II-3) an organoaluminum compound,
[1332] or the catalyst for polymerization (cat-2) having the
catalyst (cat-1) supported on a particulate support, is suitably
used. However, as long as the produced polymer shows properties
that satisfy the requirements required for the syndiotactic
propylene polymer (7A), the catalyst used in the production of the
syndiotactic polypropylene polymer (7A) is not limited to such
catalysts.
##STR00014##
[1333] In General Formula [1], R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 are each selected from a hydrogen atom, a hydrocarbon
group, and a silicon-containing group; R.sup.2 and R.sup.3 may be
linked to each other to form a ring, R.sup.5, R.sup.6, R.sup.8,
R.sup.9, R.sup.11 and R.sup.12 may be selected from hydrogen, a
hydrocarbon group, and a silicon-containing group; the two groups
of R.sup.7 and R.sup.10 are not hydrogen atoms, but are each
selected from a hydrocarbon group and a silicon-containing group,
and may be identical to or different from each other; and in one or
more combinations of adjacent groups selected from R.sup.5 and
R.sup.6, R.sup.7 and R.sup.8, R.sup.8 and R.sup.9, R.sup.9 and
R.sup.10, and R.sup.11 and R.sup.12, the adjacent groups may be
linked to each other to form a ring. R.sup.17 and R.sup.18 are each
a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
or a silicon atom-containing group, and may be identical to or
different from each other, while the substituents may be linked to
each other to form a ring. M is Ti, Zr, or Hf; Y is carbon; Q may
be selected from halogen, a hydrocarbon group, an anionic ligand,
and a neutral ligand capable of coordination with a lone electron
pair, in identical or different combinations; and j is an integer
from 1 to 4.
[1334] (I) Bridged Metallocene Compound
[1335] Specific examples of the bridged metallocene compound (I)
represented by above General Formula [1](in the present
specification, may also be referred to as "component (I)")
include:
[1336]
cyclopropylidene(cyclopentadienyl)(3,6-di-tert-fluorenyl)zirconium
dichloride,
cyclobutylidene(cyclopentadienyl)(3,6-di-tert-fluorenyl)zirconium
dichloride,
cyclopentylidene(cyclopentadienyl)(3,6-di-tert-fluorenyl)zirconium
dichloride,
cyclohexylidene(cyclopentadienyl)(3,6-di-tert-fluorenyl)zirconium
dichloride,
cycloheptylidene(cyclopentadienyl)(3,6-di-tert-fluorenyl)zirconium
dichloride,
dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride,
dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, di-n-butylmethylene
(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluorenyl)zirconium
dichloride,
di-n-butylmethylene(cyclopentadienyl(2,7-di(2,4,6-trimethylphenyl)-3,6-di-
-tert-butylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluor-
enyl)zirconium dichloride, di-n-butylmethylene
(cyclopentadienyl)(2,7-di(3,5-dimethylphenyl)-3,6-di-tert-butylfluorenyl)-
zirconium dichloride, di-n-butylmethylene(cyclopentadienyl)(2,3,6,
7-tetra-tert-butylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-di(4-methylphenyl)-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dinaphthyl-3,6-di-tert-butylflu-
orenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-di(4-tert-butylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluor-
enyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl(2,7-di(2,4,6-trimethylphenyl)-3,6-di-
-tert-butylfluorenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluor-
enyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-di(3,5-dimethylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluorenyl)z-
irconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-di(4-methylphenyl)-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-dinaphthyl-3,6-di-tert-butylflu-
orenyl)zirconium dichloride,
diisobutylmethylene(cyclopentadienyl)(2,7-di(4-tert-butylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride [also referred to as
1,3-diphenylisopropylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride, the same applies hereinafter],
dibenzylmethylene(cyclopentadienyl(2,7-di(2,4,6-trimethylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di(3,5-dimethylphenyl)-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluorenyl)zir-
conium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di(4-methylphenyl)-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dinaphthyl-3,6-di-tert-butylfluor-
enyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-di(4-tert-butylphenyl)-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
diphenethylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
diphenethylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
di(benzhydryl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(benzhydryl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(cumyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluore-
nyl)zirconium dichloride,
di(cumyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluore-
nyl)zirconium dichloride,
di(1-phenyl-ethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(1-phenyl-ethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(cyclohexylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(cyclohexylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(cyclopentylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(cyclopentylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
(benzyl)(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride, (benzyl)
(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluore-
nyl)zirconium dichloride, (benzyl)
(cumyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride, (benzyl)
(cumyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclopropylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclopropylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclobutylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cyclobutylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cyclopentylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclopentylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cyclohexylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl-
)zirconium dichloride,
cycloheptylidene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
cycloheptylidene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butylfluore-
nyl)zirconium dichloride, di-n-butylmethylene
(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butylfluorenyl)zirconium
dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dicumyl-butylfluoren-
yl)zirconium dichloride, di-n-butylmethylene
(cyclopentadienyl)(2,7-dimethyl-3,6-dicumyl-butylfluorenyl)zirconium
dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di(trimethylsilyl)-b-
utylfluorenyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di(trimethylsilyl)-
-butylfluorenyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-diphenyl-butylfluore-
nyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-diphenyl-butylfluo-
renyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dibenzyl-butylfluore-
nyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dibenzyl-butylfluo-
renyl)zirconium dichloride,
dibenzylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butylfluore-
nyl)zirconium dichloride,
di-n-butylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-dimethyl-butylfluo-
renyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-te-
rt-butylfluorenyl)zirconium dichloride,
di(p-tert-butyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-te-
rt-butylfluorenyl)zirconium dichloride,
di(p-n-butyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(p-n-butyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(1-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(1-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(naphthylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-isopropylphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(p-isopropylphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(biphenylmethyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoreny-
l)zirconium dichloride, and the like.
[1337] Furthermore, examples thereof also include compounds
resulting from replacing the "zirconium" of the compounds described
above with "hafnium" or "titanium", and metallocene compounds
resulting from replacing the "dichloride" of the compounds
described above with "difluoride", "dibromide", or "diiodide", or
resulting from replacing the "dichloride" of the compounds
described above with "dimethyl" or "methylethyl".
[1338] The bridged metallocene compound (I) can be produced by
known methods, and the method for production is not particularly
limited. Examples of the known methods for production include the
methods for production described in WO 2001/27124 and WO
2004/087775 filed by the present applicant.
[1339] Such bridged metallocene compounds (I) can be used alone or
in combination of two or more kinds.
[1340] (II-1) Organoaluminum Oxy Compound
[1341] As the organoaluminum oxy compound (II-1) used in the
production of the syndiotactic propylene polymer (7A) (in the
present specification, may also be referred to as "component
(II-1)"), a known aluminoxane may be directly used, and specific
examples thereof include a compound represented by following
General Formula [2]:
##STR00015##
and/or a compound represented by General Formula [3]:
##STR00016##
[1342] (In above Formula [2], R's each independently represent a
hydrocarbon group having 1 to 10 carbon atoms; and n represents an
integer of 2 or more.)
[1343] (In above Formula [3], R represents a hydrocarbon group
having 1 to 10 carbon atoms; and n represents an integer of 2 or
more.) In particular, methylaluminoxane in which R is a methyl
group and n is 3 or more, preferably 10 or more, is used. These
aluminoxanes may have some amount of an organoaluminum compound
entrained therein.
[1344] For the invention (7), the benzene-insoluble organoaluminum
oxy compounds as illustrated in JP-A No. 2-78687 can be also used.
The organoaluminum oxy compounds described in JP-A No. 2-167305,
aluminoxanes having 2 or more kinds of alkyl groups as described in
JP-A Nos. 2-24701 and 3-103407, and the like are also suitably
used. The "benzene-insoluble" organoaluminum oxy compound means an
organoaluminum oxy compound which is insoluble or poorly soluble in
benzene to the extent that the Al component soluble in benzene at
60.degree. C. is contained in an amount of generally 10% or less,
preferably 5% or less, and particularly preferably 2% or less,
relative to Al atoms.
[1345] Examples of the organoaluminum oxy compound also include
modified methylaluminoxane as represented by following Formula [4]
and the like:
##STR00017##
[1346] (In Formula [4], R represents a hydrocarbon group having 1
to 10 carbon atoms; and m and n each independently represent an
integer of 2 or more).
[1347] This modified methylaluminoxane is prepared using
trimethylaluminum and alkylaluminum other than trimethylaluminum.
Such modified methylaluminoxane [4] is generally referred to as
MMAO. MMAO can be prepared by the methods disclosed in U.S. Pat.
No. 4,960,878 and U.S. Pat. No. 5,041,584. In addition, such a
compound in which R is an isobutyl group, which compound is
prepared using trimethylaluminum and triisobutylaluminum, is also
commercially produced by Tosoh Finechem Corporation and the like
under the product name of MMAO or TMAO. Such MMAO is aluminoxane
having improved solubility in various solvents and storage
stability, and specifically, the compound is soluble in aliphatic
hydrocarbons and alicyclic hydrocarbons, unlike the aluminoxanes
that are insoluble or poorly soluble in benzene, such as the
compounds represented by above Formula [2] or [3].
[1348] Furthermore, examples of the organoaluminum oxy compound
also include an organoaluminum oxy compound containing boron,
represented by following General Formula [5]:
##STR00018##
[1349] (In Formula [5], R.sup.c represents a hydrocarbon group
having 1 to 10 carbon atoms; R.sup.d's, which may be identical to
or different from each other, each represent a hydrogen atom, a
halogen atom, or a hydrocarbon group having 1 to 10 carbon
atoms).
[1350] (II-2) Compound which Reacts with the Bridged Metallocene
Compound (a) to Form an Ion Pair
[1351] Examples of the compound (II-2) which reacts with the
bridged metallocene compound (I) to form an ion pair (hereinafter,
may be also referred to as "ionic compound" or "component (II-2)"),
which can be used in the production of the syndiotactic propylene
polymer (7A), include Lewis acids, ionic compounds, borane
compounds, and carborane compounds described in JP-A No. 1-501950,
JP-A No. 1-502036, JP-A No. 3-179005, JP-A No. 3-179006, JP-A No.
3-207703, JP-A No. 3-207704, U.S. Pat. No. 5,321,106, and the like.
Examples thereof also include heteropoly compounds and isopoly
compounds. An ionic compound preferably employed in the present
invention is a compound represented by following General Formula
[6]:
##STR00019##
[1352] in Formula, R.sup.e+ is exemplified by H.sup.+, a carbenium
cation, an oxonium cation, an ammonium cation, a phosphonium
cation, a cycloheptyltrienyl cation, a ferrocenium cation having a
transition metal, or the like; R.sup.f to R.sup.i may be identical
to or different from each other, and are each an organic group,
preferably an aryl group.
[1353] Specific examples of the carbenium cation include
trisubstituted carbenium cations such as triphenylcarbenium cation,
tris(methylphenyl)carbenium cation, and
tris(dimethylphenyl)carbenium cation.
[1354] Specific examples of the ammonium cation include
trialkylammonium cations such as trimethylammonium cation,
triethylammonium cation, tri(n-propyl)ammonium cation,
triisopropylammonium cation, tri(n-butyl)ammonium cation, and
triisobutylammonium cation; N,N-dialkylanilinium cations such as
N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and
N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations
such as diisopropylammonium cation and dicyclohexylammonium
cation.
[1355] Specific examples of the phosphonium cation include
triarylphosphonium cations such as triphenylphosphonium cation,
tris(methylphenyl)phosphonium cation, and
tris(dimethylphenyl)phosphonium cation.
[1356] Among them, R.sup.e+ is preferably a carbenium cation, an
ammonium cation, or the like, and particularly preferably a
triphenylcarbenium cation, an N,N-dimethylanilinium cation, or an
N,N-diethylanilinium cation.
[1357] Specific examples of the carbenium salt include
triphenylcarbenium tetraphenylborate, triphenylcarbenium
tetrakis(pentafluorophenyl)borate, triphenylcarbenium
tetrakis(3,5-ditrifluoromethylphenyl)borate,
tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate,
tris(3,5-dimethylphenyl)carbenium
tetrakis(pentafluorophenyl)borate, and the like.
[1358] Examples of the ammonium salt include trialkyl-substituted
ammonium salts, N,N-dialkylanilinium salts, dialkylammonium salts,
and the like.
[1359] Specific examples of the trialkyl-substituted ammonium salt
include triethylammonium tetraphenylborate, tripropylammonium
tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate,
trimethylammoniumtetrakis(p-tolyl)borate, trimethylammonium
tetrakis(o-tolyl)borate, tri(n-butyl)ammonium
tetrakis(pentafluorophenyl)borate, triethylammonium
tetrakis(pentafluorophenyl)borate, tripropylammonium
tetrakis(pentafluorophenyl)borate, tripropylammonium
tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(4-trifluoromethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(3,5-ditrifluoromethylphenyl)borate, tri(n-butyl)ammonium
tetrakis(o-tolyl)borate, dioctadecylmethylammonium
tetraphenylborate, dioctadecylmethylammonium
tetrakis(p-tolyl)borate, dioctadecylmethylammonium
tetrakis(o-tolyl)borate, dioctadecylmethylammonium
tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium
tetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammonium
tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammonium
tetrakis(4-trifluoromethylphenyl)borate, dioctadecylmethylammonium
tetrakis(3,5-ditrifluoromethylphenyl)borate,
dioctadecylmethylammonium, and the like.
[1360] Specific examples of the N,N-dialkylanilinium salt include
N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium
tetrakis(3,5-ditrifluoromethylphenyl)borate, N,N-diethylanilinium
tetraphenylborate, N,N-diethylanilinium
tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium
tetrakis(3,5-ditrifluoromethylphenyl)borate,
N,N-2,4,6-pentamethylanilinium tetraphenylborate,
N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate,
and the like.
[1361] Specific examples of the dialkylammonium salt include
di(l-propyl)ammonium tetrakis(pentafluorophenyl)borate,
dicyclohexylammonium tetraphenylborate, and the like.
[1362] In addition to these, ionic compounds disclosed by the
present applicant (JP-A No. 2004-51676) can also be used without
limitation.
[1363] The ionic compounds (II-2) as described above can be used as
a mixture of two or more kinds.
[1364] (II-3) Organoaluminum Compound
[1365] Examples of the organoaluminum compound (II-3) (in the
present specification, may also be referred to as "component
(II-3)") for use in the production of the syndiotactic propylene
polymer (7A) include an organoaluminum compound represented by
following General Formula [7], and a complex alkylated product of
Group 1 metal and aluminum represented by following General Formula
[8]:
R.sup.a.sub.mAl(OR.sup.b).sub.nH.sub.pX.sub.q [7]
[1366] (In Formula [7], R.sup.a and R.sup.b, which may be identical
to or different from each other, each represent a hydrocarbon group
having 1 to 15, preferably 1 to 4 carbon atoms; X represents a
halogen atom; m is a number satisfying 0<m.ltoreq.3, n is a
number satisfying 0.ltoreq.n<3, p is a number satisfying
0.ltoreq.p<3, and q is a number satisfying 0.ltoreq.q<3; and
m+n+p+q=3).
[1367] Specific examples of such compound include
tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum,
tri-n-butylaluminum, trihexylaluminum, and trioctylaluminum;
[1368] tri-branched-alkylaluminums such as triisopropylaluminum,
triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum,
tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and
tri-2-ethylhexylaluminum;
[1369] tricycloalkylaluminums such as tricyclohexylaluminum and
tricyclooctylaluminum;
[1370] triarylaluminums such as triphenylaluminum, and
tritolylaluminum;
[1371] dialkylaluminum hydrides such as diisopropylaluminum hydride
and diisobutylaluminum hydride;
[1372] alkenylaluminums represented by general formula:
(i-C.sub.4H.sub.9).sub.xAl.sub.y(C.sub.5H.sub.10).sub.z (wherein x,
y, and z are positive numbers, and z.ltoreq.2x), such as
isoprenylaluminum;
[1373] alkylaluminum alkoxides such as isobutylaluminum methoxide
and isobutylaluminum ethoxide;
[1374] dialkylaluminum alkoxides such as dimethylaluminum
methoxide, diethylaluminum ethoxide, and dibutylaluminum
butoxide;
[1375] alkylaluminum sesquialkoxides such as ethylaluminum
sesquiethoxide and butylaluminum sesquibutoxide;
[1376] partially alkoxylated alkylaluminums having an average
composition represented by general formula:
Ra.sub.2.5Al(ORb).sub.0.5 and the like;
[1377] alkylaluminum aryloxides such as diethylaluminum phenoxide
and diethylaluminum(2,6-di-t-butyl-4-methylphenoxide);
[1378] dialkylaluminum halides such as dimethylaluminum chloride,
diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum
bromide, and diisobutylaluminum chloride;
[1379] alkylaluminum sesquihalides such as ethylaluminum
sesquichloride, butylaluminum sesquichloride, and ethylaluminum
sesquibromide;
[1380] partially halogenated alkylaluminums such as alkylaluminum
dihalide such as ethylaluminum dichloride; dialkylaluminum hydrides
such as diethylaluminum hydride and dibutylaluminum hydride;
[1381] partially hydrogenated alkylaluminums such as alkylaluminum
dihydrides such as ethylaluminum dihydride and propylaluminum
dihydride; and partially alkoxylated and halogenated alkylaluminums
such as ethylaluminum ethoxychloride, butylaluminum butoxychloride,
and ethylaluminum ethoxybromide.
M.sup.2AlR.sup.a.sub.4 [8]
[1382] (In Formula [8], M.sup.2 represents Li, Na, or K; and
R.sup.a represents a hydrocarbon group having 1 to 15, preferably 1
to 4 carbon atoms).
[1383] Such compound is exemplified by LiAl(C.sub.2H.sub.5).sub.4,
LiAl(C.sub.7H.sub.15).sub.4, or the like.
[1384] A compound similar to the compound represented by the
General Formula [8] can also be used, and examples thereof include
an organoaluminum compound in which two or more aluminum compounds
are bound with a nitrogen atom interposed therebetween.
Specifically, such compound is exemplified by
(C.sub.2H.sub.5).sub.2AlN(C.sub.2H.sub.5)Al(C.sub.2H.sub.5).sub.2
or the like.
[1385] As the organoaluminum compound (II-3), trimethylaluminum and
triisobutylaluminum are preferably used from the aspect of easy
availability.
[1386] Further, the above-mentioned respective components may be
used while being supported on a particulate support.
[1387] Support (III)
[1388] The support (III) that can be used as necessary (in the
present specification, may also be referred to as "component
(III)") is an inorganic or organic compound, and is a granular or
microparticulate solid.
[1389] Among these, the inorganic compound is preferably a porous
oxide, an inorganic halide, a clay, a clay mineral, or an ion
exchangeable lamellar compound.
[1390] As the porous oxide, specifically SiO.sub.2,
Al.sub.2O.sub.3, MgO, ZrO, TiO.sub.2, B.sub.2O.sub.3, CaO, ZnO,
BaO, ThO.sub.2 and the like, or complexes or mixtures containing
these, for example, natural or synthetic zeolites, SiO.sub.2--MgO,
SiO.sub.2--Al.sub.2O.sub.3, SiO.sub.2--TiO.sub.2,
SiO.sub.2--V.sub.2O.sub.5, SiO.sub.2--Cr.sub.2O.sub.3,
SiO.sub.2--TiO.sub.2--MgO and the like can be used. Among these, it
is preferable that SiO.sub.2 and/or Al.sub.2O.sub.3 is a main
component.
[1391] The above-mentioned inorganic oxide may contain a small
amount of carbonate, sulfate, nitrate, or oxide component, such as
Na.sub.2CO.sub.3, K.sub.2CO.sub.3, CaCO.sub.3, MgCO.sub.3,
Na.sub.2SO.sub.4, Al.sub.2(SO.sub.4).sub.3, BaSO.sub.4, KNO.sub.3,
Mg(NO.sub.3).sub.2, Al(NO.sub.3).sub.3, Na.sub.2O, K.sub.2O, and
Li.sub.2O.
[1392] Such porous oxides may vary in properties depending on the
type and method for production. The support that can be preferably
used has a particle size of 3 to 300 .mu.m, preferably to 300
.mu.m, and more preferably 20 to 200 .mu.m, a specific surface area
in the range of 50 to 1000 m.sup.2/g, preferably 100 to 700
m.sup.2/g, and a pore volume preferably in the range of 0.3 to 3.0
cm.sup.3/g. Such support is calcined as necessary at 100 to
1000.degree. C., and preferably 150 to 700.degree. C. before
use.
[1393] As the inorganic halide, MgCl.sub.2, MgBr.sub.2, MnCl.sub.2,
MnBr.sub.2, and the like are used. The inorganic halide may be used
directly, or may be used after being ground with a ball mill or a
vibration mill. Furthermore, a halide obtained by dissolving the
inorganic halide in a solvent such as alcohol, and then
precipitating the compound into a microparticulate form using a
precipitating agent, can also be used.
[1394] The clay is usually comprised of a clay mineral as a main
component. The ion exchangeable lamellar compound is a compound
having a crystal structure in which planes constituted of ionic
bonding or the like are stacked on one another in parallel with
weak bonding strength, and in which the ions contained can be
exchanged. Most clay minerals are ion exchangeable lamellar
compounds. The clay, clay mineral and ion exchangeable lamellar
compound are not limited to natural products, and artificially
synthesized products can also be used.
[1395] Furthermore, examples of the clay, clay mineral, or ion
exchangeable lamellar compound include clays, clay minerals, and
ion crystalline compounds having lamellar crystal structures such
as hexagonal close packed type, antimony type, CdCl.sub.2 type, and
CdI.sub.2 type.
[1396] Examples of the clay and clay mineral include kaolin,
bentonite, kibushi clay, gairome clay, allophane, hisingerite,
pyrophyllite, mica group, montmorillonite group, vermiculite,
phyllite group, palygorskite, kaolinite, nacrite, dickite,
halloysite, and the like. Examples of the ion exchangeable lamellar
compound include crystalline acid salts of multivalent metals such
as .alpha.-Zr(HAsO.sub.4).sub.2.H.sub.2O,
.alpha.-Zr(HPO.sub.4).sub.2, .alpha.-Zr(KPO.sub.4).sub.2.3H.sub.2O,
.alpha.-Ti(HPO.sub.4).sub.2, .alpha.-Ti(HAsO.sub.4).sub.2.H.sub.2O,
.alpha.-Sn(HPO.sub.4).sub.2.H.sub.2O, .gamma.-Zr(HPO.sub.4).sub.2,
.gamma.-Ti(HPO.sub.4).sub.2, and
.gamma.-Ti(NH.sub.4PO.sub.4).sub.2.H.sub.2O.
[1397] It is preferable for such clay, clay mineral, or ion
exchangeable lamellar compound that the volume of pores having a
radius of 20 .ANG. or more as measured by mercury porosimetry is
preferably 0.1 cc/g or larger, and particularly preferably 0.3 to 5
cc/g. The pore volume is measured for the pore radius in the range
of 20 to 3.times.10.sup.4 .ANG. according to the mercury
porosimetry using a mercury porosimeter.
[1398] When a support having a volume of pores with 20 .ANG. radius
or more of less than 0.1 cc/g is used, there is a tendency that
high polymerization activity is hardly obtained.
[1399] The clay and clay mineral may preferably be subjected to a
chemical treatment.
[1400] Any of the chemical treatments such as a surface treatment
which removes impurities attached on the surface, and treatments
giving an effect on the crystal structure of the clay, can be used.
Specific examples of the chemical treatment include an acid
treatment, an alkali treatment, a treatment with salts, and a
treatment with organic compounds. The acid treatment removes
impurities on the surface, and also increases the surface area by
eluting a positive ion such as Al, Fe, and Mg in the crystal
structure. The alkali treatment destroys the crystal structure of
the clay, and brings a structural change in the clay. The treatment
with salts and the treatment with organic compounds form an ionic
complex, molecular complex, organic derivative, or the like, and
can change the surface area and the interlayer distance.
[1401] The ion exchangeable lamellar compound may be enlarged in
interlayer distance by exchanging the interlayer exchangeable ions
with other bulkier ions using the ion exchangeability. Such bulky
ion plays a supportive role to support the lamellar structure, and
is generally called pillar. Also, the introduction of other
substance between layers of the lamellar compound is known as
intercalation. Examples of the guest compound for intercalation
include cationic inorganic compounds such as TiCl.sub.4 and
ZrCl.sub.4, metal alkoxides such as Ti(OR).sub.4, Zr(OR).sub.4,
PO(OR).sub.3, and B(OR).sub.3 (wherein R is a hydrocarbon group or
the like), and metal hydroxide ions such as
[Al.sub.13O.sub.4(OH).sub.24].sup.7+, [Zr.sub.4(OH).sub.14].sup.2+,
and [Fe.sub.3O(OCOCH.sub.3).sub.6].sup.+. These compounds may be
used alone or in combination of two or more kinds. When these
compounds are intercalated, a polymer obtained by hydrolyzing metal
alkoxide such as Si(OR).sub.4, Al(OR).sub.3, or Ge(OR).sub.4 (R's
are each a hydrocarbon group, or the like), a colloidal inorganic
compound such as SiO.sub.2, or the like can be allowed to coexist.
Examples of the pillar include oxides produced by conducting
thermal dehydration of the above-mentioned metal hydroxide ions
after intercalation thereof. Among these compounds, preferred are
clays and clay minerals and particularly preferred are
montmorillonite, vermiculite, pectolite, tainiolite, and synthetic
mica.
[1402] The clays, clay minerals, and ion-exchangeable lamellar
compounds may be used directly or after subjected to a treatment
with ball mill, sieving or the like. Moreover, they may be used
after adsorbing newly added water thereonto, or after being
subjected to thermal dehydration treatment. They may be used alone
or in combination of two or more kinds.
[1403] The use of an ion-exchangeable lamellar silicate provides an
advantage that while the silicate serves as support, the ion
exchangeable properties and the lamellar structure thereof permit
reducing the amount of the organoaluminum oxy compound such as
alkylaluminoxane. Ion exchangeable lamellar silicates are mainly
obtained as a main component of natural clay minerals, but the
silicates in the invention are not limited to natural products, and
artificially synthesized products can also be used. Specific
examples of the clay, the clay mineral, and ion exchangeable
lamellar silicate include kaolinite, montmorillonite, hectorite,
bentonite, smectite, vermiculite, tainiolite, synthetic mica,
synthetic hectorite, and the like.
[1404] The organic compound may be exemplified by a granular solid
or a microparticulate solid having a particle size in the range of
3 to 300 .mu.m, and preferably 10 to 300 .mu.m. Specific examples
thereof include (co) polymers produced from an .alpha.-olefin
having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene,
or 4-methyl-1-pentene as a main component; (co)polymers or
copolymers produced from vinylcyclohexane or styrene as a main
component; and polymers or modified products having a polar
functional group that are obtained by copolymerizing or graft
polymerizing a polar monomer such as acrylic acid, acrylic ester or
maleic anhydride, with the above-mentioned polymers. These
particulate supports may be used alone or in combination of two or
more kinds.
[1405] Furthermore, the catalyst for olefin polymerization that can
be used in the production of the syndiotactic propylene polymer
(7A) may also contain a specific organic compound component (IV)
described below according to necessity, along with the
above-mentioned components.
[1406] (IV) Organic Compound Component
[1407] In the present invention, the organic compound component
(IV) (in the present specification, may also be referred to as
"component (IV)") is used as necessary, for the purpose of
improving the polymerization performance and properties of the
produced polymer. Such organic compound is exemplified by alcohols,
phenolic compounds, carboxylic acids, phosphorus compounds,
sulfonates, and the like, but the compounds are not limited to
these.
[1408] Method for Producing Syndiotactic Propylene Polymer (7A)
[1409] In the polymerization, the mode of using each of the
components, and the order of addition are arbitrarily selected, and
the following methods may be mentioned.
[1410] (1) A method comprising adding the component (I) alone into
the polymerization vessel.
[1411] (2) A method comprising adding the component (I) and
component (II) into the polymerization vessel in an arbitrary
order.
[1412] (3) A method comprising adding a catalyst component in which
the component (I) is supported on the support (III), and the
component (II) into the polymerization vessel in an arbitrary
order.
[1413] (4) A method comprising adding a catalyst component in which
the component (II) is supported on the support (III), and the
component (I) into the polymerization vessel in an arbitrary
order.
[1414] (5) A method comprising adding a catalyst component in which
the component (I) and the component (II) are supported on the
support (III) into the polymerization vessel.
[1415] In the respective methods of (2) to (5) described above, at
least two or more of the catalyst components may be brought into
contact with each other in advance.
[1416] In the respective methods of (4) and (5) described above
using the supported component (II), unsupported component (II) may
be added in any order as necessary. In this case, the components
(II) may be identical to or different from each other.
[1417] Furthermore, the solid catalyst component having the
component (I) supported on the component (III), and the solid
catalyst component having the component (I) and component (II) both
supported on the component (III) may have a prepolymerized olefin.
Such prepolymerized solid catalyst component may further have a
catalyst component supported thereon.
[1418] The syndiotactic propylene polymer (7A) can be obtained by
polymerizing or copolymerizing propylene with at least one kind of
olefin selected from .alpha.-olefins having 2 to 20 carbon atoms
(excluding propylene) in the presence of the catalyst for olefin
polymerization as mentioned above.
[1419] The polymerization can be carried out by any of a liquid
phase polymerization method such as a solution polymerization or a
suspension polymerization, and a gas phase polymerization method.
Specific examples of inert hydrocarbon medium used in the liquid
phase polymerization method include aliphatic hydrocarbons such as
propane, butane, pentane, hexane, heptane, octane, decane,
dodecane, and kerosene; alicyclic hydrocarbons such as
cyclopentane, cyclohexane, and methylcyclopentane; aromatic
hydrocarbons such as benzene, toluene, and xylene; halogenated
hydrocarbons such as ethylene chloride, chlorobenzene, and
dichloromethane; and mixtures thereof. The olefin to be polymerized
may also be used per se as the solvent.
[1420] When the polymerization of propylene with at least one kind
of olefin selected from .alpha.-olefins having 2 to 20 carbon atoms
(excluding propylene) is performed using the catalyst for olefin
polymerization as described above, the component (I) is usually
used in an amount of 10.sup.-9 to 10.sup.-1 moles, and preferably
10.sup.-8 to 10.sup.-2 moles, per liter of the reaction volume.
[1421] The component (II-1) is used in an amount such that the
molar ratio [(II-1)/M] of the component (II-1) to the total
transition metal atoms (M) in the component (I) is usually 0.01 to
5,000, and preferably 0.05 to 2,000. The component (II-2) is used
in an amount such that the molar ratio [(II-2)/M] of the component
(II-2) to the transition metal atoms (M) in the component (I) is
usually 1 to 10, and preferably 1 to 5. The component (II-3) is
used in an amount such that the molar ratio [(II-3)/M] of the
aluminum atoms in the component (II-3) to the total transition
metal atoms (M) in the component (I) is usually to 5,000, and
preferably 20 to 2,000.
[1422] The component (IV) is used, in the case where the component
(II) is component (II-1), in an amount such that the molar ratio
[(IV)/(II-1)] is usually 0.01 to 10, and preferably 0.1 to 5; in
the case where the component (II) is component (II-2), in an amount
such that the molar ratio [(IV)/(II-2)] is usually 0.01 to 10, and
preferably 0.1 to 5; and in the case where the component (II) is
component (II-3), in an amount such that the molar ratio
[(IV)/(II-3)] is usually 0.01 to 2, and preferably 0.005 to 1.
[1423] The temperature for olefin polymerization using the catalyst
for olefin polymerization is generally within the range from -50 to
+200.degree. C., preferably from 0 to 170.degree. C. The
polymerization pressure is generally from normal pressure to MPa
gauge pressure, and preferably from normal pressure to MPa gauge
pressure, and the polymerization reaction can be carried out
batchwise, semicontinuously or continuously. The polymerization can
be carried out in two or more stages under different reaction
conditions. The molecular weight of the resulting olefin polymer
can be regulated by allowing hydrogen to exist in the
polymerization system or by varying the polymerization temperature.
Moreover, the molecular weight can be regulated by changing the
amount of the component (II) used. When hydrogen is added, a
suitable amount thereof is from about 0.001 to 100 NL per 1 kg of
the olefin.
[1424] The olefins supplied to the polymerization reaction are
propylene and one or more olefins selected from .alpha.-olefins
having 2 to 20 carbon atoms (excluding propylene). The
.alpha.-olefin having 4 to 20 carbon atoms may be a linear or
branched .alpha.-olefin having 4 to 20, preferably 4 to 10 carbon
atoms, and is exemplified by 1-butene, 2-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene, or the like.
[1425] <Propylene..alpha.-Olefin Copolymer (7B)>
[1426] The propylene..alpha.-olefin copolymer (7B) is a
propylene..alpha.-olefin copolymer that contains propylene units in
an amount of 55 to 90 mol % and units of at least one
.alpha.-olefin selected from .alpha.-olefins having 2 to 20 carbon
atoms (excluding propylene) in an amount of 10 to 45 mol %, has an
MFR in the range of 0.01 to 100 g/min as measured according to JIS
K-6721 at 230.degree. C. under a load of 2.16 kg, and satisfies at
least one of the following requirements (b-1) and (b-2):
[1427] (b-1): the syndiotactic triad fraction (rr fraction) as
measured by .sup.13C-NMR is 60% or more, and
[1428] (b-2): the intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min) as measured
according to JIS K-6721 at 230.degree. C. under a load of 2.16 kg
satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
[1429] The propylene..alpha.-olefin copolymer (B) contains
propylene units in an amount of 55 to 90 mol %, and units of
.alpha.-olefin having 2 to 20 carbon atoms (excluding propylene) in
an amount of 10 to 45 mol %.
[1430] Here, the sum of amounts of the constituent units derived
from propylene and the units of .alpha.-olefin having 2 to 20
carbon atoms (excluding propylene) is 100 mol %.
[1431] The .alpha.-olefin having 2 to 20 carbon atoms (excluding
propylene) may be exemplified by ethylene, 3-methyl-1-butene,
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene,
1-eicosene, or the like. In particular, ethylene, 1-butene,
1-hexene, 4-methyl-1-pentene, and 1-octene are preferred.
[1432] Among the propylene..alpha.-olefin copolymers (7B) as
described above, a propylene-ethylene copolymer is a preferred
embodiment.
[1433] In the case of propylene-ethylene copolymer, constituent
units derived from propylene are preferably contained in an amount
of 10 to 35 mol %, more preferably 10 to 25 mol %.
[1434] Among the propylene..alpha.-olefin copolymers (7B) as
described above, a preferred embodiment is a propylene.ethylene.HAO
copolymer comprising propylene units, ethylene units, and
constituent units of any one of 1-butene, 1-hexene,
4-methyl-1-pentene, and 1-octene (may also be referred to as HAO
comonomer), wherein the proportion (mol %) of the ethylene units is
larger than the proportion (mol %) of the HAO comonomer units.
[1435] Furthermore, the propylene-ethylene copolymer and the
propylene.ethylene.HAO copolymer, which are preferred embodiments,
preferably satisfy both (b-1) and (b-2) described above.
[1436] The propylene..alpha.-olefin copolymer (7B) used in the
present invention preferably has an MFR in the range of 0.01 to 100
g/10 min, and more preferably in the range of 0.02 to 100 g/10 min,
as measured according to JIS K-6721 at 230.degree. C. under a load
of 2.16 kg.
[1437] The propylene..alpha.-olefin copolymer (7B) used in the
present invention satisfies at least one of (b-1) and (b-2)
below:
[1438] (b-1): The syndiotactic triad fraction (rr fraction, triad
syndiotacticity) as measured by .sup.13C-NMR is 60% or more;
and
[1439] (b-2): The intrinsic viscosity [.eta.] (dL/g) as measured in
decalin at 135.degree. C. and the MFR (g/10 min, 230.degree. C.,
under a load of 2.16 kg) satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
[1440] First, the requirement (b-1) will be explained.
[1441] (b-1): The syndiotactic triad fraction (rr fraction, triad
syndiotacticity) of the propylene..alpha.-olefin copolymer (7B) as
measured by .sup.13C-NMR is 60% or more, preferably 70% or more,
and more preferably 75% or more. The propylene..alpha.-olefin
copolymer (7B) having this rr fraction shows good compatibility
with the syndiotactic propylene polymer (A).
[1442] The polymer satisfying (b-1) can be obtained, for example,
by copolymerizing propylene and an .alpha.-olefin in the presence
of a catalyst capable of producing syndiotactic polypropylene, and
may also be produced using, for example, a catalyst as will be
described later.
[1443] The rr fraction is determined from the absorption
intensities of Prr (absorption intensity resulting from the methyl
group of the second unit at a site where 3 propylene units are
sequentially syndiotactically bound) and Pw (absorption intensity
resulting from the total methyl groups of propylene units) in the
.sup.13C-NMR spectrum according to the following formula (2):
rr fraction (%)=100.times.Prr/Pw (2)
[1444] Here, when the absorption resulting from mr (the absorption
resulting from at least both the syndiotactic bonding and isotactic
bonding in the 3 propylene units; used in the determination of Pmr
(absorption intensity)), the absorption resulting from rr (the
absorption resulting from the methyl group of the second unit at a
site where 3 propylene units are sequentially syndiotactically
bound; used in the determination of Prr (absorption intensity)), or
the absorption resulting from mm (the absorption resulting from the
methyl group of the second unit at a site where 3 propylene units
are sequentially isotactically bound; used in the determination of
Pmm (absorption intensity)) overlaps with the absorption resulting
from the comonomer, the absorption intensity is calculated without
subtracting the contribution of the comonomer component.
[1445] Specifically, reference is made to JP-A No. 2002-097325 that
describes a method for determining the syndiotacticity parameter
(SP value) ([0018] to [0031]). In the present invention, the
procedures described from [0018] to [0023] are performed, and
integrated intensities of the signals of the first, second and
third regions are obtained. Then, the fraction may be calculated
using the above formula (2).
[1446] In particular, in the invention, the rr, value,
specifically, a value determined by the method for determining the
"syndiotacticity parameter (SP value)" described in [0018] to
[0031] of JP-A No. 2002-097325, is 60% or greater, preferably 65%
or greater, and more preferably 70% or greater. The rr.sub.1 value
may be obtained in the same manner as the rr value with the
exception that when the absorption resulting from mr (the
absorption resulting from at least both the syndiotactic bonding
and isotactic bonding in the 3 propylene units; used in the
determination of Pmr (absorption intensity)), the absorption
resulting from rr (the absorption resulting from the methyl group
of the second unit at a site where 3 propylene units are
sequentially syndiotactically bound; used in the determination of
Prr (absorption intensity)), or the absorption resulting from mm
(the absorption resulting from the methyl group of the second unit
at a site where 3 propylene units are sequentially isotactically
bound; used in the determination of Pmm (absorption intensity))
overlaps with the absorption resulting from the comonomer, the
absorption intensity is calculated with subtraction of the
contribution of the comonomer component.
[1447] For the measurement of the rr value and rr.sub.1 value, the
NMR measurement is, for example, carried out in the following
manner. Specifically, 0.35 g of a sample is dissolved by heating in
2.0 ml of hexachlorobutadiene. This solution is filtered through a
glass filter (G2), subsequently, 0.5 ml of deuterated benzene is
added, and the mixture is placed in an NMR tube having an internal
diameter of 10 mm. Then, .sup.13C-NMR measurement is performed at
120.degree. C. using a GX-400 type NMR measuring apparatus
manufactured by JEOL, Ltd. The number of scans is 8,000 or
greater.
[1448] Next, the requirement (b-2) will be explained.
[1449] (b-2): The propylene..alpha.-olefin copolymer (B) used in
the present invention (7) is such that the intrinsic viscosity
[.eta.](dL/g) as measured in decalin at 135.degree. C. and the MFR
(g/10 min) as measured according to JIS K-6721 at 230.degree. C.
under a load of 2.16 kg satisfy the following relationship:
1.50.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.65.times.MFR.sup.(-0.-
20)
more preferably,
1.80.times.MFR.sup.(-0.20).ltoreq.[.eta.].ltoreq.2.50.times.MFR.sup.(-0.-
19)
[1450] The propylene..alpha.-olefin copolymer (7B) satisfying the
relationship has good compatibility with the syndiotactic propylene
polymer (7A), and thus is preferable.
[1451] The propylene..alpha.-olefin copolymer (7B) satisfying the
above expression can be obtained, for example, by copolymerizing
propylene with an .alpha.-olefin with a catalyst capable of
producing syndiotactic propylene, and may also be produced, for
example, using a catalyst as will be described later. Such material
is highly compatible with the syndiotactic propylene polymer
(7A).
[1452] The propylene..alpha.-olefin copolymer satisfying (b-2) has
a larger MFR compared to known isotactic propylene-based copolymers
at the same level of [.eta.].
[1453] This fact is thought to be due to the difference in
entanglement molecular weight, as described in Macromolecules, 31,
1335-1340 (1998), between the isotactic polypropylene (reported to
be Me=6900 (g/mol) in the article) and the syndiotactic
polypropylene (reported to be Me=2170 (g/mol) in the article). In
more detail, provided that [t] is identical, the syndiotactic
structure provides a larger number of entanglements than does the
isotactic structure, and the MFR is increased.
[1454] As described above, the propylene..alpha.-olefin copolymer
(7B) satisfying at least one of (b-1) and (b-2) shows different
stereospecificity from propylene..alpha.-olefin copolymers having
an isotactic structure, and thus is thought to have a syndiotactic
structure. The excellent compatibility of the
propylene..alpha.-olefin copolymer (7B) with the component (7A) is
probably due to such structure.
[1455] The intrinsic viscosity [.eta.] of the
propylene..alpha.-olefin copolymer (7B) as measured in decalin at
135.degree. C. is 0.1 to 10 dL/g, preferably 0.5 to 8.0 dL/g, more
preferably 1.0 to 7.0 dL/g, and even more preferably 1.0 to 5.0
dL/g.
[1456] This propylene..alpha.-olefin copolymer (7B) preferably has
a degree of crystallization of 20% or less, and more preferably 0
to 15%, as measured by X-ray diffractometry.
[1457] It is preferable that this propylene..alpha.-olefin
copolymer (7B) has a single glass transition temperature, and the
glass transition temperature (Tg) measured with differential
scanning calorimeter (DSC) is usually 0.degree. C. or below. If the
glass transition temperature (Tg) of the propylene..alpha.-olefin
copolymer (7B) is within the above-described range, the cold
resistance and low temperature properties are excellent.
[1458] Differential scanning calorimetric measurement is performed,
for example, in the following manner. About 10.00 mg of a sample is
placed in an aluminum pan for exclusive use, and the glass
transition temperature (Tg) is determined from an endothermal curve
obtained by heating the sample from 30.degree. C. to 200.degree. C.
at a rate of 200.degree. C./min, holding the sample at 200.degree.
C. for 5 minutes, cooling the sample from 200.degree. C. to
-100.degree. C. at a rate of 10.degree. C./min, allowing the sample
to stand at -100.degree. C. for 5 minutes, and then heating the
sample at a rate of 10.degree. C./min, using DSC RDC 220
manufactured by Seiko Instruments, Inc.
[1459] Also, the molecular weight distribution of this
propylene..alpha.-olefin copolymer (7B) as measured by GPC (Mw/Mn,
relative to polystyrene, Mw: weight average molecular weight, Mn:
number average molecular weight) is preferably 3.5 or less, more
preferably 3.0 or less, therefore even more preferably 2.5 or
less.
[1460] The propylene..alpha.-olefin copolymer (7B) that is used in
the present invention can be produced by polymerizing propylene,
and at least one olefin selected from .alpha.-olefins having 2 to
carbon atoms (excluding propylene), in the presence of a catalyst
for olefin polymerization comprising: (I') a bridged metallocene
compound represented by following General Formula [9]; and (II) at
least one compound selected from (II-1) an organoaluminum oxy
compound, (II-2) a compound which reacts with the bridged
metallocene compound (I') to form an ion pair, and (II-3) an
organoaluminum compound. However, as long as the requirements of
the propylene..alpha.-olefin copolymer (7B) are satisfied, the
method for production is not limited to this.
##STR00020##
[1461] (In Formula, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.8, R.sup.9 and R.sup.12, which may be identical to or
different from each other, are each an atom or a group selected
from a hydrogen atom, a hydrocarbon group, and a silicon-containing
group;
[1462] R.sup.6 and R.sup.11 are the same atoms or same groups
selected from a hydrogen atom, a hydrocarbon group, and a
silicon-containing group; R.sup.7 and R.sup.10 are the same atoms
or same groups selected from a hydrogen atom, a hydrocarbon group,
and a silicon-containing group; all of R.sup.6, R.sup.7, R.sup.10
and R.sup.11 cannot be simultaneously hydrogen atoms (in other
words, there will be no case where all of R.sup.6, R.sup.7,
R.sup.10 and R.sup.11 are simultaneously hydrogen atoms); R.sup.2
and R.sup.3 may be linked to each other to form a ring; among
R.sup.5 to R.sup.12, adjacent groups may be linked to each other to
form a ring;
[1463] R.sup.13 and R.sup.14, which may be identical to or
different from each other, are each selected from an aryl group
having 6 to 18 carbon atoms, an alkyl group having 1 to 40 carbon
atoms, an alkylaryl group having 6 to 40 carbon atoms, a fluoroaryl
group having 6 to 20 carbon atoms, a fluoroalkylaryl group having 7
to 40 carbon atoms, a chloroaryl group having 6 to 20 carbon atoms,
a chloroalkylaryl group having 7 to 40 carbon atoms, a bromoaryl
group having 6 to 20 carbon atoms, a bromoalkylaryl group having 7
to 40 carbon atoms, an iodoaryl group having 6 to 20 carbon atoms,
and an iodoalkylaryl group having 7 to 40 carbon atoms; at least
one of R.sup.13 and R.sup.14 is selected from an aryl group having
7 to 18 carbon atoms, a chloroaryl group having 6 to 20 carbon
atoms, a chloroalkylaryl group having 7 to 40 carbon atoms, a
bromoaryl group having 6 to 20 carbon atoms, a bromoalkylaryl group
having 7 to 40 carbon atoms, an iodoaryl group having 6 to 20
carbon atoms, an iodoalkylaryl group having 7 to 40 carbon atoms,
and a fluoroalkylaryl group having 7 to 40 carbon atoms; M is Ti,
Zr, or Hf; Y is carbon or silicon; Q is selected from halogen, a
hydrocarbon group, a neutral, conjugated or non-conjugated diene
having 10 or less carbon atoms, an anionic ligand, and a neutral
ligand capable of coordination with a lone electron pair, in
identical or different combinations; and j is an integer from 1 to
4).
[1464] Hereinafter, specific examples of the bridged metallocene
compound represented by above General Formula [9]will be given (in
the present specification, may also be referred to as "component
(I')"), but the scope of the present invention is not intended to
be particularly limited thereby. Herein,
octamethyloctahydrodibenzofluorene refers to a structure
represented by Formula [10],
octamethyltetrahydrodicyclopentafluorene refers to a structure
represented by Formula [11], and dibenzofluorene refers to a
structure represented by Formula [12].
##STR00021##
The specific examples include
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)-
zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)-
zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclo-
pentafluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-d-
i-tert-butylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di-
-tert-butylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylflu-
orenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)-
zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)-
zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclo-
pentafluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-bu-
tylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-d-
i-tert-butylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di-
-tert-butylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetratert-butylfluo-
renyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)z-
irconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)z-
irconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofl-
uorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclop-
entafluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-di-
-tert-butylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
di(p-bromophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluo-
renyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)z-
irconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)z-
irconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofl-
uorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclop-
entafluorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-but-
ylfluorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-di-
-tert-butylfluorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
di(m-bromophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluo-
renyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zi-
rconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zi-
rconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzoflu-
orenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclope-
ntafluorenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-buty-
lfluorenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-buty-
lfluorenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
di(p-iodophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluor-
enyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahyd-
rodibenzofluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahy-
drodicyclopentafluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)-
zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphen-
yl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-ter-
t-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahyd-
rodibenzofluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahy-
drodicyclopentafluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)-
zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphen-
yl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(p-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-ter-
t-butylfluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahyd-
rodibenzofluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahy-
drodicyclopentafluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)-
zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphen-
yl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(p-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-ter-
t-butylfluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-butyl-
fluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahyd-
rodibenzofluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrahy-
drodicyclopentafluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)-
zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphen-
yl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(m-trichloromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-ter-
t-butylfluorenyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirc-
onium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirc-
onium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluor-
enyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyclopent-
afluorenyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconium
dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-di-te-
rt-butylfluorenyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
di(p-biphenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylfluoren-
yl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-b-
utylfluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-b-
utylfluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloct-
ahydrodibenzofluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltet-
rahydrodicyclopentafluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluore-
nyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl--
3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl--
3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethy-
lphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethyl-
phenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-ditrifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-
-tert-butylfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-buty-
lfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-buty-
lfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloctahy-
drodibenzofluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltetrah-
ydrodicyclopentafluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluorenyl-
)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethylph-
enyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethylphe-
nyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
di(3,5-dichloromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-te-
rt-butylfluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoreny-
l)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenz-
ofluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyc-
lopentafluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconiu-
m dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(4-chloronaphthyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylf-
luorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoreny-
l)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenz-
ofluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyc-
lopentafluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)
(dibenzofluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(3-chloronaphthyl)methylene(cyclopentadienyl)(2,3,6,
7-tetra-tert-butylfluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoreny-
l)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluoreny-
l)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenz-
ofluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(octamethyltetrahydrodicyc-
lopentafluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirconiu-
m dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-tert--
butylfluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3,6-
-di-tert-butylfluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,6--
di-tert-butylfluorenyl)zirconium dichloride,
di(5-chloronaphthyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-butylf-
luorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluore-
nyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluore-
nyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibe-
nzofluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodic-
yclopentafluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zircon-
ium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3-
,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,-
6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-buty-
lfluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluore-
nyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluore-
nyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibe-
nzofluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrodic-
yclopentafluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zircon-
ium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-3-
,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-3,-
6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-buty-
lfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-b-
utylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-b-
utylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyloct-
ahydrodibenzofluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyltet-
rahydrodicyclopentafluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluore-
nyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphenyl--
3,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl--
3,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimethy-
lphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimethyl-
phenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
phenyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-
-tert-butylfluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluo-
renyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodi-
benzofluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrod-
icyclopentafluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirc-
onium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-
-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)--
3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(p-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-bu-
tylfluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluo-
renyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylfluo-
renyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodi-
benzofluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydrod-
icyclopentafluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zirc-
onium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-
ert-butylfluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl)-
-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)--
3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-bu-
tylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-tert-
-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-tert-
-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethylo-
ctahydrodibenzofluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethylt-
etrahydrodicyclopentafluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzofluo-
renyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dipheny-
l-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethy-
l-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trimet-
hylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimeth-
ylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
naphthyl(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-tet-
ra-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylflu-
orenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylflu-
orenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrod-
ibenzofluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydro-
dicyclopentafluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zir-
conium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl-
)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-
-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(p-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-b-
utylfluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-di-tert-butylflu-
orenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(3,6-di-tert-butylflu-
orenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrod-
ibenzofluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyltetrahydro-
dicyclopentafluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(dibenzofluorenyl)zir-
conium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di--
tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(trimethylphenyl-
)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,7-(dimethylphenyl)-
-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-chlorophenyl)methylene(cyclopentadienyl)(2,3,6,7-tetra-tert-b-
utylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-di-ter-
t-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(3,6-di-ter-
t-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyl-
octahydrodibenzofluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(octamethyl-
tetrahydrodicyclopentafluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(dibenzoflu-
orenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-diphen-
yl-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimeth-
yl-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(trime-
thylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-(dimet-
hylphenyl)-3,6-di-tert-butylfluorenyl)zirconium dichloride,
(p-tolyl)(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,3,6,7-te-
tra-tert-butylfluorenyl)zirconium dichloride, and the like.
[1466] Furthermore, compounds resulting from replacing the
"zirconium" of the compounds described above with "hafnium" or
"titanium", and metallocene compounds having "difluoride",
"dibromide" or "diiodide" instead of "dichloride", or having
"dimethyl" or "methylethyl" instead of "dichloride", and the like
are also examples of the metallocene compound represented by
General Formula [9].
[1467] The bridged metallocene compound (I') described above can be
produced by referring to known methods. As the known method for
production, for example, the method for production described in the
pamphlet of WO 04/029062 filed by the present applicant may be
mentioned.
[1468] The metallocene compounds as described above can be used
individually or in combination of two or more kinds.
[1469] As the organoaluminum oxy compound (II-1) used in the
production of the propylene..alpha.-olefin copolymer (7B), the same
compounds mentioned as the organoaluminum oxy compounds (II-1) used
in the production of the syndiotactic propylene polymer (7A)
described above, may be used.
[1470] As the compound (II-2) reacting with the bridged metallocene
compound (I') to form an ion pair used in the production of the
propylene..alpha.-olefin copolymer (7B), the same compounds
mentioned as the compounds (II-2) reacting with the bridged
metallocene compound (I) to form an ion pair used in the production
of the syndiotactic propylene polymer (7A) described above, may be
used.
[1471] As the organoaluminum compound (II-3) used in the production
of the propylene..alpha.-olefin copolymer (7B), the same compounds
mentioned as the organoaluminum compounds (II-3) used in the
production of the syndiotactic propylene polymer (7A), may be
used.
[1472] Further, the above-mentioned respective components may be
used while being supported on a particulate support. As the support
used as necessary, the same supports used in the production of the
syndiotactic propylene polymer (7A) can be used.
[1473] Method for Producing Propylene..alpha.-Olefin Copolymer
(7B)
[1474] In the polymerization, the mode of using each of the
components, and the order of addition are arbitrarily selected, and
the following methods may be mentioned:
[1475] a method of adding the component (I') and the component (II)
into the polymerization vessel in an arbitrary order.
[1476] In the method described above, at least two or more of the
catalyst components may be brought into contact in advance.
[1477] When the polymerization of olefins is performed using the
catalyst for olefin polymerization as described above, the
component (I') is usually used in an amount of 10.sup.-9 to
10.sup.-1 moles, and preferably 10.sup.-8 to 10.sup.-2 moles, per
liter of the reaction volume.
[1478] The component (II-1) is used in an amount such that the
molar ratio of the component (II-1) to the total transition metal
atoms (M) in the component (I') [(II-1)/M] is usually 0.01 to
5,000, and preferably 0.05 to 2,000. The component (II-2) is used
in an amount such that the molar ratio of the aluminum atoms in the
component (II-2) to the total transition metal atoms (M) in the
component (I') [(II-2)/M] is usually 1 to 1,000, and preferably 1
to 500. The component (II-3) is used in an amount such that the
molar ratio of the component (II-3) to the transition metal atoms
(M) in the component (a) [(II-3)/M] is usually 1 to 10,000, and
preferably 1 to 5,000.
[1479] For the propylene..alpha.-olefin copolymer (7B), propylene
and at least one olefin selected from .alpha.-olefins having 2 to
20 carbon atoms (excluding propylene) are usually copolymerized in
the liquid phase in the presence of the catalyst for olefin
polymerization as described above. Here, hydrocarbon solvents are
generally used, but the .alpha.-olefins may also be used as the
solvent. As the hydrocarbon medium, the same compounds as those
described above may be specifically mentioned. The copolymerization
can be performed in any mode such as batch mode or continuous
mode.
[1480] Examples of the .alpha.-olefin that can be used in the
polymerization include ethylene, 1-butene, 1-pentene,
3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene,
3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene, and the like. The
.alpha.-olefins can be used alone or in combination of two or more
kinds.
[1481] When performing the copolymerization in batch mode using the
catalyst for olefin polymerization, the concentration of the
metallocene compound in the polymerization system is usually
0.00005 to 1 millimoles, and preferably 0.0001 to 0.50 millimoles,
per 1 liter of the polymerization volume.
[1482] Furthermore, the reaction time (average residence time in
the case of performing the copolymerization in the continuous mode)
may vary depending on the conditions such as catalyst
concentration, polymerization temperature, and the like, but it is
usually 5 minutes to 3 hours, and preferably 10 minutes to 1.5
hours.
[1483] The propylene and the at least one olefin selected from
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene)
are each supplied in an amount such that the
propylene..alpha.-olefin copolymer (7B) of specific composition can
be obtained. In the copolymerization, a molecular weight modifier
such as hydrogen can also be used.
[1484] When propylene and at least one olefin selected from
.alpha.-olefins having 2 to 20 carbon atoms (excluding propylene)
are copolymerized as described above, the propylene..alpha.-olefin
copolymer (7B) is usually obtained as a polymerization solution
containing the same. This polymerization solution is treated
according to conventional methods to give the
propylene..alpha.-olefin copolymer (7B).
[1485] The copolymerization reaction is usually performed under the
conditions of a temperature of 40.degree. C. to 200.degree. C.,
preferably 40.degree. C. to 180.degree. C., and more preferably
50.degree. C. to 150.degree. C., and of a pressure of greater than
0 to 10 Mpa, preferably 0.5 to 10 Mpa, and more preferably 0.5 to 7
Mpa.
[1486] <Ethylene..alpha.-Olefin Random Copolymer (7C)>
[1487] The ethylene..alpha.-olefin random copolymer (7C) used in
the present invention (7) is desirably an ethylene..alpha.-olefin
copolymer containing 50 to 99 mol % of ethylene units, and 1 to 50
mol % of units of .alpha.-olefin having 3 to 20 carbon atoms other
than ethylene (the sum of amounts of ethylene and .alpha.-olefin is
100 mol %).
[1488] Preferably, the copolymer contains ethylene units in an
amount of 60 to 95 mol %, and units of an .alpha.-olefin having 3
to carbon atoms other than ethylene in an amount of 5 to 40 mol %
(the sum of amounts of ethylene and .alpha.-olefin is 100 mol %),
has a density of 910 to 850 kg/m.sup.3, and has an MFR in the range
of 0.01 to 100 g/10 min, as measured according to JIS K-6721 at
190.degree. C. under a load of 2.16 kg.
[1489] More preferably, the copolymer contains ethylene units in an
amount of 80 to 95 mol %, and units of an .alpha.-olefin having 3
to 20 carbon atoms other than ethylene in an amount of 5 to mol %
(the sum of amounts of ethylene and .alpha.-olefin is 100 mol %),
has a density of 900 to 860 kg/m.sup.3, and has an MFR in the range
of 0.05 to 10 g/10 min, as measured according to JIS K-6721 at
190.degree. C. under a load of 2.16 kg.
[1490] The .alpha.-olefin to be copolymerized with ethylene is an
.alpha.-olefin having 3 to 20 carbon atoms, and specific examples
thereof include propylene, 1-butene, 1-pentene, 1-hexene,
1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,
1-hexadodecene, 1-octadecene, 1-nonadecene, 1-eicosene,
4-methyl-1-pentene, and the like. Among these, the .alpha.-olefins
having 3 to 10 carbon atoms are preferred. In particular,
propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene are
preferred. These .alpha.-olefins are used individually or in
combination of two or more kinds.
[1491] Also, the ethylene..alpha.-olefin random copolymer (7C) may
contain other polymerizable monomer units in addition to those
units, within the scope of not impairing the purpose of the present
invention.
[1492] Examples of these other polymerizable monomers include vinyl
compounds such as styrene, vinylcyclopentene, vinylcyclohexane, and
vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated
organic acids or derivatives thereof, such as maleic anhydride;
conjugated dienes such as butadiene, isoprene, pentadiene, and
2,3-dimethylbutadiene; and non-conjugated polyenes such as
1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene,
6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene,
cyclohexadiene, dicyclooctadiene, methylenenorbornene,
5-vinylnorbornene, 5-ethylidene-2-norbornene,
5-methylene-2-norbornene, 5-isopropylidene-2-norbornene,
6-chloromethyl-5-isopropenyl-2-norbornene,
2,3-diisopropylidene-5-norbornene,
2-ethylidene-3-isopropylidene-5-norbornene, and
2-propenyl-2,2-norbornadiene. According to a preferred embodiment,
the copolymer does not contain non-conjugated dienes and
non-conjugated polyenes.
[1493] The ethylene..alpha.-olefin random copolymer (7C) may
contain such other polymerizable monomer units in an amount of 10
mol % or less, preferably 5 mol % or less, and more preferably 3
mol % or less.
[1494] Specific examples of the ethylene..alpha.-olefin random
copolymer (7C) include an ethylene.propylene random copolymer, an
ethylene.1-butene random copolymer, an ethylene.propylene.1-butene
random copolymer, an ethylene.propylene.ethylidenenorbornene random
copolymer, an ethylene.1-butene.1-octene random copolymer, an
ethylene.4-methyl-1-pentene random copolymer, an ethylene.1-hexene
random copolymer, an ethylene.1-octene random copolymer, and the
like. Among these, an ethylene-propylene random copolymer, an
ethylene.1-butene random copolymer, an ethylene.1-butene-1-octene
random copolymer, an ethylene.1-hexene random copolymer, an
ethylene.1-octene random copolymer, and the like are particularly
preferably used. These copolymers may be used in combination of two
or more kinds.
[1495] Also, the ethylene..alpha.-olefin random copolymer (7C) used
in the present invention (7) has a degree of crystallization, as
measured by X-ray diffractometry, of usually 40% or less,
preferably 0 to 39%, and more preferably 0 to 35%. Also, the
ethylene..alpha.-olefin random copolymer (7C) used in the present
invention has an intrinsic viscosity [.eta.], as measured in
decalin at 135.degree. C., of usually 0.1 to 10 dL/g, and more
preferably 0.5 to 5 dL/g.
[1496] According to the present invention (7), by using the
component (7C), the balance between impact resistance and
transparency in particular is improved.
[1497] The ethylene..alpha.-olefin random copolymer as described
above can be produced by conventionally known methods using a
vanadium-based catalyst, a titanium-based catalyst, or a
metallocene-based catalyst. As the ethylene..alpha.-olefin random
copolymer (7C), for example, commercially available products such
as "TAFMER.TM." manufactured by Mitsui Chemicals, Inc., and the
like may be used.
[1498] [Polypropylene-Based Resin Composition]
[1499] The polypropylene-based resin composition containing the
syndiotactic propylene polymer (7A), the propylene..alpha.-olefin
copolymer (7B), and if necessary, the ethylene..alpha.-olefin
random copolymer (7C), may be obtained by melt-kneading these
components optionally together with various additives such as an
antioxidant, an ultraviolet absorbing agent, an antistatic agent, a
nucleating agent, a lubricant, a flame retardant, an anti-blocking
agent, a coloring agent, an inorganic or organic filler, and
various synthetic resins. The composition thus obtained is
palletized to form pellets.
[1500] The polypropylene resin that can be used in the present
invention (7) preferably contains:
[1501] 85 to 25 parts by weight of the syndiotactic propylene
polymer (7A);
[1502] 15 to 75 parts by weight of the propylene..alpha.-olefin
copolymer (7B) (the sum of amounts of (7A) and (7B) is 100 parts by
weight); and, if necessary,
[1503] 1 to 100 parts by weight of the ethylene..alpha.-olefin
copolymer (7C) based on 100 parts by weight of the sum of amounts
of (7A) and (7B).
[1504] When the contents of respective components are within this
range, the polypropylene resin gives a film particularly excellent
in heat resistance (Tm of film) and further excellent in
transparency, flexibility, and low temperature impact
resistance.
[1505] Where a polypropylene-based resin film having good
flexibility and excellent low temperature impact resistance is
required, the polypropylene resin preferably contains:
[1506] 80 to 25 parts by weight of the syndiotactic propylene
polymer (7A);
[1507] 20 to 75 parts by weight of the propylene..alpha.-olefin
copolymer (7B) (the sum of amounts of (7A) and (7B) is 100 parts by
weight); and
[1508] 1 to 100 parts by weight of the ethylene..alpha.-olefin
copolymer (7C) based on 100 parts by weight of the sum of amounts
of (7A) and (7B).
[1509] More preferably, the syndiotactic propylene polymer (7A)
content is in the range of 75 to 25 parts by weight, more
preferably 75 to 35 parts by weight, and the
propylene..alpha.-olefin copolymer (7B) content is in the range of
preferably 25 to 75 parts by weight, more preferably 25 to 65 parts
by weight. The polypropylene resin as described above can be molded
into the polypropylene-based resin film of the present invention by
an extrusion or inflation molding method.
[1510] <Requirement (6)>
[1511] The polypropylene-based resin constituting the
polypropylene-based resin film of the present invention (7) has a
propylene unit concentration (Sp) of 40 to 95 mol %, preferably to
90 mol %, an ethylene unit concentration (SE) of 60 to 5 mol %,
preferably 55 to 8 mol %, and a C4-10 .alpha.-olefin unit
concentration (S.alpha.) of 0 to 15 mol %, preferably 2 to 13 mol %
(Sp+SE+S.alpha.=100 mol %, and Sp/SE>1). Here, these values are
measured according to a measurement method that will be described
later in Examples. When the propylene units, the ethylene units,
and the .alpha.-olefin units of 4 to 10 carbon atoms are contained
in such ranges, the polypropylene-based resin film tends to exhibit
sufficient transparency, flexibility, mechanical strength, heat
resistance, and impact resistance.
[1512] <Requirement (7)>
[1513] The polypropylene-based resin film of the present invention
(7) satisfies the requirement that the intrinsic viscosity [.eta.]
of a n-decane-soluble component (Dsol) which is soluble in n-decane
at room temperature is 1.5 to 4.0 dl/g, preferably 1.5 to 3.5 dl/g,
and more preferably 1.7 to 3.2 dl/g. When the intrinsic viscosity
[.eta.] of the n-decane-soluble component (Dsol) which is soluble
in n-decane at room temperature falls within this range, the
polypropylene-based resin film is particularly excellent in heat
resistance, transparency, low temperature impact strength,
flexibility, and flowability, and is especially excellent in the
balance between low temperature impact resistance and
transparency.
[1514] [Method for Producing Polypropylene-Based Resin Film]
[1515] The polypropylene-based resin constituting the
polypropylene-based resin film of the present invention (7) may be
any resin having propylene units, and may be a composition of
crystalline propylene polymer and elastomer. For the
polypropylene-based resin film of the present invention, the
production method, constitution, and molding method for the
polypropylene-based resin are not particularly limited as long as
the properties as described above are satisfied.
[1516] For the molding method, an inflation method and a
(co)extrusion T die method are preferably employed in consideration
of the hygienic and economical aspects. Specifically, the
aforementioned pellets may be melt-extruded using an extruder and a
circular die, then further extruded through a spiral or slit die,
and inflated by predetermined air flow to prepare a film (inflation
method). As the cooling method, a water-cooling method or an
air-cooling method can be employed.
[1517] Conditions for the water-cooling inflation molding method
are not particularly limited, but preferably the molding
temperature is from 190 to 280.degree. C., and the water-cooling
temperature is from 10 to 60.degree. C.
[1518] Alternatively, the pellets may be melt-extruded using an
extruder and a circular die, then further extruded using a
coat-hanger die and a T-die, and cooled to prepare a film
(extrusion molding). In order to produce a multilayer, a multilayer
T-die method, a dry lamination method, an extrusion lamination
method, or the like can be employed. The molding conditions are not
particularly limited, but preferably the molding temperature is
from 190 to 280.degree. C., and the cooling temperature of chill
rolls is from 10 to 80.degree. C.
[1519] [Multilayer Film]
[1520] The polypropylene-based resin monolayer film of the present
invention (7) is not only used as the monolayer but can also be
suitably used for the production of the multilayer film by a
co-extrusion film-forming method. The present invention (7) relates
to a multilayer film which can be obtained by the co-extrusion
film-forming method and comprises the polypropylene-based resin
monolayer film as a base layer and an outer layer comprising a
polyolefin-based resin on at least one side of the base layer.
[1521] In a preferred embodiment of the multilayer film, it is
preferable that propylene-based resins (random, homo, syndio or
alloy composition) each having a thickness of 10 to 50 .mu.m,
preferably 15 to 40 .mu.m are laminated on both outer surfaces of
the polypropylene-based resin monolayer film of the present
invention (7), from the viewpoints of heat resistance and
inter-adhesiveness. In addition, it is preferable that a
propylene-based resin (random, homo, syndio or alloy composition)
having a thickness of 10 to 50 .mu.m, preferably 15 to 40 .mu.m is
laminated in between two polypropylene monolayer films of the
present invention, from the viewpoint of barrier properties.
[1522] With regard to the constitution of layers of the multilayer
film, there may be a case where the multilayer film has 4 or more
layers. Although there is no particular limitation, the thickness
of the polypropylene-based resin monolayer film of the present
invention (7) is preferably 150 .mu.m or more when the thickness of
the multilayer film is 250 .mu.m. Within this thickness range, an
excellent balance between flexibility, transparency, and impact
resistance can be provided. The multilayer may include a gas
barrier layer, an adhesive layer, and the like. Examples of the gas
barrier layer include a PET layer, an EVOH layer, a cyclic olefin
polymer layer, and an aluminum-deposition film. Examples of the
adhesive layer include a layer of an olefin polymer (Admer) in
which a polar group is introduced.
[1523] [Method for Manufacturing Food and Medical Containers]
[1524] The food and medical containers comprising the monolayer or
multilayer film of the present invention (7) can be manufactured by
cutting by a general method the tube-shaped or sheet-shaped film
obtained by the molding method described above, then heat sealing
the cut film, and attaching a mouth member by a heat sealing method
or the like, thereby producing containers having predetermined
shape and size. Conditions for the heat sealing of the film vary
depending on the thickness of the film, but it is preferable that
the temperature is usually around 120 to 250.degree. C.
EXAMPLES
[1525] Hereinafter, the present inventions (1) to (7) will be
described in more detail with reference to [Example I] to Example
VII, respectively.
Example I
[1526] Hereinafter, the present invention (1) will be described in
more detail based on Synthesis Examples and Examples, but the
present invention is not intended to be limited to these Examples.
The methods described in the following patent documents were used
for synthesizing
dibenzylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride,
cyclohexylidene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zir-
conium dichloride,
cyclohexylidene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zir-
conium dichloride,
dimethylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride,
dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, and
diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride.
[1527] JP-A No. 2000-212194,
[1528] JP-A No. 2004-168744,
[1529] JP-A No. 2004-189666.
[1530] The structures of the compounds obtained in Synthesis
Examples were determined using 270 MHz .sup.1H-NMR (JEOL LTD.
GSH-270), FD-mass analysis (JEOL LTD. SX-102 A) and the like.
Synthesis Example 1-1
Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride
(i) Synthesis of 2,7-dibromo-3,6-ditert-butylfluorene
[1531] Under a nitrogen atmosphere, a 300-mL three-necked flask was
charged with 15.22 g (54.7 mmol) of 3,6-ditert-butylfluorene
synthesized according to the method described in Bull. Chem. Soc.
Jpn., 59, 97 (1986) and 170 mL of propylene carbonate, and the
mixture was stirred. To this solution, 20.52 g (115 mmol) of
N-bromosuccinimide was added, and the mixture was heated and
stirred at 80.degree. C. for 5 hours. Subsequently, the mixture was
left to be naturally cooled. The reaction solution was added to 800
mL of water, and the mixture was stirred at room temperature for 15
minutes. Then, solids precipitated were separated by filtration.
The solids obtained were washed 5 times with 10 mL of ethanol.
Subsequently, a mixture solution of n-hexane and a small amount of
dichloromethane was added to the solids, and the mixture was heated
to 60.degree. C. to dissolve the solids completely. The resultant
solution was left to stand overnight at -20.degree. C. Crystals
precipitated were washed 3 times with 5 mL of hexane to obtain a
target product (yield 21.16 g (76%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1532] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.60 (s,
tBu(Flu), 18H), 3.75 (s, Flu-9H, 2H), 7.73 (s, Flu, 2H), 7.81 (s,
Flu, 2H).
[1533] MS (FD): M/z 436 (M.sup.+).
(ii) Synthesis of 2,7-diphenyl-3,6-ditert-butyl-fluorene
[1534] Under a nitrogen atmosphere, a 300-mL three-necked flask was
charged with 8.15 g (18.7 mmol) of
2,7-dibromo-3,6-ditert-butyl-fluorene and 1.08 g (0.93 mmol) of
Pd(PPh.sub.3), and further charged with 120 mL of dehydrated
1,2-dimethoxyethane. The mixture was stirred at room temperature
for 20 minutes. To this solution, 20 mL of an ethanol solution in
which 5.01 g (41.1 mmol) of phenylboric acid was dissolved was
added, and the mixture was then stirred at room temperature for 20
minutes. Thereafter, 37.4 mL (74.8 mmol) of a 2.0 mol/L aqueous
solution of sodium carbonate was added. Subsequently, the mixture
was heated to reflux for 18 hours, left to be naturally cooled, and
quenched with dilute hydrochloric acid in an ice bath. Thereafter,
ether was added to extract the soluble fraction, and the organic
layer was washed two times with a saturated aqueous solution of
sodium hydrogen carbonate, two times with water, and two times with
saturated brine, and then dried over magnesium sulfate.
Subsequently, the solvent was distilled off, and the resulting
solids were subjected to separation by column chromatography to
obtain a target product (yield 4.36 g (54%)). The target product
was identified by .sup.1H-NMR and FD-MS spectroscopy.
[1535] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.29 (s,
tBu(Flu), 18H), 3.78 (s, Flu-9H, 2H), 7.16 (s, Flu, 2H), 7.34 (br,
PhFlu, 10H), 7.97 (s, Flu, 2H).
[1536] MS (FD): M/z 430 (M.sup.+).
(iii) Synthesis of 6,6-dibenzofulvene
[1537] Under a nitrogen atmosphere, a 500-mL three-necked flask was
charged with 8.0 g (121 mmol) of cyclopentadiene and 100 mL of
dehydrated tetrahydrofuran, and the mixture was stirred. This mixed
solution was cooled in an ice bath, and 80 mL (125.6 mmol) of a
1.57 mol/L hexane solution of n-butyllithium was then added.
Thereafter, the mixture was stirred at room temperature for 3
hours. The resulting white slurry was cooled in an ice bath, and
then a solution prepared by dissolving 25.0 g (118 mmol) of
1,3-diphenyl-2-propanone in 50 mL of dehydrate tetrahydrofuran was
added. Subsequently, the mixture was stirred at room temperature
for 12 hours. The resulting yellow solution was quenched with a
saturated aqueous solution of ammonium chloride. The soluble
fraction was extracted with 100 mL of n-hexane, and this organic
phase was washed with water and saturated brine, and then dried
over magnesium sulfate. The solvent was distilled off, and the
residue was purified by column chromatography to obtain a target
product as a yellow solid (yield 3.7 g (12%)). The target product
was identified by .sup.1H-NMR.
[1538] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 3.69 (s,
PhCH.sub.2, 4H), 6.60-6.72 (m, Cp, 4H), 7.13-7.32 (m, PhCH.sub.2,
10H).
(iv) Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorene-
)
[1539] Under a nitrogen atmosphere, mL of dehydrate tetrahydrofuran
was added to 1.60 g (3.71 mmol) of
2,7-diphenyl-3,6-ditert-butylfluorene, and the mixture was stirred.
This solution was cooled in an ice bath, and 2.65 mL (4.13 mmol) of
a 1.56 mol/L hexane solution of n-butyllithium was added. The
mixture was stirred at room temperature for 2 hours. The resulting
red solution was cooled to -78.degree. C. in a dry ice-methanol
bath, a solution of 1.06 g (4.10 mmol) prepared by dissolving
6,6-dibenzofulvene in 20 mL of tetrahydrofuran was added dropwise
over 20 minutes. Subsequently, the mixture was stirred for 18 hours
while gradually warming to room temperature. To the resulting
red-black solution, 60 mL of 1 N hydrochloric acid was added to
terminate the reaction. 80 mL of diethyl ether was added to perform
liquid-liquid phase separation, and the soluble fraction was
extracted. This organic layer was washed two times with a saturated
aqueous solution of sodium hydrogen carbonate, two times with
water, and once with saturated brine, and then dried over magnesium
sulfate. The solvent was distilled off, and the residue was
purified by silica gel chromatography to obtain a target product as
a pale yellow powder (yield 0.59 g (23%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1540] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.25 (s,
tBu(Flu), 18H), 2.66 (br, CpH, 1H), 3.22 (br, CH.sub.2Ph, 4H), 4.41
(br, Flu-9H, 1H), 5.85-6.51 (m, Cp, 4H), 6.82-7.40 (m, Ph(Flu) and
CH.sub.2Ph and Flu, 22H), 7.67 (s, Flu, 2H).
[1541] MS (FD): M/z 688 (M.sup.+).
(v) Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride
[1542] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 0.59 g (0.855 mmol) of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorene-
) and 40 mL of dehydrated diethyl ether, and the mixture was
stirred. This mixed slurry solution was cooled in an ice bath, and
1.21 mL (1.88 mmol) of a 1.56 mol/L hexane solution of
n-butyllithium was added. The mixture was stirred for 45 hours
while gradually warming to room temperature. The resulting red
reaction solution was cooled to -78.degree. C. in a dry
ice/methanol bath, and then 0.200 g (0.858 mmol) of zirconium
tetrachloride was added. Subsequently, the mixture was stirred for
42 hours while gradually warming to room temperature to obtain a
red-orange suspension. The solvent was removed by distillation
under reduced pressure. Under a nitrogen atmosphere, the residue
was dissolved in n-hexane, and the liquid was passed through a
glass filter filled with Celite, insolubles were washed n-hexane,
and the orange colored powder insoluble in n-hexane was subjected
to extraction with dichloromethane. The solvent in which the
dichloromethane-solubles were dissolved was distilled off. The
residue was washed with diethyl ether/cold n-pentane and dried to
obtain a target product as an orange-colored powder (yield 515 mg
(71%)). The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1543] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.30 (s,
tBu(Flu), 18H), 3.82 (d, J=15.5 Hz, CH.sub.2Ph, 2H), 3.93 (d,
J=15.5 Hz, CH.sub.2Ph, 2H), 5.80 (t, J=2.6 Hz, Cp, 2H), 6.25 (t,
J=2.6 Hz, Cp, 2H), 6.97-7.34 (m, Ph(Flu) and CH.sub.2Ph, 20H), 7.37
(s, Flu, 2H), 8.32 (s, Flu, 2H).
[1544] MS (FD): M/z 848 (M.sup.+).
Synthesis Example 1-2
Synthesis of
di(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride
(i) Synthesis of 6,6-di(n-butyl)fulvene
[1545] Under a nitrogen atmosphere, a 200-mL three-necked flask was
charged with 15 mL of methanol and 11.8 mL (146 mmol) of
pyrrolidine. The mixture was cooled in an ice bath. Subsequently,
20.21 g (144 mmol) of 5-nonanone and 11.0 mL (146 mmol) of
cyclopentadiene were added, and the mixture was stirred at room
temperature for 22 hours. 100 mL of diethyl ether and 100 mL of
water were added to extract the soluble fraction. This organic
layer was washed two times with water and once with saturated
brine, and dried over magnesium sulfate. The solvent was distilled
off, and the residue was purified by column chromatography to
obtain a target product as a yellow oil (yield 22.53 g (82%)). The
target product was identified by .sup.1H-NMR.
[1546] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.93 (t,
J=7.3 Hz, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 6H), 1.38 (sex, J=7.3
Hz, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 4H), 1.53 (quin, J=7.3 Hz,
CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 4H), 2.53 (t, J=7.3 Hz,
CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 4H), 6.40-6.57 (m, Cp, 4H).
(ii) Synthesis of
di(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluor-
ene)
[1547] Under a nitrogen atmosphere, 30 mL of dehydrated
tetrahydrofuran was added to 1.51 g (3.51 mmol) of
2,7-diphenyl-3,6-ditert-butyl-fluorene synthesized in Synthesis
Example 1-1 (ii), and the mixture was stirred. This solution was
cooled in an ice bath, and 2.50 mL (3.90 mmol) of a 1.56 mol/L
hexane solution of n-butyllithium was added. The mixture was
stirred at room temperature for 2 hours. The resulting dark red
solution was cooled to -78.degree. C. in a dry ice/methanol bath,
and a tetrahydrofuran solution prepared by dissolving 0.757 g (3.98
mmol) of 6,6-di(n-butyl)fulvene in 15 mL of tetrahydrofuran was
added dropwise over 15 minutes. Subsequently, the mixture was
stirred for 18 hours while gradually warming to room temperature.
50 mL of 1 N hydrochloric acid was added to the resulting red
solution to terminate the reaction. 100 mL of diethyl ether was
added to perform liquid-liquid phase separation, and the soluble
fraction was extracted. This organic layer was washed two times
with a saturated aqueous solution of sodium hydrogen carbonate, two
times with water and once with saturated brine, and dried over
magnesium sulfate. The solvent was distilled off, and the residue
was recrystallized from hexane to obtain a target product as a
white powder (yield 1.54 g (70%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1548] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.72 (t,
J=7.3 Hz, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 6H), 0.86-1.24 (m,
CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 8H), 1.26 (s, tBu(Flu), 18H),
1.57-1.72 (m, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 4H), 2.68 (br, CpH,
1H), 3.97 (br, Flu-9H, 1H), 5.70-6.55 (m, Cp, 4H), 6.78 (s, Flu,
2H), 7.15-7.50 (m, Ph(Flu), 10H), 7.81 (s, Flu, 2H).
[1549] MS (FD): M/z 620 (M.sup.+).
(iii) Synthesis of
di(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride
[1550] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 0.71 g (1.15 mmol) of
di(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluor-
ene) and 30 mL of dehydrated diethyl ether, and the mixture was
stirred. This mixed slurry solution was cooled in an ice bath, 1.62
mL (2.53 mmol) of a 1.56 mol/L hexane solution of n-butyllithium
was added. The mixture was stirred for 47 hours while gradually
warming to room temperature. The resulting red-orange reaction
solution was cooled to -78.degree. C. in a dry ice/methanol bath,
and then 0.265 g (1.14 mmol) of zirconium tetrachloride was added.
Subsequently, the mixture was stirred for 42 hours while gradually
warming to room temperature to obtain a red suspension. The solvent
was removed by distillation under reduced pressure. Under a
nitrogen atmosphere, the residue was dissolved in n-hexane, and the
mixture was passed through a glass filter filled with Celite,
insolubles were washed with n-hexane and the red powder insoluble
in n-hexane was subjected to extraction with dichloromethane. The
solvent in which the dichloromethane-solubles was dissolved was
distilled off. The residue was recrystallized from
dichloromethane/n-hexane to obtain a target product as an
orange-colored powder (yield 217 mg (24%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1551] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.82 (t,
J=7.3 Hz, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 6H), 1.12-1.70 (m,
CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 8H), 1.24 (s, tBu(Flu), 18H),
2.30-2.60 (m, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 4H), 5.53 (t, J=2.6
Hz, Cp, 2H), 6.26 (t, J=2.6 Hz, Cp, 2H), 7.15-7.40 (m, Ph(Flu) and
Flu, 12H), 8.19 (s, Flu, 2H).
[1552] MS (FD): M/z 780 (M.sup.+).
Synthesis Example 1-3
Synthesis of
di(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride
(i) Synthesis of 2,7-dimethyl-3,6-ditert-butyl-fluorene
[1553] Under a nitrogen atmosphere, 100 mL of dehydrated tertbutyl
methyl ether was added to 5.03 g (11.5 mmol) of
2,7-dibromo-3,6-ditert-butyl-fluorene synthesized in Synthesis
Example 1-1 (i) and 0.196 g (0.24 mmol) of PdCl.sub.2
(dppf).CH.sub.2Cl.sub.2, and the mixture was stirred. This solution
was cooled in an ice bath, and 19.2 mL (57.6 mmmol) of a 3 mol/L
diethyl ether solution of methyl magnesium bromide was added
dropwise over 15 minutes. The mixture was heated to reflux for 5
days. The mixture was left to be naturally cooled, and 1 N
hydrochloric acid was then added dropwise in an ice bath to
terminate the reaction. Diethyl ether was added to perform
liquid-liquid phase separation, and the organic layer was washed
two times with a saturated aqueous solution of sodium hydrogen
carbonate, two times with water, and once with saturated brine, and
dried over magnesium sulfate. The solvent was distilled off, and
the residue was subjected to separation by silica gel
chromatography to obtain a target product as a white powder (yield
2.07 g (63%)). The target product was identified by
.sup.1H-NMR.
[1554] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.50 (s,
tBu(Flu), 18H), 2.60 (s, Me(Flu), 6H), 7.26 (s, Flu, 2H), 7.75 (s,
Flu, 2H).
(ii) Synthesis of
di(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluor-
ene)
[1555] Under a nitrogen atmosphere, dehydrated tetrahydrofuran was
added to 0.783 g (2.55 mmol) of
2,7-dimethyl-3,6-ditert-butyl-fluorene, and the mixture was
stirred. This solution was cooled in an ice bath, and 1.85 mL (2.85
mmol) of a 1.54 mol/L hexane solution of n-butyllithium was added.
The mixture was stirred at room temperature for 2 hours. The
resulting orange-colored solution was cooled to -78.degree. C. in a
dry ice/methanol bath, and a solution prepared by dissolving 0.571
g (3.00 mmol) of 6,6-di(n-butyl)fulvene synthesized in Synthesis
Example 1-2 (i) in 15 mL of dehydrated tetrahydrofuran was added
dropwise over 20 minutes, and the mixture was stirred for 2 hours.
100 mL of 1 N hydrochloric acid was added to the resulting
orange-colored solution to terminate the reaction. 100 mL of
diethyl ether was added to perform liquid-liquid phase separation,
and the soluble fraction was extracted. This organic layer was
washed two times with a saturated aqueous solution of sodium
hydrogen carbonate, two times with water, and once with saturated
brine, and dried over magnesium sulfate. The solvent was distilled
off, and the residue was recrystallized from diethyl ether/methanol
to obtain a target product as a white powder (yield 0.63 g (50%)).
The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1556] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.76 (t,
J=7.3 Hz, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 6H), 0.80-1.90 (m,
CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 10H), 1.46 (s, tBu(Flu), 18H),
2.50 (s, Me(Flu), 6H), 3.00 (br, CpH, 1H), 4.01 (br, Flu-9H, 1H),
5.85-6.70 (m, Cp, 4H), 6.93 (s, Flu, 2H), 7.60 (s, Flu, 2H).
[1557] MS (FD): M/z 496 (M.sup.+).
(iii) Synthesis of
di(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride
[1558] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 0.614 g (1.24 mmol) of
di(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluor-
ene) and 30 mL of dehydrated diethyl ether, and the mixture was
stirred. This mixed slurry solution was cooled in an ice bath, 1.78
mL (2.74 mmol) of a 1.54 mol/L hexane solution of n-butyllithium
was added, and the mixture was stirred for 16 hours while gradually
warming to room temperature. This red orange reaction solution was
cooled to -78.degree. C. in a dry ice/methanol bath, and then 0.239
g (1.02 mmol) of zirconium tetrachloride was added. Subsequently,
the mixture was stirred for 22 hours while gradually warming to
room temperature to obtain a red brown suspension. The solvent was
removed by distillation under reduced pressure. Under a nitrogen
atmosphere, the residue was dissolved in n-hexane, and the mixture
was passed through a glass filter filled with Celite, insolubles
were washed with n-hexane and a red powder insoluble in n-hexane
was subjected to extraction with dichloromethane. The solvent in
which the dichloromethane-solubles were dissolved was distilled
off. The residue was recrystallized from dichloromethane/n-hexane
to obtain a target product as an orange-colored powder (yield 286
mg (41%)). The target product was identified by .sup.1H-NMR and
FD-MS spectroscopy.
[1559] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.99 (t,
J=7.3 Hz, CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 6H), 1.30-1.78 (m,
CH.sub.2CH.sub.2CH.sub.2CH.sub.3, 8H), 1.46 (s, tBu(Flu), 18H),
2.53 (s, Me(Flu), 2.60-2.80 (m, CH.sub.2CH.sub.2CH.sub.2CH.sub.3,
4H), 5.60 (t, J=2.6 Hz, Cp, 2H), 6.21 (t, J=2.6 Hz, Cp, 2H), 7.38
(s, Flu, 2H), 7.95 (s, Flu, 2H).
[1560] MS (FD): M/z 656 (M.sup.+).
Synthesis Example 1-4
Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride
(i) Synthesis of 6,6-di(p-chlorophenyl)fulvene
[1561] Under a nitrogen atmosphere, a reaction vessel equipped with
a dropping funnel was charged with 40 mL of dry tetrahydrofuran and
2.15 mL (25.89 mmol) of cyclopentadiene. While cooling this
solution to 0.degree. C., 18 mL (28.47 mmol) of a 1.58 mol/L hexane
solution of n-butyllithium was slowly added dropwise and the
mixture was stirred. Subsequently, a dropping funnel was charged
with a solution prepared by dissolving 5.00 g (19.91 mmol) of
4,4'-dichlorobenzophenone in 30 mL of tetrahydrofuran, and the
solution was slowly added dropwise. The mixture was left to be
stand so that the temperature of the mixture was at room
temperature, and stirred for one day. This reaction solution was
then subjected to extraction with diethyl ether. The organic layer
was washed with 1 N hydrochloric acid, a saturated aqueous solution
of sodium hydrogen carbonate and saturated brine, and then dried
over magnesium sulfate. The solvent was removed by distillation
under reduce pressure. The residue was purified by using a silica
gel column to obtain a target product (yield 3.37 g (57%)). The
target product was identified by .sup.1H-NMR.
[1562] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm
6.21-6.24 (m, 2H), 6.60-6.63 (m, 2H), 7.23 (d, 2H, J=8.1 Hz), 7.37
(d, 2H, J=8.6 Hz).
(ii) Synthesis of
di-(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-bu-
tylfluorene)
[1563] Under a nitrogen atmosphere, a 200-mL three-necked flask was
charged with 3.5 g (8.1 mmol) of
2,7-diphenyl-3,6-ditert-butylfluorene synthesized in Synthesis
Example 1-1 (ii) and 100 mL of dehydrated tetrahydrofuran, and the
mixture was stirred. This solution was cooled to -78.degree. C. in
a dry ice/methanol bath, and 5.7 mL (8.87 mmol) of a 1.56 mol/L
hexane solution of n-butyllithium was added dropwise. Subsequently,
the mixture was stirred at room temperature for 3 hours. The
resulting solution was cooled again to -40.degree. C., a
tetrahydrofuran solution of 2.22 g (7.39 mmol) of
6,6-di(p-chlorophenyl)fulvene was added dropwise, and the mixture
was stirred at room temperature for 5 hours. Subsequently, the
solution was quenched with an aqueous solution of dilute
hydrochloric acid. 100 mL of n-hexane was added to the reaction
solution to extract the soluble fraction, and this organic layer
was washed with a saturated solution of sodium hydrogen carbonate,
water and saturated brine, and dried over magnesium sulfate.
Subsequently, the solvent was concentrated, and then the residue
was washed with n-hexane and methanol to obtain a target product
(yield 3.2 g (54%)). The target product was identified by
.sup.1H-NMR and FD-MS spectroscopy.
[1564] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.2 (s,
18H), 2.9 (s, 2H), 5.2 (s, 1H), 6.0 (d, 1H), 6.2 (d, 1H), 6.3 (s,
1H), 6.6 (s, 2H), 6.9 (s, 10H), 7.2-7.4 (m+s, 8H), 7.6 (s, 2H), MS
(FD): M/z 729 (M.sup.+)
(iii) Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert
butyl-fluorenyl)zirconium dichloride
[1565] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 60 mL of dehydrate diethyl ether and 1.0 g (1.4 mmol)
of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
yl-fluorene), and the mixture was stirred. This solution was cooled
to -78.degree. C. in a dry ice/methanol bath, and 1.8 mL (2.88
mmol) of a 1.56 mol/L hexane solution of n-butyllithium was added
dropwise, and the mixture was stirred at room temperature for 20
hours. Subsequently, the mixture was cooled to -60.degree. C. in a
dry ice/methanol bath, and then 0.37 g (1.59 mmol) of zirconium
tetrachloride was added. The mixture was then stirred at room
temperature for 20 hours. The solvent was removed by distillation
under reduced pressure, the residue was subjected to extraction
with n-hexane and dichloromethane under a nitrogen atmosphere, and
the residue was recrystallized from the respective solutions to
obtain a target product (yield 0.47 g (38%)). The target product
was identified by .sup.1H-NMR and FD-MS spectroscopy.
[1566] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.2 (s,
18H), 5.4 (m, 2H), 5.8 (s, 2H), 6.3 (m, 2H), 7-7.2 (s+m+m, 6H),
7.5-7.7 (m, 12H), 8.3 (s, 2H)
[1567] MS (FD): M/z 888 (M.sup.+)
Synthesis Example 1-5
Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-but-
yl-fluorenyl)zirconium dichloride
(i) Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-but-
yl-fluorene)
[1568] Under a nitrogen atmosphere, a 200-mL three-necked flask was
charged with 2.6 g (8.48 mmol) of
2,7-dimethyl-3,6-ditert-butyl-fluorene synthesized in Synthesis
Example 1-3 (i) and 100 mL of dehydrated tetrahydrofuran, and the
mixture was stirred. This mixed solution was cooled in an ice bath
to -78.degree. C., and 5.7 mL (8.9 mmol) of a 1.56 mol/L hexane
solution of n-butyllithium was added dropwise. Thereafter, the
mixture was stirred at room temperature for 3 hours. Then, solution
thus obtained was cooled to -40.degree. C. in a dry ice/methanol
bath, 60 mL of a tetrahydrofuran solution in which 2.78 g (9.33
mmol) of 6,6-di(p-chlorophenyl)fulvene synthesized in Synthesis
Example 1-4 (i) was dissolved was added dropwise. Subsequently, the
mixture was stirred for 1 hour while gradually warming to room
temperature. To the reaction solution, 100 mL of 1N hydrochloric
acid and 100 mL of n-hexane was sequentially added to extract the
soluble fraction. This organic layer was washed with water and
saturated brine, and then dried over magnesium sulfate. The solvent
was distilled off, and the residue was recrystallized from n-hexane
to obtain a target product (yield 4.4 g (86%)). The target product
was identified by .sup.1H-NMR and FD-MS spectroscopy.
[1569] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.3 (s,
18H), 2.3 (s, 6H), 3.0 (s, 2H), 5.2 (s, 2H), 6.1-6.3 (s, 4H), 6.7
(s, 2H), 7.0 (s, 6H), 7.4 (s, 2H)
[1570] MS (FD): M/z 604 (M.sup.+)
(ii) Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-but-
yl-fluorenyl)zirconium dichloride
[1571] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 1.0 g (1.65 mmol) of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-but-
yl-fluorene) and 50 mL of dehydrated diethyl ether, and the mixture
was stirred. This mixed slurry solution was cooled to -40.degree.
C. in an dry ice/methanol bath, and 2.2 mL (3.38 mmol) of a 1.56
mol/L hexane solution of n-butyllithium was then added. The mixture
was stirred for 22 hours while gradually warming to room
temperature. This reaction solution was cooled to -78.degree. C. in
a dry ice/methanol bath, and then 0.38 g (1.65 mmol) of zirconium
tetrachloride was added. Subsequently, the mixture was stirred for
20 hours while gradually warming to room temperature. The solvent
was removed by distillation under reduced pressure. Under a
nitrogen atmosphere, about 30 mL of n-hexane was added, and the
mixture was stirred. The insolubles were removed by filtration
through celite. Subsequently, the insolubles were dissolved in
dichloromethane and the insolubles were removed by filtration
through celite. The n-hexane extract was concentrated, and then the
solids precipitated were washed with n-hexane and n-pentane to
obtain a target product (yield 0.122 g (10%)). The target product
was identified by .sup.1H-NMR and FD-MS spectroscopy.
[1572] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.5 (s,
18H), 2.3 (s, 6H), 5.6 (m, 2H), 6.0 (m, 2H), 6.3 (m, 2H), 7.3 (dd,
2H), 7.4 (dd, 2H), 7.7 (dd, 2H), 7.8 (dd, 2H), 8.1 (s, 2H)
[1573] MS (FD): M/z 764 (M.sup.+)
Synthesis Example 1-6
Synthesis of
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
ditert-butylfluorenyl)zirconium dichloride
(i) Synthesis of 6,6-di(m-trifluoromethylphenyl)fulvene
[1574] Under a nitrogen atmosphere, 2.08 mL (25.14 mmol) of
cyclopentadiene was added to 70 mL of dehydrated tetrahydrofuran,
and the mixture was stirred. This solution was cooled to 0.degree.
C., and 16.3 mL (25.77 mmol) of a 1.58 mol/L hexane solution of
n-butyllithium was added dropwise. The mixture was stirred at room
temperature for 20 hours. The resultant solution was again cooled
to 0.degree. C., and 4.08 g (12.6 mmol) of 3,3'-ditrifluoromethyl
benzophenone in 30 mL of dehydrated tetrahydrofuran was added
dropwise over 15 minutes. The mixture was stirred at room
temperature for 2.5 hours, and 1N hydrochloric acid was added to
terminate the reaction. A liquid-liquid phase separation was
performed, and the aqueous layer was subjected to extraction with
diethyl ether twice. The resultant was then combined with the
organic layer obtained previously. The resulting liquid was washed
with a saturated aqueous solution of sodium hydrogen carbonate,
water, and saturated brine, and then dried over magnesium sulfate.
The solvent was distilled off, and the resultant was subjected to
separation by silica gel chromatography to obtain a target product
(yield 1.2 g (26%)). The target product was identified by
.sup.1H-NMR and FD-MS spectroscopy.
[1575] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm
6.17-6.21 (m, 2H), 6.64-6.66 (m, 2H), 7.44-7.58 (m, 6H), 7.68 (d,
2H).
[1576] MS (FD): m/z 366 (M.sup.+).
(ii) Synthesis of
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
ditert-butylfluorene)
[1577] Under a nitrogen atmosphere, a 300-mL three-necked flask was
charged with 2.1 g (6.85 mmol) of
2,7-diphenyl-3,6-ditert-butyl-fluorene synthesized in Synthesis
Example 1-1 (ii) and 60 mL of dehydrated tetrahydrofuran, and the
mixture was stirred. This solution was cooled to 0.degree. C., and
4.83 mL (7.5 mmol) of a 1.56 mol/L hexane solution of
n-butyllithium was added. Thereafter, the mixture was stirred at
room temperature for 2 hours. The solution thus obtained was cooled
to -78.degree. C. in a dry ice/methanol bath, and 2.39 g (6.52
mmol) of 6,6'-di(m-trifluoromethylphenyl) fulvene in 50 mL of
dehydrated tetrahydrofuran was added dropwise over 15 minutes. The
mixture was stirred for 10 minutes, and 1N hydrochloric acid was
added to the reaction solution to terminate the reaction. An
oil-liquid separation was performed, and the aqueous layer was
extracted twice with 50 mL of diethyl ether. The resultant was then
combined with the organic layer obtained previously. The resulting
liquid was washed with a saturated aqueous solution of sodium
hydrogen carbonate, water, and saturated brine, and then dried over
magnesium sulfate. The solvent was distilled off, and 4.8 g of the
residue was dissolved in 15 mL of dichloromethane. The liquid was
then added dropwise to 300 mL of methanol. The methanol solution
was cooled to 0.degree. C., and the resulting crystals were
separated by filtration to obtain a target product (yield 2.3 g
(50%)). The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1578] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.37 (s,
18H), 2.35 (s, 6H) 3.16 (s, 1H), 5.30 (s, 1H), 6.38-6.52 (m, 2H),
6.86 (m, 2H), 7.06-7.28 (m, 12H).
[1579] MS (FD): m/z 673 (M.sup.+).
(iii) Synthesis of
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
ditert-butylfluorenyl)zirconium dichloride
[1580] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 0.672 g (1 mmol) of
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
ditert-butylfluorene) and 40 mL of dehydrated diethyl ether, and
the mixture was stirred. This solution was cooled to -78.degree. C.
in a dry ice/methanol bath, and 1.3 mL (2.05 mmol) of a 1.56 mol/L
hexane solution of n-butyllithium was added. The mixture was
stirred at room temperature for 19 hours until the clouded solution
becomes a clear orange color. This reaction solution was cooled
again to -78.degree. C. in a dry ice/methanol bath, and then 0.23 g
(1 mmol) of zirconium tetrachloride was added. Subsequently, the
mixture was stirred for 23 hours while gradually warming to room
temperature. The solvent was then removed by distillation under
reduced pressure. Subsequently, about 50 mL of n-hexane was added
under a nitrogen atmosphere and insolubles were removed by a
filtration through celite. The n-hexane solution thus obtained was
concentrated to about 5 mL and left to stand at -18.degree. C. for
24 hours. The solids precipitated were separated by filtration, and
washed with n-hexane and n-pentane to obtain a target product as an
orange powder (yield 0.2 g (24%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1581] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.44 (s,
18H), 2.20 (s, 6H), 5.59 (d, 2H), 5.80 (m, 2H), 6.31 (m, 2H),
7.19-8.14 (m, 10H).
[1582] MS (FD): m/z 833 (M.sup.+).
Synthesis Example 1-7
Synthesis of
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)-
zirconium dichloride
(i) Synthesis of
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorene)
[1583] Under a nitrogen atmosphere, 30 mL of dehydrated
tetrahydrofuran was added to 1.14 g (2.65 mmol) of
2,7-diphenyl-3,6-ditert-butyl-fluorene synthesized in Synthesis
Example 1-1(ii), and the mixture was stirred. This solution was
cooled in an ice bath, and 1.90 mL (2.96 mmol) of a 1.56 mol/L
hexane solution n-butyllithium was added. The mixture was stirred
at room temperature for 2 hours. The resulting dark red solution
was cooled to -78.degree. C. in a dry ice/methanol bath, and a
solution prepared by dissolving 0.49 g (3.35 mmol) of
cyclohexylfulvene, which was synthesized according to a method
described in JP-A No. 2000-26490, in 20 mL of tetrahydrofuran was
added dropwise over 15 minutes. Subsequently, the mixture was
stirred for 19 hours while gradually warming to room temperature.
30 mL of 1 N hydrochloric acid was added to the resulting dark red
solution to terminate the reaction. 100 mL of diethyl ether was
added to perform liquid-liquid phase separation, and the soluble
fraction was extracted. This organic layer was washed two times
with a saturated aqueous solution of sodium hydrogen carbonate, two
times with water, and once with saturated brine, and dried over
magnesium sulfate. The solvent was distilled off, and the residue
was recrystallized with diethylether and methanol to obtain a
target product as a pale yellow powder (yield 0.98 g (64%)). The
target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1584] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.26 (s,
tBu(Flu), 18H), 0.90-1.85 (m, C6, 10H), 2.75 (br, CpH, 1H), 3.79
(br, Flu-9H, 1H), 5.80-6.52 (m, Cp, 4H), 6.73 (s, Flu, 2H),
7.20-7.60 (m, Ph(Flu), 10H), 7.82 (s, Flu, 2H).
[1585] MS (FD): M/z 577 (M.sup.+).
(ii) Synthesis of
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)-
zirconium dichloride
[1586] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 0.98 g (1.70 mmol) of
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorene)
and 40 mL of dehydrated diethyl ether, and the mixture was stirred.
This mixed slurry solution was cooled to 0.degree. C. in an ice
bath, and 2.40 mL (3.74 mmol) of a 1.56 mol/L hexane solution of
n-butyllithium was added. The mixture was stirred for 23 hours
while gradually warming to room temperature. This red reaction
solution was cooled to -78.degree. C. in a dry ice/methanol bath,
and then 0.391 g (1.68 mmol) of zirconium tetrachloride was added.
Subsequently, the mixture was stirred for 22 hours while gradually
warming to room temperature to obtain an orange suspension. The
solvent was removed by distillation under reduced pressure. Under a
nitrogen atmosphere the residue was dissolved in n-hexane. The
liquid was passed through a glass filter filled with Celite, and
insolubles were washed with n-hexane, and the red powders insoluble
in n-hexane was subjected to extraction with dichloromethane. The
solvent in which the dichloromethane-solubles were dissolved was
distilled off. The residue was washed with cold diethyl ether/cold
n-hexane to obtain a target product as an orange solid (yield 0.71
g (57%)). The target product was identified by .sup.1H-NMR and
FD-MS spectroscopy.
[1587] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.25 (s,
tBu(Flu), 18H), 1.45-1.90 (m, C6, 6H), 2.10-2.35 (m, C6, 2H),
2.85-3.00 (m, C6, 2H), 5.55 (t, J=2.6 Hz, Cp, 2H), 6.29 (t, J=2.6
Hz, Cp, 2H), 7.15-7.45 (m, Ph(Flu) and Flu, 12H), 8.22 (s, Flu,
2H).
[1588] MS (FD): M/z 736 (M.sup.+).
Synthesis Example 1-8
Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-di[2-naphthyl]-3,6-ditert-butylfl-
uorenyl)zirconium dichloride
(i) Synthesis of 2,7-di(2-naphthyl)-3,6-ditert-butyl-fluorene
[1589] Under a nitrogen atmosphere, 45 mL of dehydrated
1,2-dimethoxyethane was added to 3.02 g (6.92 mmol) of
2,7-dibromo-3,6-ditert-butyl-fluorene synthesized in Synthesis
Example 1-1(i) and 0.40 g (0.35 mmol) of Pd(PPh.sub.3), and the
mixture was stirred at room temperature for 20 minutes. To this
solution, a solution prepared by dissolving 2.62 g (15.2 mmol) of
2-naphthylboric acid in 15 mL of ethanol was added, and the mixture
was stirred at room temperature for 20 minutes. Then, 13.8 mL (27.7
mmol) of a 2.0 mol/L aqueous solution of sodium carbonate was
added. The mixture was heated to reflux for 21 hours, and then left
to be naturally cooled. Subsequently, the reaction was terminated
with 1N hydrochloric acid in an ice bath. Thereafter,
dichloromethane was added to perform liquid-liquid phase
separation. The aqueous layer was subjected to extraction with
diethyl ether twice, and the resultant was combined with the
organic layer obtained previously. The resulting liquid was washed
two times with a saturated aqueous solution of sodium hydrogen
carbonate, two times with water, and once with saturated brine, and
then dried over magnesium sulfate. Subsequently, the solvent was
distilled off, and the resulting solids were subjected to
separation by silica gel chromatography. To the yellow powder
obtained, a mixed solution of n-hexane and a small amount of
dichloromethane was added. The mixture was heated to 65.degree. C.
to dissolve the powder completely, and was then left to stand
overnight at room temperature. Crystals precipitated were washed
three times with 10 mL of n-hexane to obtain a target product as a
white powder (yield 2.71 g (74%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1590] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.32 (s,
tBu(Flu), 18H), 3.81 (s, Flu-9H, 2H), 7.22 (s, Flu, 2H), 7.46-7.52
(m, NapFlu, 6H), 7.77-7.90 (m, NapFlu, 8H), 8.03 (s, Flu, 2H).
[1591] MS (FD): M/z 530 (M.sup.+).
(ii) Synthesis of dibenzylmethylene(cyclopentadienyl)(2,7-di
[2-naphthyl]-3,6-ditert-butylfluorene)
[1592] Under a nitrogen atmosphere, 80 mL of dehydrated
tert-butylmethylether was added to 0.82 g (1.54 mmol) of
2,7-di(2-naphthyl)-3,6-ditert-butyl-fluorene, and the mixture was
stirred. This solution was cooled in an ice bath, and 1.10 mL (1.76
mmol) of a 1.60 mol/L hexane solution of n-butyllithium was added.
The mixture was stirred at room temperature for 22 hours. To the
yellow suspension thus obtained, 0.44 g (1.70 mmol) of
6,6-dibenzofulvene synthesized in Synthesis Example 1-1 (iii) was
added, and the mixture was heated to reflux for 19 hours.
Subsequently, 30 mL of 1N hydrochloric acid was added to the light
orange-brown solution obtained to terminate the reaction. Then, 100
mL of diethylether was added to perform a liquid-liquid phase
separation, and the soluble fraction was extracted. This organic
layer was washed two times with a saturated aqueous solution of
sodium hydrogen carbonate, two times with water, and once with
saturated brine, and then dried over magnesium sulfate. The solvent
was distilled off, and the residue was purified by column
chromatography to obtain a target product as a pale yellow solid
(yield 0.64 g (53%)). The target product was identified by
.sup.1H-NMR and FD-MS spectroscopy.
[1593] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.28 (s,
tBu(Flu), 18H), 2.65 (br, CpH, 1H), 3.28 (br, CH.sub.2Ph, 4H), 4.46
(br, Flu-9H, 1H), 5.85-6.48 (m, Cp, 4H), 6.80-7.92 (m, Nap(Flu) and
CH.sub.2Ph and Flu, 26H).
[1594] MS (FD): M/z 788 (M.sup.+).
(iii) Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-di[2-naphthyl]-3,6-ditert-butylfl-
uorenyl)zirconium dichloride
[1595] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 0.64 g (0.811 mmol) of
dibenzylmethylene(cyclopentadienyl)(2,7-di[2-naphthyl]-3,6-ditert-butylfl-
uorene) and 40 mL of dehydrated diethyl ether, and the mixture was
stirred. This mixed slurry solution was cooled in an ice bath, 1.14
mL (1.82 mmol) of a 1.60 mol/L hexane solution of n-butyllithium
was added. The mixture was stirred for 42 hours while gradually
warming to room temperature. This red reaction solution was cooled
to -78.degree. C. in a dry ice/methanol bath, and then 0.180 g
(0.772 mmol) of zirconium tetrachloride was added. Subsequently,
the mixture was stirred for 47 hours while gradually warming to
room temperature to obtain an orange colored suspension. The
solvent was removed by distillation under reduced pressure. Under a
nitrogen atmosphere, the residue was dissolved in n-hexane, and the
liquid was passed through a glass filter filled with Celite,
insolubles were washed with n-hexane, and the red powder insoluble
in n-hexane was subjected to extraction with dichloromethane. The
solvent in which the dichloromethane-solubles were dissolved was
distilled off. The residue was washed with diethyl ether/n-hexane
to obtain a target product as a red-orange powder (yield 379 mg
(49%)). The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1596] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.35 (s,
tBu(Flu), 18H), 3.72-4.00 (m, CH.sub.2Ph, 4H), 5.83 (br, Cp, 2H),
6.52 (br, Cp, 2H), 6.95-7.90 (m, Nap(Flu) and CH.sub.2Ph, 26H),
8.40 (s, Flu, 2H).
[1597] MS (FD): M/z 948 (M.sup.+).
Synthesis Example 1-9
Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-di[p-tolyl]-3,6-ditert-butylfluor-
enyl)zirconium dichloride
(i) Synthesis of 2,7-di(p-tolyl)-3,6-ditert-butyl-fluorene
[1598] Under a nitrogen atmosphere, 120 mL of dehydrated
1,2-dimethoxyethane was added to 8.00 g (18.3 mmol) of
2,7-dibromo-3,6-ditert-butyl-fluorene synthesized in Synthesis
Example 1-1(i) and 1.05 g (0.909 mmol) of Pd(PPh.sub.3), and the
mixture was stirred at room temperature for 20 minutes. To this
solution, a solution prepared by dissolving 5.50 g (40.5 mmol) of
4-methylphenylboric acid in 20 mL of ethanol was added. The mixture
was stirred at room temperature for 20 minutes, and then 36.8 mL
(73.6 mmol) of a 2.0 mol/L aqueous solution of sodium carbonate was
added. Subsequently, the mixture was heated to reflux for 21 hours,
left to be naturally cooled, and then 1N hydrochloric acid was
added in an ice bath to terminate the reaction. Dichloromethane was
then added to perform a liquid-liquid phase separation, and the
aqueous layer was subjected to extraction with diethyl ether twice.
The resultant was combined with the organic layer obtained
previously. The resultant liquid was then washed two times with a
saturated aqueous solution of sodium hydrogen carbonate, two times
with water, and once with saturated brine, and then dried over
magnesium sulfate. Subsequently, the solvent was distilled off, and
the resultant was subjected to separation by silica gel
chromatography. To the whitish yellow powder obtained, small amount
of a mixed solution of n-hexane and ethanol was added. The mixture
was heated to 65.degree. C., and then was left to stand for 1 hour
at room temperature. Crystals Precipitated were washed 10 times
with 2 mL of cold methanol and 20 times with 1 mL of cold n-hexane
to obtain a target product as a white powder (yield 6.95 g (83%)).
The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1599] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.29 (s,
tBu(Flu), 18H), 2.41 (s, MePhFlu, 6H), 3.76 (s, Flu-9H, 2H),
7.12-7.26 (m, Flu and MePhFlu 10H), 7.95 (s, Flu, 2H).
[1600] MS (FD): M/z 458 (M.sup.+).
(ii) Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-di[p-tolyl]-3,6-ditert-butylfluor-
ene)
[1601] Under a nitrogen atmosphere, 100 mL of dehydrated
tert-butylmethylether was added to 1.30 g (2.84 mmol) of
2,7-di(p-tolyl)-3,6-ditert-butyl-fluorene, and the mixture was
stirred. This solution was cooled in an ice bath, and 2.10 mL (3.36
mmol) of a 1.60 mol/L hexane solution of n-butyllithium was added.
The solution was stirred at room temperature for 21 hours. To the
yellowy-black suspension obtained, 0.808 g (3.12 mmol) of
6,6-dibenzofulvene synthesized in Synthesis Example 1-1(iii) was
added. Subsequently, the mixture was heated to reflux for 19 hours.
Subsequently, 30 mL of 1N hydrochloric acid was added to the
red-brown solution obtained to terminate the reaction. Then, 100 mL
of diethylether was added to perform a liquid-liquid phase
separation, and the soluble fraction was extracted. This organic
layer was washed two times with a saturated aqueous solution of
sodium hydrogen carbonate, two times with water, and once with
saturated brine, and then dried over magnesium sulfate. The solvent
was solvent was distilled off, and the residue was subjected to
separation by column chromatography. The whitish yellow powder
obtained was washed once with 10 mL of cold hexane, three times
with 5 mL of cold ethanol, and 3 times with 2 mL of cold hexane to
obtain a target product as a white powder (yield 1.04 g (51%)). The
target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1602] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.25 (s,
tBu(Flu), 18H), 2.38 (s, MePhFlu, 6H), 2.69 (br, CpH, 1H), 3.27
(br, CH.sub.2Ph, 4H), 4.40 (br, Flu-9H, 1H), 5.80-6.48 (m, Cp, 4H),
6.80-7.30 (m, MePh(Flu) and CH.sub.2Ph and Flu, 20H), 7.66 (s, Flu,
2H).
[1603] MS (FD): M/z 717 (M.sup.+).
(iii) Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-di[p-tolyl]-3,6-ditert-butylfluor-
enyl)zirconium dichloride
[1604] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 1.04 g (1.45 mmol) of
dibenzylmethylene(cyclopentadienyl)(2,7-di[p-tolyl]-3,6-ditert-butylfluor-
ene) and 60 mL of dehydrated diethyl ether, and the mixture was
stirred. This mixed slurry solution was cooled 15 in an ice bath,
and 2.00 mL (3.20 mmol) of a 1.60 mol/L hexane solution of
n-butyllithium was added. The mixture was stirred for 51 hours
while gradually warming to room temperature. This red-orange
reaction solution was cooled to -78.degree. C. in a dry
ice/methanol bath, and then 0.363 g (1.60 mmol) of zirconium
tetrachloride was added. Subsequently, the mixture was stirred for
43 hours while gradually warming to room temperature to obtain an
orange colored suspension. The solvent was removed by distillation
under reduced pressure. Under a nitrogen atmosphere, the residue
was dissolved in n-hexane, the liquid was passed through a glass
filter filled with Celite, insolubles were washed with n-hexane,
and the orange powder insoluble in n-hexane was subjected to
extraction with dichloromethane. The solvent in which the
dichloromethane-solubles were dissolved was distilled off. The
residue was washed with diethyl ether/n-hexane to obtain a target
product as an orange powder (yield 744 mg (58%)). The target
product was identified by .sup.1H-NMR and FD-MS spectroscopy.
[1605] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.32 (s,
tBu(Flu), 18H), 2.37 (s, MePhFlu, 6H), 3.86 (d, J=15.5 Hz,
CH.sub.2Ph, 2H), 3.94 (d, J=15.5 Hz, CH.sub.2Ph, 2H), 5.81 (t,
J=2.6 Hz, Cp, 2H), 6.46 (t, J=2.6 Hz, Cp, 2H), 6.90-7.40 (m,
MePh(Flu) and CH.sub.2Ph and Flu, 20H), 8.32 (s, Flu, 2H).
[1606] MS (FD): M/z 876 (M.sup.+).
Synthesis Example 1-10
Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-di[o-tolyl]-3,6-ditert-butylfluor-
enyl)zirconium dichloride
(i) Synthesis of 2,7-di(p-tolyl)-3,6-ditert-butyl-fluorene
[1607] Under a nitrogen atmosphere, 50 mL of dehydrated
tetrahydrofuran was added to 3.50 g (8.02 mmol) of
2,7-dibromo-3,6-ditert-butyl-fluorene synthesized in Synthesis
Example 1-1(i), 0.186 g (0.20 mmol) of Pd.sub.2(dba).sub.3, 0.115 g
(0.57 mmol) of P(tBu).sub.3, and 6.81 g (32.1 mmol) of tripotassium
phosphate, and the mixture was stirred at room temperature for 20
minutes. To the solution, a solution of 2.73 g (20.0 mmol) prepared
by dissolving o-tolylboronic acid in 15 mL of dehydrated
tetrahydrofuran was added. Subsequently, the mixture was heated to
reflux for 72 hours, left to be naturally cooled, and then 1N
hydrochloric acid was added in an ice bath to terminate the
reaction. Thereafter, diethylether was added to perform
liquid-liquid phase separation. The aqueous layer was extracted
twice with diethylether and the resultant was combined with the
organic layer obtained previously. Then, the resultant liquid
washed two times with a saturated aqueous solution of sodium
hydrogen carbonate, two times with water, and once with saturated
brine, and dried over magnesium sulfate. Subsequently, the solvent
was distilled off, and the resultant was subjected to separation by
silica gel chromatography to obtain a target product as a white
powder (yield 0.532 g (14%)). The target product was identified by
.sup.1H-NMR.
[1608] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.27 (s,
tBu(Flu), 18H), 2.07 (s, Me(o-tolyl), 6H), 3.79 (s, Flu-9H, 2H),
7.07 (s, Flu, 2H), 7.19-7.25 (m, o-tolylFlu, 10H), 8.00 (s, Flu,
2H).
(ii) Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-di[o-tolyl]-3,6-ditert-butylfluor-
ene)
[1609] Under a nitrogen atmosphere, 40 mL of dehydrated
tert-butylmethylether was added to 0.92 g (2.00 mmol) of
2,7-di(p-tolyl)-3,6-ditert-butyl-fluorene, and the mixture was
stirred. This solution was cooled in an ice bath, and 1.45 mL (2.20
mmol) of a 1.52 mol/L hexane solution of n-butyllithium was added.
The mixture was stirred at room temperature for 4 hours. The
resulting red solution was cooled in an ice bath, a solution
prepared by dissolving 0.58 g (2.24 mmol) of 6,6-dibenzofulvene,
which was synthesized in Synthesis Example 1-2 (iii), in 20 mL of
THF was added dropwise over 25 minutes.
[1610] Subsequently, the mixture was stirred for 18 hours while
gradually warming to room temperature, and then heated to reflux
for 3 hours. The reddish black solution obtained was left to be
naturally cooled, and then 1N hydrochloric acid was added in an ice
bath to terminate the reaction. Thereafter, diethylether was added
to perform liquid-liquid phase separation, and the aqueous layer
was subjected to extraction with diethylether twice. The resultant
was combined with the organic layer obtained previously. The
resultant liquid was washed two times with a saturated aqueous
solution of sodium hydrogen carbonate, two times with water, and
once with saturated brine, and dried over magnesium sulfate. The
solvent was distilled off, and the resultant was subjected to
separation by silica gel chromatography to obtain a yellow powder.
To this yellow powder, a mixed solvent of hexane and ethanol was
added, and the mixture was heated to 60.degree. C. to dissolve the
powder completely, and the liquid was left to stand overnight at
-20.degree. C. Crystals precipitated were washed with ethanol to
obtain a target product as a pale yellow powder (yield 0.57 g
(40%)). The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1611] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm
1.21-1.23 (m, tBu(Flu), 18H), 1.96-1.99 (m, CH.sub.3(o-tolyl), 3H),
2.14-2.19 (m, CH.sub.3(o-tolyl), 3H), 2.66 (br, CpH, 1H), 3.06-3.34
(br, CH.sub.2Ph, 4H), 4.45 (br, Flu-9H, 1H), 5.80-6.48 (br, Cp,
4H), 6.75-7.20 (m, o-tolyl(Flu) and CH.sub.2Ph and Flu, 20H),
7.64-7.79 (m, Flu, 2H).
[1612] MS (FD): M/z 716 (M.sup.+).
(iii) Synthesis of
dibenzylmethylene(cyclopentadienyl)(2,7-di[o-tolyl]-3,6-ditert-butylfluor-
enyl)zirconium dichloride
[1613] Under a nitrogen atmosphere, a 50-mL Schlenk flask was
charged with 0.36 g (0.50 mmol) of
dibenzylmethylene(cyclopentadienyl)(2,7-di[o-tolyl]-3,6-ditert-butylfluor-
ene) and 25 mL of dehydrated diethyl ether, and the mixture was
stirred. This mixed slurry solution was cooled in an ice bath, 0.72
mL (1.09 mmol) of a 1.52 mol/L hexane solution of n-butyllithium
was added, and the mixture was stirred for 40 hours while gradually
warming to room temperature. This red reaction solution was cooled
to -78.degree. C. in a dry ice/methanol bath, and then 0.251 g
(1.08 mmol) of zirconium tetrachloride was added. Subsequently, the
mixture was stirred for 17 hours while gradually warming to room
temperature to obtain a red-orange suspension. The solvent was
dried under reduced pressure. Under a nitrogen atmosphere, the
residue was dissolved in n-hexane, and the liquid was passed
through a glass filter filled with Celite, insolubles were washed
with n-hexane, and the orange powder insoluble in n-hexane was
subjected to extraction with dichloromethane. The solvent in which
the dichloromethane-solubles were dissolved was distilled off. The
residue was washed with diethyl ether/cold n-pentane and dried to
obtain a target product as a dark pink powder (yield 167 mg (38%)).
The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1614] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm
1.28-1.33 (m, tBu(Flu), 18H), 1.68, 1.87, 2.16 (s, s, s,
CH.sub.3(o-tolyl), 6H), 3.34-4.30 (m, CH.sub.2Ph, 4H), 5.73-5.82
(m, Cp, 2H), 6.45-6.48 (m, Cp, 2H), 6.95-7.30 (m, o-tolyl(Flu) and
CH.sub.2Ph, 18H), 7.48 (s, Flu, 2H), 8.37-8.41 (m, Flu, 2H).
[1615] MS (FD): M/z 876 (M.sup.+).
Synthesis Example 1-11
Synthesis of
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride
(i) Synthesis of bis(4-chlorobenzyl)ketone
[1616] Under a nitrogen atmosphere, a 500-mL three-necked flask was
charged with 15.12 g (73.3 mmol) of dicyclohexylcarbodiimide and
2.24 g (18.3 mmol) of dimethylaminopyridine, further charged with
150 mL of absolute dichloromethane, and the mixture was stirred at
room temperature. To this solution, 12.50 g (73.3 mmol) of
4-chlorophenylacetic acid dissolved in 120 mL of absolute
dichloromethane was added dropwise. The solution was stirred at
room temperature for 3 days, and then white crystals precipitated
were separated by filtration using Kiriyama funnel. The filtrate
was concentrated, and the residue was subjected to separation by
silica gel column chromatography to obtain a mixed product of white
crystal/yellowy oil. To this mixed product, ethanol was added. The
mixture was heated to 50.degree. C. to dissolve the mixed product
completely, and then left to stand overnight at room temperature.
Crystals precipitated were washed with a small amount of ethanol to
obtain a target product as a white powder (yield 5.52 g (54%)). The
target product was identified by .sup.1H-NMR.
[1617] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 3.69 (s,
4-Cl-PhCH.sub.2, 4H), 7.05 (d, 4-Cl-PhCH.sub.2, 4H), 7.28 (d,
4-Cl-PhCH.sub.2, 4H).
(ii) Synthesis of 6,6-di(4-chlorobenzyl)fulvene
[1618] Under a nitrogen atmosphere, a 100-mL three-necked flask was
charged with 0.66 g (9.22 mmol) of lithium cyclopentadiene and 10
mL of dehydrated THF, and the mixture was stirred. This solution
was cooled (to -78.degree. C.) in a dry ice/methanol bath, and 2.50
g (8.96 mmol) of bis(4-chlorobenzyl)ketone dissolved in 15 mL of
dehydrated THF was added dropwise. Subsequently, the mixture was
stirred for 17 hours while gradually warming to room temperature.
Then, 1 N hydrochloric acid was added to the resulting brown-black
solution to terminate the reaction. Thereafter, hexane was added to
perform liquid-liquid phase separation, and the aqueous layer was
subjected to extraction with hexane twice. The resultant was
combined with the organic layer obtained previously. The resultant
liquid was then washed two times with a saturated aqueous solution
of sodium hydrogen carbonate, two times with water, and once with
saturated brine, and dried over magnesium sulfate. The solvent was
distilled off, and the residue was purified by column
chromatography to obtain a target product as a yellow powder (yield
0.65 g (22%)). The target product was identified by
.sup.1H-NMR.
[1619] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 3.65 (s,
PhCH.sub.2, 4H), 6.64 (s, Cp, 4H), 7.02 (d, 4-Cl-PhCH.sub.2, 4H),
7.23 (d, 4-Cl-PhCH.sub.2, 4H).
(iii) Synthesis of
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorene)
[1620] Under a nitrogen atmosphere, 15 mL of absolute THF was added
to 0.69 g (1.60 mmol) of 2,7-diphenyl-3,6-ditert-butyl-fluorene
synthesized in Synthesis Example 1-1(ii), and the mixture was
stirred. This solution was cooled (to -78.degree. C.) in a
methanol/dry ice bath, and 1.26 mL (1.92 mmol) of a 1.52 mol/L
hexane solution of n-butyllithium was added. Subsequently, the
mixture was stirred for 19 hours while gradually warming to room
temperature. The resulting dark red solution was cooled (to
-78.degree. C.) in a dry ice/methanol bath, and 0.62 g (1.88 mmol)
of 6,6-di(4-chlorobenzyl)fulvene dissolved in 10 mL of THF was
added dropwise over 20 minutes. The mixture was stirred for 30
minutes, and 1N hydrochloric acid was added to the dark red
solution obtained to terminate the reaction. Thereafter, hexane was
added to perform liquid-liquid phase separation, and the aqueous
layer was subjected to extraction with hexane twice. The resultant
was combined with the organic layer obtained previously. The
resultant liquid was then washed two times with a saturated aqueous
solution of sodium hydrogen carbonate, two times with water, and
once with saturated brine, and dried over magnesium sulfate. The
solvent was distilled off to obtain a whitish yellow powder. This
whitish yellow powder was washed with a mixed solvent of hexane and
ethanol to obtain a target product as a white powder (yield 0.80 g
(66%)). The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1621] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.27 (s,
tBu(Flu), 18H), 2.70 (br, CpH, 1H), 3.12 (br, 4-C1-PhCH.sub.2, 4H),
4.34 (s, Flu-9H, 1H), 5.87-6.62 (m, Cp, 4H), 6.70-7.30 (m, Ph(Flu)
and 4-Cl-PhCH.sub.2 and Flu, 20H), 7.67 (br, Flu, 2H).
[1622] MS (FD): M/z 756 (M.sup.+).
(iv) Synthesis of
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride
[1623] Under a nitrogen atmosphere, a 50-mL Schlenk flask was
charged with 0.79 g (1.01 mmol) of
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorene) and 40 mL of absolute diethyl ether, and the mixture
was stirred. This mixed slurry solution was cooled (to -78.degree.
C.) in a dry ice/methanol bath, and 1.45 mL (2.20 mmol) of a 1.52
mol/L hexane solution of n-butyllithium was added. Subsequently,
the mixture was stirred for 18 hours while gradually warming to
room temperature. This red reaction solution was cooled (to
-78.degree. C.) in a dry ice/methanol bath, and 0.32 g (1.37 mmol)
of zirconium tetrachloride was added. The mixture was stirred for
22 hours while gradually warming to room temperature, to obtain an
orange colored suspension. The solvent was dried under reduced
pressure. Under a nitrogen atmosphere, the resultant was filtered
through a glass filter filled with Celite, and insolubles were
washed with a small amount of diethyl ether. The filtrate was
concentrated to obtain an orange colored solid. Extraction was
carried out using a mixed solvent of diethylether/hexane/pentane,
and the solvent in which solubles were dissolved was distilled off.
The residue was dried to obtain a target product as a dark pink
powder (yield 366 mg (40%)). The target product was identified by
.sup.1H-NMR and FD-MS spectroscopy.
[1624] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.32 (s,
tBu(Flu), 18H), 3.70 (d, J=15.5 Hz, 4-Cl-PhCH.sub.2, 2H), 3.86 (d,
J=15.5 Hz, 4-Cl-PhCH.sub.2, 2H), 5.79 (t, J=2.6 Hz, Cp, 2H), 6.48
(t, J=2.6 Hz, Cp, 2H), 6.92-7.33 (m, Ph(Flu) and 4-Cl-PhCH.sub.2
and Flu, 20H), 8.35 (s, Flu, 2H).
[1625] MS (FD): M/z 916 (M.sup.+).
Example 1-1
Propylene Polymerization
[1626] A thoroughly nitrogen purged glass autoclave with an
internal volume of 500 ml was charged with 250 ml of toluene, and
then charged with propylene at a rate of 150 liter/hour, which was
kept at 25.degree. C. for 20 minutes. Meanwhile, a magnetic stirrer
was placed in a thoroughly nitrogen purged side arm flask with an
internal volume of 30 ml, and the flask was sequentially charged
with 5.00 mmol of a toluene solution of methylaluminoxane (Al=1.53
mol/l) in terms of aluminum atom and 5.0 .mu.mol of a toluene
solution of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride in terms of zirconium atom. The mixture was
stirred for 20 minutes. This solution was then added to toluene in
the glass autoclave which had been charged with propylene, and the
polymerization was initiated. Propylene gas was continuously
supplied at a rate of 150 liter/hour, and the polymerization was
performed at 25.degree. C. for 10 minutes under normal pressure.
Thereafter, a small amount of methanol was added to terminate the
polymerization. The polymer solution was added to an excessive
amount of methanol to precipitate a polymer. The polymer was then
dried under reduced pressure at 80.degree. C. for 12 hours to
obtain a polymer in an amount of 6.32 g. The polymerization
activity was 7.58 kg-PP/mmol-Zrhr. The polymer obtained had
[.eta.]=2.54 dl/g, Tm.sub.1=157.0.degree. C.,
Tm.sub.2=162.0.degree. C., and rrrr=95.3%.
Example 1-2
Propylene Polymerization
[1627] The polymerization was performed in the same manner as in
Example 1-1, except that the temperature inside the autoclave
before the polymerization and during the polymerization was kept at
50.degree. C., and that the polymerization time was changed to 15
minutes. The amount of the polymer obtained was 12.74 g and the
polymerization activity was 10.19 kg-PP/mmol-Zrhr. The polymer
obtained had [.eta.]=1.64 dl/g, Tm.sub.1=142.9.degree. C., and
Tm.sub.2=150.1.degree. C.
Example 1-3
Propylene Polymerization
[1628] A thoroughly nitrogen purged glass autoclave with an
internal volume of 500 ml was charged with 250 ml of toluene, and
then charged with propylene at a rate of 150 liter/hour, which kept
at 25.degree. C. for 20 minutes. Meanwhile, a magnetic stirrer was
placed in a thoroughly nitrogen purged side arm flask with an
internal volume of 30 ml, and the flask sequentially charged with
5.00 mmol of a toluene solution of methylaluminoxane (Al=1.53
mol/l) in terms of aluminum atom and 5.0 .mu.mol of a toluene
solution of
di(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride in terms of zirconium atom. The mixture
was stirred for 20 minutes. This solution was then added to toluene
in the glass autoclave which had been charged with propylene, and
the polymerization was initiated. Propylene gas was continuously
supplied at a rate of 150 liter/hour, and the polymerization was
performed at 25.degree. C. for 25 minutes under normal pressure.
Thereafter, a small amount of methanol was added to terminate the
polymerization. The polymer solution was added to an excessive
amount of methanol to precipitate a polymer. The polymer was then
dried under reduced pressure at 80.degree. C. for 12 hours to
obtain a polymer in an amount of 7.35 g. The polymerization
activity was 3.53 kg-PP/mmol-Zrhr. The polymer obtained had
[.eta.]=2.43 dl/g, Tm.sub.1=154.9.degree. C.,
Tm.sub.2=160.0.degree. C., and rrrr=95.2%.
Example 1-4
Propylene Polymerization
[1629] The polymerization was performed in the same manner as in
Example 1-3, except that the temperature inside the autoclave
before the polymerization and during the polymerization was kept at
50.degree. C. The amount of polymer obtained was 11.00 g and the
polymerization activity was 5.28 kg-PP/mmol-Zrhr. The polymer
obtained had [.eta.]=1.54 dl/g, Tm.sub.1=138.6.degree. C., and
Tm.sub.2=146.2.degree. C.
Example 1-5
Propylene Polymerization
[1630] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-1, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
di(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride, and that the polymerization time was
changed to 40 minutes. As a result, a polymer was obtained in an
amount of 3.31 g and the polymerization activity was 0.99
kg-PP/mmol-Zrhr. The polymer obtained had [.eta.]=2.52 dl/g,
Tm.sub.1=142.6.degree. C., and Tm.sub.2=151.8.degree. C.
Example 1-6
Propylene Polymerization
[1631] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-1, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, and that the polymerization time
was changed to 30 minutes. As a result, a polymer was obtained in
an amount of 8.35 g and the polymerization activity was 3.34
kg-PP/mmol-Zrhr. The polymer obtained had [.eta.]=5.98 dl/g and
Tm.sub.2=153.3.degree. C.
Example 1-7
Propylene Polymerization
[1632] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-2, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, and that the polymerization time
was changed to 40 minutes. As a result, a polymer was obtained in
an amount of 2.90 g and the polymerization activity was 0.87
kg-PP/mmol-Zrhr. The polymer obtained had [.eta.]=3.22 dl/g,
Tm.sub.1=139.1.degree. C., and Tm.sub.2=143.8.degree. C.
Example 1-8
Propylene Polymerization
[1633] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-1, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, and that the polymerization time
was changed to 60 minutes. As a result, a polymer was obtained in
an amount of 7.30 g and that the polymerization activity was 1.46
kg-PP/mmol-Zrhr. The polymer obtained had [.eta.]=5.96 dl/g,
Tm.sub.1=142.6.degree. C., and Tm.sub.2=149.0.degree. C.
Example 1-9
Propylene Polymerization
[1634] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-1, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
di(m-trifluoromethyl-fluorenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3-
,6-ditert-butylfluorenyl)zirconium dichloride, and that the
polymerization time was changed to 60 minutes. As a result, a
polymer was obtained in an amount of 2.90 g and the polymerization
activity was 0.58 kg-PP/mmol-Zrhr. The polymer obtained had
[.eta.]=4.64 dl/g, Tm.sub.1=135.7.degree. C., and
Tm.sub.2=141.9.degree. C.
Example 1-10
Propylene Polymerization
[1635] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-1, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)-
zirconium dichloride, and that the polymerization time was changed
to 15 minutes. As a result, a polymer was obtained in an amount of
6.55 g and the polymerization activity was 5.24 kg-PP/mmol-Zrhr.
The polymer obtained had [.eta.]=2.17 dl/g, Tm.sub.1=153.7.degree.
C., and Tm.sub.2=157.7C.
Example 1-11
Propylene Polymerization
[1636] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-2, except that, in Example 1-1,
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)-
zirconium dichloride, and that the polymerization time was changed
to 15 minutes. As a result, a polymer was obtained in an amount of
5.64 g and the polymerization activity was 4.51 kg-PP/mmol-Zrhr.
The polymer obtained had [.eta.]=1.42 dl/g, Tm.sub.1=136.9.degree.
C., and Tm.sub.2=145.8.degree. C.
Example 1-12
Propylene Polymerization
[1637] A thoroughly nitrogen purged glass autoclave with a internal
volume of 500 ml was charged with 250 ml of toluene, and then
charged with propylene at a rate of 150 liter/hour, which was kept
at 25.degree. C. for 20 minutes. Subsequently, the autoclave was
sequentially charged with 2.0 mmol of 1.0 mmol/ml toluene solution
of triisobutylaluminum in terms of aluminum atom, 5.0 .mu.mol of a
toluene solution of
dibenzylmethylene(cyclopentadienyl)2,7-diphenyl-3,6-ditert-butylfluorenyl-
)zirconium dichloride in terms of zirconium atom, and 0.020
millimole/liter of a toluene solution of N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate. Then, polymerization was
initiated. Propylene gas was continuously supplied at a rate of 150
liter/hour, and the polymerization was performed at 25.degree. C.
for 20 minutes under normal pressure. Thereafter, a small amount of
methanol was added to terminate the polymerization. The polymer
solution was added to an excessive amount of methanol to
precipitate a polymer. The polymer was then dried under reduced
pressure at 80.degree. C. for 12 hours to obtain a polymer in an
amount of 10.56 g. The polymerization activity was 6.34
kg-PP/mmol-Zrhr. The polymer obtained had [.eta.]=1.25 dl/g,
Tm.sub.1=144.9.degree. C., and Tm.sub.2=151.8.degree. C.
Comparative Example 1-1
Propylene Polymerization
[1638] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-1, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride, and that the polymerization time was changed to 15
minutes. As a result, a polymer was obtained in an amount of 8.94 g
and the polymerization activity was 7.15 kg-PP/mmol-Zrhr. The
polymer obtained had [.eta.]=2.12 dl/g, Tm.sub.1=150.2.degree. C.,
Tm.sub.2=155.2.degree. C., and rrrr=94.1%.
Comparative Example 1-2
Propylene Polymerization
[1639] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-2, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride. As a result, a polymer was obtained in an amount of
8.23 g and the polymerization activity was 6.58 kg-PP/mmol-Zrhr.
The polymer obtained had [.eta.]=1.23 dl/g, Tm.sub.1=132.2.degree.
C., and Tm.sub.2=142.1.degree. C.
Comparative Example 1-3
Propylene Polymerization
[1640] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-1, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
cyclohexylidene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zir-
conium dichloride, and that the polymerization time was changed to
60 minutes. As a result, a polymer was obtained in an amount of
0.06 g and the polymerization activity was 0.02 kg-PP/mmol-Zrhr.
The polymer obtained had [.eta.]=1.61 dl/g, Tm.sub.1=149.1.degree.
C., and Tm.sub.2=153.7.degree. C.
Comparative Example 1-4
Propylene Polymerization
[1641] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-1, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dimethylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride, and that the polymerization time was changed to 30
minutes. As a result, a polymer was obtained in an amount of 1.70 g
and the polymerization activity was 0.68 kg-PP/mmol-Zrhr. The
results of the polymer analysis were Tm.sub.2=150.1.degree. C.
Comparative Example 1-5
Propylene Polymerization
[1642] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-2, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dimethylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride, and that the polymerization time was changed to 60
minutes. As a result, a polymer was obtained in an amount of 2.65 g
and the polymerization activity was 0.53 kg-PP/mmol-Zrhr. The
polymer obtained had [.eta.]=1.22 dl/g and Tm.sub.2=131.0.degree.
C.
Comparative Example 1-6
Propylene Polymerization
[1643] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-1, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, and that the polymerization time was changed
to 45 minutes. As a result, a polymer was obtained in an amount of
2.38 g and the polymerization activity was 0.63 kg-PP/mmol-Zrhr.
The polymer obtained had [.eta.]=2.15 dl/g, Tm.sub.1=150.1.degree.
C., Tm.sub.2=155.4.degree. C., and rrrr=94.2%.
Comparative Example 1-7
Propylene Polymerization
[1644] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-2, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, and that the polymerization time was changed
to 45 minutes. As a result, a polymer was obtained in an amount of
2.14 g and the polymerization activity was 0.57 kg-PP/mmol-Zrhr.
The polymer obtained had [.eta.]=1.32 dl/g, Tm.sub.1=125.4.degree.
C., and Tm.sub.2=136.1.degree. C.
Comparative Example 1-8
Propylene Polymerization
[1645] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-2, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, and that the polymerization time was changed
to 60 minutes. As a result, a polymer was obtained in an amount of
0.75 g and the polymerization activity was 0.15 kg-PP/mmol-Zrhr.
The polymer obtained had [.eta.]=1.85 dl/g, Tm.sub.1=98.0.degree.
C., and Tm.sub.2=104.0.degree. C.
Example 1-13
Ethylene Polymerization
[1646] A thoroughly nitrogen purged glass autoclave with an
internal volume of 500 ml was charged with 400 ml of toluene, and
then charged with ethylene at a rate of 100 liter/hour, which was
kept at 75.degree. C. for 10 minutes. The autoclave was
sequentially charged with 1.3 mmol of a toluene solution of
methylaluminoxane (Al=1.21 mol/l) in terms of aluminum atom, and
2.0 .mu.mol of a toluene solution of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride in terms of zirconium atom. Then,
polymerization was initiated. Ethylene gas was continuously
supplied at a rate of 100 liter/hour, and the polymerization was
performed at 75.degree. C. for 6 minutes under normal pressure.
Thereafter, a small amount of methanol was added to terminate the
polymerization. The polymer solution was added to an excessive
amount of methanol to precipitate a polymer. The polymer was then
dried under reduced pressure at 80.degree. C. for 12 hours to
obtain a polymer in an amount of 4.59 g. The polymerization
activity was 23.0 kg-PE/mmol-Zrhr. The polymer obtained had
[.eta.]=3.69 dl/g.
Example 1-14
Ethylene Polymerization
[1647] A thoroughly nitrogen purged glass autoclave with an
internal volume of 500 ml was charged with 400 ml of toluene, and
then charged with ethylene at a rate of 100 liter/hour, which was
kept at 75.degree. C. for 10 minutes. The autoclave was
sequentially charged with 0.52 mmol of a toluene solution of
methylaluminoxane (Al=1.21 mol/l) in terms of aluminum atom and 0.8
.mu.mol of a toluene solution of
di(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride in terms of zirconium atom. Then,
polymerization was initiated. Ethylene gas was continuously
supplied at a rate of 100 liter/hour, and the polymerization was
performed at 75.degree. C. for 3 minutes under normal pressure.
Thereafter, a small amount of methanol was added to terminate the
polymerization. The polymer solution was added to an excessive
amount of methanol to precipitate a polymer. The polymer was then
dried under reduced pressure at 80.degree. C. for 12 hours to
obtain a polymer in an amount of 2.70 g. The polymerization
activity was 67.5 kg-PE/mmol-Zrhr. The polymer obtained had
[.eta.]=4.32 dl/g.
Example 1-15
Ethylene Polymerization
[1648] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-14, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
di(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride. As a result, a polymer was obtained in
an amount of 4.72 g. The polymerization activity was 118.0
kg-PE/mmol-Zrhr and the polymer obtained had [.eta.]=3.53 dl/g.
Example 1-16
Ethylene Polymerization
[1649] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-14, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride. As a result, a polymer was
obtained in an amount of 3.68 g. The polymerization activity was
92.0 kg-PE/mmol-Zrhr and the polymer obtained had [.eta.]=7.32
dl/g.
Example 1-17
Ethylene Polymerization
[1650] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-14, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
ditert-butylfluorenyl)zirconium dichloride, and that the
polymerization time was changed to 2 minutes. As a result, a
polymer was obtained in an amount of 4.24 g. The polymerization
activity was 159.0 kg-PE/mmol-Zrhr and the polymer obtained had
[.eta.]=7.61 dl/g.
Example 1-18
Ethylene Polymerization
[1651] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-13, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)-
zirconium dichloride, and that the polymerization time was changed
to 4 minutes. As a result, a polymer was obtained in an amount of
4.07 g. The polymerization activity was 30.5 kg-PE/mmol-Zrhr and
the polymer obtained had [.eta.]=4.05 dl/g.
Comparative Example 1-9
Ethylene Polymerization
[1652] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-13, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
cyclohexylidene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zir-
conium dichloride, and that the polymerization time was changed to
2 minutes. As a result, a polymer was obtained in an amount of 1.21
g. The polymerization activity was 18.2 kg-PE/mmol-Zrhr and the
polymer obtained had [.eta.]=2.23 dl/g.
Comparative Example 1-10
Ethylene Polymerization
[1653] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-13, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, and that the polymerization time was changed
to 2.5 minutes. As a result, a polymer was obtained in an amount of
1.76 g. The polymerization activity was 21.1 kg-PE/mmol-Zrhr and
the polymer obtained had [.eta.]=2.62 dl/g.
Comparative Example 1-11
Ethylene Polymerization
[1654] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-13, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, and that the polymerization time was changed
to 3 minutes. As a result, a polymer was obtained in an amount of
4.15 g. The polymerization activity was 41.5 kg-PE/mmol-Zrhr.
Example 1-19
Preparation of Supported Catalyst
[1655] In a 100 ml three-neck flask thoroughly purged with
nitrogen, a stirrer rod was placed and the flask was charged with
0.501 g of silica-supported methylaluminoxane (Al=16.1 wt %). The
flask was then charged with 15 ml of dehydrated toluene at room
temperature, and further charged with 10 ml of toluene solution in
which 10.2 mg of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was dissolved while stirring. The mixture
was stirred for 1 hour. The slurry obtained was filtered, and a
powder on the filter was washed once with 10 ml of dehydrated
toluene, and subsequently washed three times with 10 ml of
dehydrated hexane. The washed powder was dried under reduced
pressure for 2 hours to obtain a powder in an amount of 0.422 g.
The powder obtained was mixed with 3.80 g of a mineral oil to
obtain a 10.0 wt % slurry.
Example 1-20
Propylene Bulk Polymerization
[1656] In a 50 ml side-arm flask thoroughly purged with nitrogen, a
magnetic stirrer chip was placed, and the flask was charged with
0.596 g of a supported catalyst slurry prepared in Example 1-19
above mentioned, 1.0 mmol of hexane solution (Al=1.0M) of
triisobutylalminium, and 5.0 ml of dehydrated hexane. The resultant
mixture was introduced to a thoroughly nitrogen purged SUS
autoclave with an internal volume of 2000 ml. Thereafter, 500 g of
liquid propylene was charged. Subsequently, the polymerization was
carried out at 70.degree. C. for 40 minutes, and then the autoclave
was cooled and propylene was purged to terminate the
polymerization. The amount of the syndiotactic polypropylene
obtained was 38.7 g. The polymerization activity was 45.8
kg-PP/mmol-Zrhr. The results of polymer analysis were [.eta.]=0.99
dl/g, Mw=72800, Mw/Mn=1.87, Tm.sub.1=135.9.degree. C., and
Tm.sub.2=145.7.degree. C.
Example 1-21
Propylene Bulk Polymerization
[1657] The polymerization was carried out under the same condition
as in Example 1-20 described above, except that 0.194 g of the
supported catalyst slurry prepared in Example 1-19 above mentioned
was used and that 0.3 NL of hydrogen was added after charging 500 g
of liquid propylene. The amount of the syndiotactic polypropylene
obtained was 42.2 g, and the polymerization activity was 153.5
kg-PP/mmol-Zrhr. The results of polymer analysis were [.eta.]=1.00
dl/g, Mw=74200, Mw/Mn=1.99, Tm.sub.1=134.6.degree. C., and
Tm.sub.2=145.8.degree. C.
Comparative Example 1-12
Preparation of Supported Catalyst
[1658] In a 100 ml three-neck flask thoroughly purged with
nitrogen, a stirrer rod was placed, and the flask was charged with
0.506 g of silica-supported methylaluminoxane (AL=16.1 wt %). The
flask was then charged with 15 ml of dehydrated toluene at room
temperature, and further charged with 10 ml of toluene solution in
which 10.3 mg of the
isopropylidene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride was dissolved while stirring. The mixture was stirred
for 1 hour. The slurry obtained was filtered, and a powder on the
filter was washed once with 10 ml of dehydrated toluene, and
subsequently washed three times with 10 ml of dehydrated hexane.
The washed powder was dried under reduced pressure for 2 hours to
obtain a powder in an amount of 0.410 g. The powder obtained was
mixed with 3.69 g of a mineral oil to obtain a 10.0 wt %
slurry.
Comparative Example 1-13
Propylene Bulk Polymerization
[1659] In a 50 ml side-arm flask thoroughly purged with nitrogen, a
magnetic stirrer chip was placed, and the flask was charged with
0.205 g of a supported catalyst slurry prepared in Comparative
Example 1-12 above mentioned, 1.0 mmol of hexane solution (Al=1.0M)
of triisobutylalminium, and 5.0 ml of dehydrated hexane. The
resultant mixture was introduced to a thoroughly nitrogen purged
SUS autoclave with an internal volume of 2000 ml. Thereafter, 500 g
of liquid propylene was charged. Subsequently, the polymerization
was carried out at 70.degree. C. for 40 minutes, and then the
autoclave was cooled and propylene was purged to terminate the
polymerization. The polymer was dried under reduced pressure at
80.degree. C. for 10 hours. The amount of a syndiotactic
polypropylene obtained was 6.9 g. The polymerization activity was
16.9 kg-PP/mmol-Zrhr. The results of polymer analysis were
[.eta.]=1.15 dl/g, Mw=88200, Mw/Mn=1.76, Tm.sub.1=126.9.degree. C.,
and Tm.sub.2=136.9.degree. C.
Comparative Example 1-14
Propylene Bulk Polymerization
[1660] The polymerization was carried out under the same condition
as in Comparative Example 1-13 described above, except that 0.198 g
of the supported catalyst slurry prepared in Comparative Example
1-12 above mentioned was used and that 0.3 NL of hydrogen was added
after charging 500 g of liquid propylene. The amount of a
syndiotactic polypropylene obtained was 168.9 g and the
polymerization activity was 429.7 kg-PP/mmol-Zrhr. The results of
polymer analysis were [.eta.]=1.07 dl/g, Mw=84700, Mw/Mn=1.96,
Tm.sub.1=122.3.degree. C., and Tm.sub.2=136.4.degree. C.
Example 1-22
Propylene Polymerization
[1661] A thoroughly nitrogen purged glass autoclave with an
internal volume of 500 ml, was charged with 400 mL of n-heptane,
and then charged with propylene at a rate of 150 liter/hour, which
was kept at 25.degree. C. for 20 minutes. Meanwhile, a magnetic
stirrer was placed in a thoroughly nitrogen purged side arm flask
with an internal volume of 30 ml, and the flask was sequentially
charged with 5.00 mmol of a toluene solution of methylaluminoxane
(Al=1.53 mol/L), and 5.0 mol of a toluene solution of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride. The mixture was stirred for 20 minutes.
This solution was then added to n-heptane in the glass autoclave
which had been charged with propylene, and the polymerization was
initiated. Propylene gas was continuously supplied at a rate of 150
liter/hour, and the polymerization was performed at 25.degree. C.
for 7.5 minutes under normal pressure. Thereafter, a small amount
of methanol was added to terminate the polymerization. The polymer
solution was added to an excessive amount of methanol to
precipitate a polymer. The polymer was then dried under reduced
pressure at 80.degree. C. for 12 hours to obtain a polymer in an
amount of 9.00 g. The polymerization activity was 14.40
kg-PP/mmol-Zrhr. The polymer obtained had [.eta.]=2.73 dl/g and
Tm.sub.2=159.0.degree. C.
Example 1-23
Propylene Polymerization
[1662] The polymerization was carried out in the same manner as in
Example 1-22, except that the temperature inside the autoclave
before the polymerization and during the polymerization was kept at
50.degree. C., and that the polymerization time was changed to 31
minutes. The amount of the polymer obtained was 19.60 g, and the
polymerization activity was 7.59 kg-PP/mmol-Zrhr. The polymer
obtained had [.eta.]=1.72 dl/g, Tm.sub.1=149.9.degree. C., and
Tm.sub.2=154.8.degree. C.
Example 1-24
Propylene Polymerization
[1663] A thoroughly nitrogen purged glass autoclave with an
internal volume of 500 ml was charged with 250 ml of toluene was
charged, and then charged with propylene at a rate of 150
liter/hour, which was kept at 25.degree. C. for 20 minutes.
Meanwhile, a magnetic stirrer was placed in a thoroughly nitrogen
purged side arm flask with an internal volume of 30 ml, and the
flask was sequentially charged with 5.00 mmol of a toluene solution
of methylaluminoxane (Al=1.53 mol/L) and 5.0 .mu.mol of a toluene
solution of
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-di
tert-butylfluorenyl)zirconium dichloride. The mixture was stirred
for 20 minutes. This solution was then added to toluene in the
glass autoclave which had been charged with propylene, and the
polymerization was initiated. Propylene gas was continuously
supplied at a rate of 150 liter/hour, and the polymerization was
performed at 25.degree. C. for 15 minutes under normal pressure.
Thereafter, a small amount of methanol was added to terminate the
polymerization. The polymer solution was added to an excessive
amount of methanol to precipitate a polymer. The polymer was then
dried under reduced pressure at 80.degree. C. for 12 hours to
obtain a polymer in an amount of 12.19 g. The polymerization
activity was 9.75 kg-PP/mmol-Zrhr. The polymer obtained had
[.eta.]=2.27 dl/g, Tm.sub.1=156.5.degree. C., and
Tm.sub.2=161.0.degree. C.
Example 1-25
Propylene Polymerization
[1664] Polymerization was carried out in the same manner as in
Example 1-24, except that the temperature inside the autoclave
before the polymerization and during the polymerization was kept at
50.degree. C., and that the polymerization time was changed to 20
minutes. The amount of the polymer obtained was 12.30 g, and the
polymerization activity was 7.38 kg-PP/mmol-Zrhr. The polymer
obtained had [.eta.]=1.43 dl/g, Tm.sub.1=143.0.degree. C., and
Tm.sub.2=150.6.degree. C.
Example 1-26
Propylene Polymerization
[1665] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-23, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride, and that the polymerization time was
changed to 15 minutes. As a result, a polymer was obtained in an
amount of 5.75 g. The polymerization activity was 4.60
kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=1.59 dl/g,
Tm.sub.1=147.2.degree. C., and Tm.sub.2=154.1.degree. C.
Example 1-27
Propylene Polymerization
[1666] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-24, except that
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(2,7-[p-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, and that the polymerization time was
changed to 10 minutes. As a result, a polymer was obtained in an
amount of 29.81 g. The polymerization activity was 35.77
kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=1.00 dl/g,
Tm.sub.1=155.1.degree. C., and Tm.sub.2=160.0.degree. C.
Example 1-28
Propylene Polymerization
[1667] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-25, except that
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(2,7-[p-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, and that the polymerization time was
changed to 15 minutes. As a result, a polymer was obtained in an
amount of 39.08 g. The polymerization activity was 31.26
kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=0.71 dl/g,
Tm.sub.1=140.5.degree. C., and Tm.sub.2=148.9.degree. C.
Example 1-29
Propylene Polymerization
[1668] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-23, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(2,7-[p-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, and that the polymerization time was
changed to 15 minutes. As a result, a polymer obtained in an amount
of 7.42 g. The polymerization activity was 5.94 kg-PP/mmol-Zrhr,
and the polymer obtained had [.eta.]=1.87 dl/g,
Tm.sub.1=147.2.degree. C., and Tm.sub.2=153.6.degree. C.
Example 1-30
Propylene Polymerization
[1669] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-24, except that
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(2,7-[o-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, and that the polymerization time was
changed to 5 minutes. As a result, a polymer was obtained in an
amount of 2.24 g. The polymerization activity was 5.38
kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=3.63 dl/g and
Tm.sub.2=156.0.degree. C.
Example 1-31
Propylene Polymerization
[1670] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-25, except that
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(2,7-[o-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, and that the polymerization time was
changed to 8 minutes. As a result, a polymer was obtained in an
amount of 3.98 g. The polymerization activity was 5.97
kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=2.46 dl/g,
Tm.sub.1=138.4.degree. C., and Tm.sub.2=145.8.degree. C.
Example 1-32
Propylene Polymerization
[1671] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-22, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(2,7-[o-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, and that the polymerization time was
changed to 9 minutes. As a result, a polymer was obtained in an
amount of 3.75 g. The polymerization activity was 5.00
kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=3.88 dl/g and
Tm.sub.2=156.2.degree. C.
Example 1-33
Propylene Polymerization
[1672] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-23, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(2,7-[o-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, and that the polymerization time was
changed to 20 minutes. As a result, a polymer was obtained in an
amount of 6.66 g. The polymerization activity was 4.00
kg-PP/mmol-Zrhr, and the polymer obtained had
Tm.sub.1=141.9.degree. C. and Tm.sub.2=149.0.degree. C.
Example 1-34
Ethylene Polymerization
[1673] A thoroughly nitrogen purged glass autoclave with an
internal volume of 500 ml was charged with 400 ml of toluene, and
then charged with ethylene at a rate of 100 liter/hour, which was
kept at 75.degree. C. for 10 minutes. Then, the flask was
sequentially charged with 1.3 mmol of a toluene solution of
methylaluminoxane (Al=1.21 mol/l) and 2.0 .mu.mol of a toluene
solution of
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride. Thereafter, the polymerization was
initiated. Ethylene gas was continuously supplied at a rate of 100
liter/hour, and the polymerization was performed at 75.degree. C.
for 4 minutes under normal pressure. Thereafter, a small amount of
methanol was added to terminate the polymerization. The polymer
solution was added to an excessive amount of methanol to
precipitate a polymer. The polymer was then dried under reduced
pressure at 80.degree. C. for 12 hours to obtain a polymer in an
amount of 3.76 g. The polymerization activity was 28.2
kg-PE/mmol-Zrhr. The polymer obtained had [.eta.]=3.74 dl/g.
Example 1-35
Ethylene Polymerization
[1674] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-34, except that
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(2,7-[p-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, and that the polymerization time was
changed to 5 minutes. As a result, a polymer was obtained in an
amount of 6.00 g. The polymerization activity was 36.0
kg-PE/mmol-Zrhr and the polymer obtained had [.eta.]=4.58 dl/g.
Example 1-36
Ethylene Polymerization
[1675] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-34, except that
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride was changed to
dibenzylmethylene(cyclopentadienyl)(2,7-[o-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, and that the polymerization time was
changed to 6 minutes. As a result, a polymer was obtained in an
amount of 4.41 g. The polymerization activity was 22.1
kg-PE/mmol-Zrhr and the polymer obtained had [.eta.]=6.37 dl/g.
Example 1-37
Propylene Polymerization
[1676] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-24, except that
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride was changed to
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride. As a result, a polymer was
obtained in an amount of 6.54 g. The polymerization activity was
5.23 kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=2.29
dl/g, Tm.sub.1=157.6.degree. C., and Tm.sub.2=163.0.degree. C.
Example 1-38
Propylene Polymerization
[1677] The preparation of the catalyst solution and the
polymerization were carried out in the same manner as in Example
1-25, except that
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride was changed to
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, and that the polymerization time
was changed to 15 minutes. As a result, a polymer obtained in an
amount of 6.17 g. The polymerization activity was 4.94
kg-PP/mmol-Zrhr, and the polymer obtained had [11]=1.48 dl/g,
Tm.sub.1=146.6.degree. C., and Tm.sub.2=154.1.degree. C.
Example 1-39
Propylene Polymerization
[1678] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-22, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, and that the polymerization time
was changed to 8 minutes. As a result, a polymer was obtained in an
amount of 2.76 g. The polymerization activity was 4.14
kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=2.68 dl/g and
Tm.sub.2=160.5.degree. C.
Example 1-40
Propylene Polymerization
[1679] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-23, except that
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride was changed to
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, and that the polymerization time
was changed to 10 minutes. As a result, a polymer was obtained in
an amount of 1.69 g. The polymerization activity was 2.03
kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=1.55 dl/g,
Tm.sub.1=150.2.degree. C., and Tm.sub.2=156.8.degree. C.
Comparative Example 1-15
Propylene Polymerization
[1680] A thoroughly nitrogen purged glass autoclave with an
internal volume of 500 ml was charged with 400 mL of n-hexane, and
then charged with propylene at a rate of 150 liter/hour, which was
kept at 45.degree. C. for 20 minutes. Meanwhile, a magnetic stirrer
was placed in a thoroughly nitrogen purged side arm flask with an
internal volume of 30 ml, and the flask was sequentially charged
with 5.00 mmol of a toluene solution of methylaluminoxane (Al=1.53
mol/L) and 5.0 .mu.mol of a toluene solution of
dibenzylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride. The mixture was stirred for 20 minutes. This solution
was then added to toluene in the glass autoclave which had been
charged with propylene, and the polymerization was initiated.
Propylene gas was continuously supplied at a rate of 150
liter/hour, and the polymerization was performed at 45.degree. C.
for 30 minutes under normal pressure. Thereafter, a small amount of
methanol was added to terminate the polymerization. The polymer
solution was added to an excessive amount of methanol to
precipitate a polymer. The polymer was then dried under reduced
pressure at 80.degree. C. for 12 hours to obtain a polymer in an
amount of 2.15 g. The polymerization activity was 0.86
kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=1.31 dl/g,
Tm.sub.1=134.1.degree. C., and Tm.sub.2=143.5.degree. C.
Example 1-41
Ethylene Polymerization
[1681] Preparation of a catalyst solution and polymerization were
carried out in the same manner as in Example 1-34, except that
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride was changed to
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, and that the polymerization time
was changed to 6 minutes. As a result, a polymer was obtained in an
amount of 2.00 g. The polymerization activity was 10.0
kg-PE/mmol-Zrhr, and the polymer obtained had [.eta.]=3.36
dl/g.
Example 1-42
Ethylene Polymerization
[1682] A thoroughly nitrogen purged glass autoclave with the
internal volume of 500 ml was charged with 400 mL of toluene, and
then charged with ethylene at a rate of 100 liter/hour, which was
kept at 75.degree. C. for 10 minutes. Thereafter, the flask was
sequentially charged with 0.52 mmol of a toluene solution of
methylaluminoxane (Al=1.21 mol/l) and 0.8 mol of a toluene solution
of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, and the polymerization was
initiated. Ethylene gas was continuously supplied at a rate of 100
liter/hour, and the polymerization was performed at 75.degree. C.
for 6 minutes under normal pressure. Thereafter, a small amount of
methanol was added to terminate the polymerization. The polymer
solution was added to an excessive amount of methanol to
precipitate a polymer, which was then dried under reduced pressure
at 80.degree. C. for 12 hours to obtain a polymer in an amount of
0.42 g. The polymerization activity was 5.3 kg-PE/mmol-Zrhr. The
polymer obtained had [.eta.]=8.44 dl/g.
[1683] The results for the propylene polymerization according to
Examples 1-1 to -12 and Comparative Examples 1-1 to -8 are arranged
in Table 1-1. The results for the ethylene polymerization according
to Examples 1-13 to -18 and Comparative Examples 1-9 to -11 are
arranged in Table 1-2. The results for the propylene polymerization
according to Examples 1-22 to -33, and -37 to -40, and Comparative
Example 1-12, are arranged in Table 1-3. The results for the
ethylene polymerization according to Examples 1-34 to -36, 41, and
42, are arranged in Table 1-4.
[1684] [Table 1-1]
TABLE-US-00001 TABLE 1-1 Propylene Polymerization Transition metal
Polymerization compound activity *1 *2 *3 Yield (Kg-PP/mmol-
[.eta.] Tm.sub.1/Tm.sub.2 rrrr Type (.mu.mol) (.degree. C.) (min)
(g) Zr hr) (dl/g) (.degree. C.) (%) Ex. 1-1 Catalyst a 5 25 10 6.32
7.58 2.54 157.0/162.0 95.3 Ex. 1-2 Catalyst a 5 50 15 12.74 10.19
1.64 142.9/150.1 -- Ex. 1-3 Catalyst b 5 25 25 7.35 3.53 2.43
154.9/160.0 95.2 Ex. 1-4 Catalyst b 5 50 25 11.00 5.28 1.54
138.6/146.2 -- Ex. 1-5 Catalyst c 5 25 40 3.31 0.99 2.52
142.6/151.8 -- Ex. 1-6 Catalyst d 5 25 30 8.35 3.34 5.98 --/153.3
-- Ex. 1-7 Catalyst d 5 50 40 2.90 0.87 3.22 139.1/143.8 -- Ex. 1-8
Catalyst e 5 25 60 7.30 1.46 5.96 142.6/149.0 -- Ex. 1-9 Catalyst f
5 25 60 2.90 0.58 4.64 135.7/141.9 -- Ex. 1-10 Catalyst g 5 25 15
6.55 5.24 2.17 153.3/157.7 -- Ex. 1-11 Catalyst g 5 50 15 5.64 4.51
1.42 136.9/145.8 -- Ex. 1-12 Catalyst a 5 25 20 10.56 6.34 1.25
144.9/151.8 -- C.E. 1-1 Catalyst h 5 25 15 8.94 7.15 2.12
150.2/155.2 94.1 C.E. 1-2 Catalyst h 5 50 15 8.23 6.58 1.23
132.2/142.1 -- C.E. 1-3 Catalyst i 5 25 60 0.06 0.02 1.61
149.1/153.7 -- C.E. 1-4 Catalyst j 5 25 30 1.70 0.68 -- --/150.1 --
C.E. 1-5 Catalyst j 5 50 60 2.65 0.53 1.22 --/131.0 -- C.E. 1-6
Catalyst k 5 25 45 2.38 0.63 2.15 150.1/155.4 94.2 C.E. 1-7
Catalyst k 5 50 45 2.14 0.57 1.32 125.4/136.1 -- C.E. 1-8 Catalyst
l 5 50 60 0.75 0.15 1.85 98.0/104.0 -- Ex: Example C.E.:
Comparative Example *1: Amount in terms of Zr atom *2:
Polymerization temperature *3: Polymerization time Catalyst a:
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride, Catalyst b:
di(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride, Catalyst c:
di(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride, Catalyst d:
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, Catalyst e:
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, Catalyst f:
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
ditert-butylfluorenyl)zirconium dichloride, Catalyst g:
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)-
zirconium dichloride, Catalyst h:
dibenzylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride, Catalyst i:
cyclohexylidene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zir-
conium dichloride, Catalyst j:
dimethylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride, Catalyst k:
dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, Catalyst l:
diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride,
TABLE-US-00002 TABLE 1-2 Ethylene Polymerization Transition metal
Polymerization compound Ethylene MAO activity *1 flow amount *2 *3
Yield (Kg-PE/mmol- [.eta.] Type (mmol) (l/hr) (mmol) (min) (g) Zr
hr) (dl/g) Ex. 1-13 Catalyst a 2.0 100 1.30 6 4.59 23.0 3.69 Ex.
1-14 Catalyst b 0.8 100 0.52 3 2.7 67.5 4.32 Ex. 1-15 Catalyst c
0.8 100 0.52 3 4.72 118.0 3.53 Ex. 1-16 Catalyst e 0.8 100 0.52 3
3.68 92.0 7.32 Ex. 1-17 Catalyst f 0.8 100 0.52 2 4.24 159.0 7.61
Ex. 1-18 Catalyst g 2.0 100 1.30 4 4.07 30.5 4.05 C.E. 1-9 Catalyst
i 2.0 100 1.30 2 1.21 18.2 2.23 C.E. 1-10 Catalyst k 2.0 100 1.30
2.5 1.76 21.1 2.62 C.E. 1-11 Catalyst l 2.0 100 1.30 3 4.15 41.5
Ex: Example C.E.: Comparative Example *1: Amount in terms of Zr
atom *2: Amount in terms of Al atom *3: Polymerization time
Catalyst a:
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride, Catalyst b:
di(n-butyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride, Catalyst c:
di(n-butyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-butylfluor-
enyl)zirconium dichloride, Catalyst e:
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, Catalyst f:
di(m-trifluoromethyl-phenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6--
ditert-butylfluorenyl)zirconium dichloride, Catalyst g:
cyclohexylidene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluorenyl)-
zirconium dichloride, Catalyst i:
cyclohexylidene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zir-
conium dichloride, Catalyst k:
dibenzylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride, Catalyst l:
diphenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)z-
irconium dichloride,
TABLE-US-00003 TABLE 1-3 Propylene Polymerization Transition metal
Polymerization compound activity *1 *2 *3 Yield (Kg-PP/mmol-
[.eta.] Tm.sub.1/Tm.sub.2 Type (.mu.mol) (.degree. C.) (Min) (g) Zr
hr) (dl/g) (.degree. C.) Ex. 1-22 Catalyst a 5 25 7.5 9.00 14.40
2.73 --/159.0 Ex. 1-23 Catalyst a 5 50 31 19.60 7.59 1.72
149.9/154.8 Ex. 1-24 Catalyst m 5 25 15 12.19 9.75 2.27 156.5/161.0
Ex. 1-25 Catalyst m 5 50 20 12.30 7.38 1.43 143.0/150.6 Ex. 1-26
Catalyst m 5 50 15 5.75 4.60 1.59 147.2/154.1 Ex. 1-27 Catalyst n 5
25 10 29.81 35.77 1.00 155.1/160.0 Ex. 1-28 Catalyst n 5 50 15
39.08 31.26 0.71 140.5/148.9 Ex. 1-29 Catalyst n 5 50 15 7.42 5.94
1.87 147.2/153.6 Ex. 1-30 Catalyst o 5 25 5 2.24 5.38 3.63 --/156.0
Ex. 1-31 Catalyst o 5 50 8 3.98 5.97 2.46 138.4/145.8 Ex. 1-32
Catalyst o 5 25 9 3.75 5.00 3.88 --/156.2 Ex. 1-33 Catalyst o 5 50
20 6.66 4.00 -- 141.9/149.0 Ex. 1-37 Catalyst p 5 25 15 6.54 5.23
2.29 157.6/163.0 Ex. 1-38 Catalyst p 5 50 15 6.17 4.94 1.48
146.6/154.1 Ex. 1-39 Catalyst p 5 25 8 2.76 4.14 2.68 --/160.5 Ex.
1-40 Catalyst p 5 50 10 1.69 2.03 1.55 150.2/156.8 C.E. 1-15
Catalyst h 5 45 30 2.15 0.86 1.31 134.1/143.5 Ex: Example C.E.:
Comparative Example *1: Amount in terms of Zr atom *2:
Polymerization temperature *3: Polymerization time Catalyst a:
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfluoreny-
l)zirconium dichloride, Catalyst h:
dibenzylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirconium
dichloride, Catalyst m:
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride, Catalyst n:
dibenzylmethylene(cyclopentadienyl)(2,7-[p-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, Catalyst o:
dibenzylmethylene(cyclopentadienyl)(2,7-[o-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, Catalyst p:
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride,
TABLE-US-00004 TABLE 1-4 Ethylene Polymerization Transition metal
Polymerization compound MAO activity *1 *2 *3 Yield (Kg-PE/mmol-
[.eta.] Type (.mu.mol) (mmol) (Minute) (g) Zr hr) (dl/g) Ex. 1-34
Catalyst m 2.0 1.30 4 3.76 28.2 3.74 Ex. 1-35 Catalyst n 2.0 1.30 5
6.00 36.0 4.58 Ex. 1-36 Catalyst o 2.0 1.30 6 4.41 22.1 6.37 Ex.
1-41 Catalyst p 2.0 1.30 6 2.00 10.0 3.36 Ex. 1-42 Catalyst d 0.8
0.52 6 0.42 5.3 8.44 Ex: Example *1: Amount in terms of Zr atom *2:
Amount in terms of Al atom *3: Polymerization time Catalyst d:
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride, Catalyst m:
dibenzylmethylene(cyclopentadienyl)(2,7-[2-naphthyl]-3,6-ditert-butylfluo-
renyl)zirconium dichloride, Catalyst n:
dibenzylmethylene(cyclopentadienyl)(2,7-[p-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, Catalyst o:
dibenzylmethylene(cyclopentadienyl)(2,7-[o-tolyl]-3,6-ditert-butylfluoren-
yl)zirconium dichloride, Catalyst p:
di(4-chlorobenzyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-but-
ylfluorenyl)zirconium dichloride,
Example II
[1685] Hereinafter, the present invention (2) will be further
explained in detail with the reference to Examples, but the present
invention is not limited to Examples.
[1686] The structures of the metallocene compounds and the
precursors thereof were determined with use of 270 MHz .sup.1H-NMR
(JEOL LTD. GSH-270), FD-mass analysis (JEOL LTD. SX-102 A), and the
like.
[1687] Hereinbelow, the conditions of property tests and the like
are described.
[1688] 1. The intrinsic viscosity [.eta.] was measured in decalin
at 135.degree. C.
[1689] 2. Butene content and ethylene content were determined by
.sup.13C-NMR spectrum.
[1690] [Synthesis Method of Known Metallocene Compound]
[1691] Diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride used in Comparative Examples was a known metallocene
compound and was synthesized in accordance with a method described
in JP-A No. 2-274703.
Synthesis Example 2-1
Synthesis of
di(m-(trifluoromethyl)phenyl)methylene(cyclopentadienyl)(octamethyloctahy-
drodibenzofluorenyl)zirconium dichloride
(i) Synthesis of octamethyloctahydrodibenzofluorene
[1692] To a 500-ml three-necked flask which was thoroughly purged
with nitrogen and equipped with a three-way cock, a dropping funnel
and a magnetic stirrer, 9.72 g (58.6 mmol) of fluorine and 19.6 g
(134 mmol) of 2,5-dimethyl-2,5-hexanediol were added at room
temperature. Then, 85 ml of dehydrated dichloromethane was added.
The mixture was stirred with a magnetic stirrer, and cooled to
-8.degree. C. in an ice bath. Subsequently, 38.9 g (292 mmol) of
pulverized anhydrous aluminum chloride was added thereto over 70
minutes, and the mixture was then stirred for 2 hours at 0.degree.
C. Thereafter, the ice bath was removed, and the mixture was
further stirred at room temperature for 19 hours. Disappearance of
fluorine was confirmed by G.C., and then the dark brown solution
was poured into 150 ml of ice water to quench the solution.
Subsequently, the soluble fraction was extracted with 500 ml of
diethyl ether, and then the organic layer was neutralized with a
saturated aqueous solution of sodium hydrogen carbonate, and washed
with water. The organic phase collected by separation was dried
over anhydrous magnesium sulfate. Subsequently, magnesium sulfate
was separated by filtration, and the filtrate was subjected to
distillation under reduced pressure with use of a rotary evaporator
to remove the solvent. The residue was transferred onto a Kiriyama
funnel, washed 6 times with 10 ml of hexane, and dried under
reduced pressure to obtain a target product (yield 12.0 g (53%)).
The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1693] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.3 (s,
12H), 1.4 (s, 12H), 1.7 (s, 8H), 3.8 (s, 2H), 7.4 (s, 2H), 7.6 (s,
2H).
[1694] MS (FD): M/z 386 (M.sup.+).
(ii) Synthesis of 6,6-di[m-(trifluoromethyl)phenyl]fulvene
[1695] A reaction vessel equipped with a dropping funnel was
charged with 80 ml of dehydrated tetrahydrofuran and 2.0 ml (24.1
mmol) of cyclopentadiene under a nitrogen atmosphere. Then, 17.0 ml
(26.5 mmol) of a 1.56 mol/L hexane solution of n-butyllithium was
slowly added dropwise while cooling this solution to 0.degree. C.,
and the mixture was stirred overnight at room temperature.
Subsequently, the dropping funnel was charged with a solution
prepared by dissolving 8.43 g (26.5 mmol) of
3,3'-(trifluoromethyl)benzophenone in 50 ml of dehydrated
tetrahydrofuran. The solution was slowly added dropwise while
cooling to 0.degree. C. Thereafter, the mixture was left to stand
and the temperature thereof was returned to room temperature. The
mixture was then stirred for one day. This reaction solution was
subjected to extraction with diethyl ether. The organic layer was
washed with 1 N hydrochloric acid, a saturated aqueous solution of
sodium hydrogen carbonate and saturated brine. The organic phase
collected by separation was dried over anhydrous magnesium sulfate.
Subsequently, magnesium sulfate was separated by filtration, and
the filtrate was subjected to distillation under reduced pressure
with use of a rotary evaporator to remove the solvent. The residue
was purified using a silica gel column to obtain a target product
(yield 4.14 g (47%)). The target product was identified by
.sup.1H-NMR.
[1696] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm
6.17-6.21 (m, 2H), 6.64-6.66 (m, 2H), 7.44-7.58 (m, 6H), 7.68 (d,
2H, J=7.56 Hz).
(iii) Synthesis of
di[m-(trifluoromethyl)phenyl]cyclopentadienyl(octamethyloctahydrodibenzof-
luorenyl)methane
[1697] A reaction vessel equipped with a dropping funnel was
charged with 30 m of dehydrated tetrahydrofuran and 0.82 g (2.11
mmol) of octamethyloctahydrodibenzofluorene under a nitrogen
atmosphere. Then, 1.50 ml (2.32 mmol) of a 1.56 mol/L hexane
solution of n-butyllithium was slowly added dropwise while cooling
this solution to 0.degree. C. Thereafter, the mixture was stirred
overnight at room temperature. Subsequently, the dropping funnel
was charged with a solution prepared by dissolving 1.00 g (2.32
mmol) of 6,6-di{m-(trifluoromethyl)phenyl}fulvene in 20 ml of
dehydrated tetrahydrofuran. The solution was slowly added dropwise
while cooling to -78.degree. C. Thereafter, the mixture was stirred
for one day while returning the temperature thereof slowly to room
temperature. This reaction solution was subjected to extraction
with diethyl ether. The organic layer was washed with 1 N
hydrochloric acid, a saturated aqueous solution of sodium hydrogen
carbonate and saturated brine. The organic phase collected by
separation was dried over anhydrous magnesium sulfate, and
magnesium sulfate was separated by filtration. The filtrate was
subjected to distillation under reduced pressure with use of a
rotary evaporator to remove the solvent. The residue was purified
by using a silica gel column to obtain a target product (yield 0.74
g (47%)). The target product was identified by .sup.1H-NMR and
FD-MS spectroscopy.
[1698] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.94 (b,
5H), 1.14 (s, 6H) 1.21 (s, 7H), 1.26 (s, 7H), 1.62 (s, 8H), 3.14
(b, 2H), 5.46 (s, 1H), 6.48 (m, 2H), 7.06-7.28 (m, 12H).
[1699] MS (FD): m/z 752 (M.sup.+).
(iv) Synthesis of
di[m-(trifluoromethyl)phenyl]methylene(cyclopentadienyl)(octamethyloctahy-
drodibenzofluorenyl)zirconium dichloride
[1700] Under a nitrogen atmosphere, 0.79 g (1.05 mmol) of
di[m-(trifluoromethyl)phenyl]cyclopentadienyl(octamethyloctahydrodibenzof-
luorenyl)methane was added to 30 m of dehydrated diethyl ether.
Then, 1.39 mL (2.20 mmol) of a 1.58 mol/L hexane solution of
n-butyllithium was slowly added dropwise while cooling this
solution to 0.degree. C., and the mixture was stirred overnight.
Subsequently, 438 mg (1.16 mmol) of zirconium
tetrachloride-tetrahydrofuran complex (1:2) was added while cooling
to -78.degree. C., and the mixture was stirred overnight. The
volatile fraction of this slurry was removed by distillation under
reduced pressure. The residue was washed with 40 ml of dehydrated
hexane, and the wash liquid was separated by filtration. The
filtrate in which the hexane-solubles were dissolved was
concentrated, dehydrated pentane was added to the resulting solids,
and the solid was recrystallized to obtain a target product (yield
70 mg (7%)). The target product was identified by .sup.1H-NMR and
FD-MS spectroscopy.
[1701] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.827
(s, 6H), 0.93 (s, 6H), 1.42 (s, 6H), 1.49 (s, 6H), 1.60-1.69 (m,
8H), 5.52-5.56 (m, 2H), 6.042 (s, 1H), 6.088 (s, 1H), 6.32-6.38 (m,
2H), 7.56-7.66 (m, 4H), 8.09-8.12 (m, 4H), 8.16-8.25 (m, 2H).
[1702] MS (FD): m/z 912 (M.sup.+).
Synthesis Example 2-2
Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride
(i) Synthesis of 6,6-di(p-chlorophenyl)fulvene
[1703] A reaction vessel equipped with a dropping funnel was
charged with 40 ml of dehydrated tetrahydrofuran and 2.15 ml (25.9
mmol) of cyclopentadiene under a nitrogen atmosphere. Then, 18.0 mL
(28.5 mmol) of a 1.58 mol/L hexane solution of n-butyllithium was
slowly added dropwise while cooling this solution to 0.degree. C.,
and the mixture was stirred. Subsequently, the dropping funnel was
charged with a solution prepared by dissolving 5.00 g (19.9 mmol)
of 4,4'-dichlorobenzophenone in 30 ml of dehydrated tetrahydrofuran
was placed in. The solution was slowly added dropwise while cooling
to -0.degree. C. Thereafter, the mixture was left to stand and the
temperature thereof was returned to room temperature. The mixture
was then stirred for one day. This reaction solution was subjected
to extraction with diethyl ether. The organic layer was washed with
1 N hydrochloric acid, a saturated aqueous solution of sodium
hydrogen carbonate and saturated brine. The organic phase collected
by separation was dried over anhydrous magnesium sulfate.
Subsequently, magnesium sulfate was separated by filtration, and
the filtrate was subjected to distillation under reduced pressure
with use of a rotary evaporator to remove the solvent. The residue
was purified by using a silica gel column to obtain a target
product (yield 3.37 g (57%)). The target product was identified by
.sup.1H-NMR.
[1704] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm
6.21-6.24 (m, 2H), 6.60-6.63 (m, 2H), 7.23 (d, 2H, J=8.1 Hz), 7.37
(d, 2H, J=8.6 Hz).
(ii) Synthesis of
di(p-chlorophenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)me-
thane
[1705] A reaction vessel equipped with a dropping funnel was
charged with 40 ml of dehydrated tetrahydrofuran and 2.35 g (6.08
mmol) of octamethyloctahydrodibenzofluorene synthesized in
Synthesis Example 2-1 under a nitrogen atmosphere. Then, 4.62 ml
(7.30 mmol) of a 1.58 mol/L hexane solution of n-butyllithium was
slowly added dropwise and while cooling this solution to 0.degree.
C., and the mixture was stirred. Then, 0.86 ml (7.90 mmol) of
1,3-dimethyl-2-imidazolidinone was added to the solution and the
mixture was stirred for 30 minutes. Subsequently, the dropping
funnel was charged with a solution prepared by dissolving 2.00 g
(6.68 mmol) of 6,6-di{p-chlorophenyl}fulvene in 30 ml of dehydrated
tetrahydrofuran. The solution was slowly added dropwise while
cooling the solution to -78.degree. C. The mixture was stirred for
one day while returning the temperature thereof slowly to room
temperature. This reaction solution was subjected to extraction
with diethyl ether. The organic layer was washed with 1 N
hydrochloric acid, a saturated aqueous solution of sodium hydrogen
carbonate and saturated brine. The organic phase collected by
separation was dried over anhydrous magnesium sulfate and magnesium
sulfate was separated by filtration. The filtrate was subjected to
distillation under reduced pressure using a rotary evaporator to
remove the solvent. The residue was purified by using a silica gel
column and recrystallized from toluene to obtain a target product
(yield 0.714 g (17%)). The target product was identified by
.sup.1H-NMR and FD-MS spectroscopy.
[1706] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.94 (s,
6H), 1.14 (s, 6H), 1.27 (s, 12H), 1.62 (s, 8H), 3.06 (b, 2H), 5.30
(s, 1H), 6.38-6.50 (b, 3H), 7.00-7.29 (m, 8H).
[1707] MS (FD): m/z 684 (M.sup.+).
(iii) Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride
[1708] Under a nitrogen atmosphere, 428 mg (0.62 mmol) of
di[p-chlorophenyl]cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)me-
thane was added to 15 ml of dehydrated diethyl ether. Then, 0.87 ml
(1.37 mmol) of a 1.58 mol/L hexane solution of n-butyllithium was
slowly added dropwise while cooling this solution to 0.degree. C.,
and the mixture was stirred overnight. Subsequently, 224 mg (0.59
mmol) of zirconium tetrachloride.tetrahydrofuran complex (1:2) was
added while cooling the mixture to -78.degree. C., and the mixture
was stirred overnight. The volatile fraction of this slurry was
removed by distillation under reduced pressure. The residue was
washed with 40 ml of dehydrated hexane, and the washed liquid was
separated by filtration. The filtrate in which the hexane-solubles
were dissolved was concentrated, dehydrated hexane was added to the
resulting solids and the solid was recrystallized to obtain a
target product (yield 90 mg (18%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1709] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.87 (s,
6H), 0.99 (s, 6H), 1.42 (s, 6H), 1.49 (s, 6H), 1.64-1.71 (m, 8H),
5.51-5.53 (m, 2H), 6.17 (s, 2H), 6.29-6.31 (m, 2H), 7.33 (dd, 2H,
J=2.16 Hz, 8.37 Hz), 7.46 (dd, 2H, J=1.89 Hz, 8.64 Hz), 7.74 (dd,
2H, J=2.43 Hz, 8.1 Hz), 7.88 (dd, 2H, J=2.16 Hz, 8.37 Hz), 8.08 (s,
2H).
[1710] MS (FD): m/z 844 (M.sup.+).
Synthesis Example 2-3
Synthesis of
di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride
(i) Synthesis of di(m-chloro)benzophenone
[1711] To a 500-ml three-necked flask which was thoroughly purged
with nitrogen and equipped with a dropping funnel and a magnetic
stirrer, 7.51 g (31.5 mmol) of 1-chloro-3-iodobenzene and 40 ml of
dehydrated diethyl ether were added, and the mixture was stirred.
The mixture was cooled to -78.degree. C., and 19.7 ml (31.5 mmol)
of a 1.60 mol/L hexane solution of n-butyllithium was added over 10
minutes. The progress of reaction was confirmed by gas
chromatography, and subsequently 1.98 g (12.6 mmol) of ethyl
piperidine-1-carboxylate was added over 30 minutes. After the
dropwise addition, the mixture was stirred at -78.degree. C. for 30
minutes. Dilute hydrochloric acid was added to terminate the
reaction. Then, 50 ml of diethyl ether was added, and the organic
phase was collected by separation with a separatory funnel. The
aqueous phase was subjected to extraction with 30 ml of diethyl
ether. The organic phase was combined and washed two times with 50
ml of water and once with 50 ml of saturated brine. The organic
phase collected by separation was dried over anhydrous magnesium
sulfate. Then, magnesium sulfate was separated by filtration, and
the filtrate was subjected to distillation under reduced pressure
using a rotary evaporator to remove the solvent. The residue was
purified by column chromatography to obtain a target product (yield
3.70 g (82%)). The target product was identified by .sup.1H-NMR and
FD-MS spectroscopy.
[1712] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 7.4-7.8
(m, Ph, 8H).
[1713] MS (FD): m/z 250 (M.sup.+).
(ii) Synthesis of 6,6-di(m-chloro)phenylfulvene
[1714] To a 500-ml three-necked flask which was thoroughly purged
with nitrogen and equipped with a dropping funnel and a magnetic
stirrer, 3.80 g (15.0 mmol) of di(m-chloro)benzophenone and 20 ml
of dehydrated tetrahydrofuran were added, and the mixture was
stirred. To this solution, 11.25 ml (22.5 mmol) of a 2.0 mol/L
tetrahydrofuran solution of sodium cyclopentadienide was added
dropwise from the dropping funnel. After the dropwise addition, the
mixture was stirred at 0.degree. C. for 30 minutes. Then, 50 ml of
a saturated aqueous solution of ammonium chloride and 50 ml of
ether were added, and the organic phase was collected by separation
with a separatory funnel. The aqueous phase was subjected to
extraction with 30 ml of ether. The organic phases were combined
and washed two times with 50 mL of water and once with 50 ml of
saturated brine. The organic phase collected by separation was
dried over anhydrous magnesium sulfate. Then, magnesium sulfate was
separated by filtration, and the filtrate was subjected to
distillation under reduced pressure using a rotary evaporator to
remove the solvent. The residue was purified by column
chromatography to obtain a target product (yield 3.70 g (82%)). The
target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1715] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 6.2 (m
Cp 2H), 6.6 (m, Cp, 2H), 7.1-7.4 (m, Ph, 10H).
[1716] MS (FD): m/z 299 (M.sup.+).
(iii) Synthesis of
di(m-chloro)phenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)
[1717] To a 200-ml three-necked flask which was thoroughly purged
with nitrogen and equipped with a three-way cock, a dropping funnel
and a magnetic stirrer, 2.13 g (5.50 mmol) of
octamethyloctahydrodibenzofluorene synthesized by the method
described in Synthesis Example 2-1(i) and 80 ml of dehydrated
tetrahydrofuran were added. The mixture was stirred with a magnetic
stirrer, and the mixture was cooled to 0.degree. C. To this
mixture, 3.90 ml (6.01 mmol) of a 1.54 mol/L hexane solution of
n-butyllithium was added, the ice bath was subsequently removed,
and the mixture was stirred at room temperature for 4 hours.
Thereafter, this slurry was cooled to -78.degree. C., and then a
solution prepared by dissolving 1.50 g (5.00 mmol) of
6,6-di(m-chloro)phenylfulvene in 10 mL of dehydrated
tetrahydrofuran was added over 15 minutes. This mixture was stirred
at -78.degree. C. for 2 hours. This solution was quenched with 1 N
hydrochloric acid, and the soluble fraction was extracted with 50
ml of diethyl ether. The organic phase collected by separation was
washed with 100 ml of saturated brine, and then dried over
anhydrous magnesium sulfate. Then, magnesium sulfate was separated
by filtration, and the filtrate was subjected to distillation under
reduced pressure using a rotary evaporator to remove the solvent.
The resulting crude purification product was recrystallized from
dichloromethane/methanol to obtain a target product (yield 3.40 g
(91%)). The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1718] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.9-1.5
(m, 24H), 1.6 (s+s, 8H), 3.0 (br, 2H), 5.4 (s+s, 1H), 6.2-6.5
(m(br), 3H), 7.0-7.4 (br+s, 12H).
[1719] MS (FD): M/z 684 (M.sup.+).
(iv) Synthesis of
di(m-chloro)phenylmethylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride
[1720] To a 30-ml Schlenk flask which was thoroughly purged with
nitrogen and equipped with a dropping funnel and a magnetic
stirrer, 1.37 g (2.00 mmol) of
di(m-chloro)phenylmethylene(cyclopentadienyl)(octamethyloctahydr-
odibenzofluorenyl) and 15 ml of dehydrated diethyl ether were
added. The mixture was stirred with a magnetic stirrer, and then
cooled to -78.degree. C. To this mixture, 2.90 ml (4.47 mmol) of a
1.54 mol/L hexane solution of n-butyllithium was added. Then, the
temperature was gradually increased, and the mixture was stirred at
room temperature for 22 hours. This slurry was cooled again to
-78.degree. C., and 0.73 g (1.94 mmol) of zirconium
tetrachloride.tetrahydrofuran complex (1:2) was added.
Subsequently, the mixture was stirred at room temperature for 19
hours. The volatile fraction of this slurry was removed by
distillation under reduced pressure. Subsequently, the residue was
washed with 40 ml of dehydrated hexane, and the insoluble was
separated by filtration. The solution obtained by filtration was
subjected to recrystallization using pentane to obtain a target
product (yield 0.40 g (24%)). The target product was identified by
FD-MS spectroscopy.
[1721] MS (FD): M/z 845 (M.sup.+).
Synthesis Example 2-4
Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butyl-
-fluorenyl)zirconium dichloride
(i) Synthesis of 2,7-di-bromo-3,6-di-t-butyl-fluorene
[1722] Under a nitrogen stream, a 300-ml three-necked flask was
charged with 15.2 g (54.7 mmol) of 3,6-di-t-butyl-fluorene and 170
ml of propylene carbonate, and the mixture was stirred. To this
solution, 20.5 g (115 mmol) of N-bromosuccinimide was added, and
the mixture was heated and stirred at 80.degree. C. for 5 hours.
Subsequently, the mixture was left to be naturally cooled. The
reaction solution was then added to 800 ml of water, and stirred at
room temperature for 15 minutes. The solids precipitated were
separated by filtration. The solids obtained were washed times with
10 ml of ethanol. Subsequently, a mixed solution of hexane and a
small amount of dichloromethane was added to these solids, and the
mixture was heated to 60.degree. C. to dissolve the solids
completely. Then, the solution was left to stand overnight at
20.degree. C. Crystals precipitated were washed three times with 5
mL of hexane to obtain a target product (yield 21.2 g (76%)). The
target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1723] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.5 (s,
18H), 3.7 (s, 2H), 7.7 (s, 2H), 7.8 (s, 2H).
[1724] MS (FD): M/z 436 (M.sup.+).
(ii) Synthesis of 2,7-diphenyl-3,6-di-t-butyl-fluorene
[1725] Under a nitrogen stream, a 300-mL three-necked flask was
charged with 8.15 g (18.7 mmol) of
2,7-dibromo-3,6-di-t-butyl-fluorene and 1.08 g (0.93 mmol) of
Pd(PPh.sub.3), and further charged with 120 ml of
1,2-dimethoxyethane. The mixture was stirred at room temperature
for 20 minutes. To this solution, 20 ml of an ethanol solution in
which 5.01 g (41.1 mmol) of phenylboric acid was dissolved was
added, and the mixture was stirred at room temperature for 20
minutes. Thereafter, 37.4 ml (74.8 mmol) of a 2.0 mol/L aqueous
solution of sodium carbonate was added. Subsequently, the mixture
was heated to reflux for 18 hours, left to be naturally cooled, and
quenched with dilute hydrochloric acid in an ice bath. Thereafter,
ether was added to extract the soluble fraction, and the organic
layer was washed two times with a saturated aqueous solution of
sodium hydrogen carbonate, two times with water, and two times with
saturated brine, and then dried over magnesium sulfate. Then,
magnesium sulfate was separated by filtration, and the filtrate
distillation under reduced pressure using a rotary evaporator to
remove the solvent. The resulting solids were purified by column
chromatography to obtain a target product (yield 4.36 g (54%)). The
target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1726] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.3 (s,
18H), 3.8 (s, 2H), 7.1 (s, 2H), 7.3 (s, 10H), 7.9 (s, 2H).
[1727] MS (FD): M/z 430 (M.sup.+).
(iii) Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butyl-
-fluorenyl)
[1728] Under a nitrogen atmosphere, a 200-ml three-necked flask was
charged with 3.50 g (8.14 mmol) of
2,7-diphenyl-3,6-di-t-butyl-fluorene and 100 ml of dehydrated
tetrahydrofuran, and the mixture was stirred. This solution was
cooled in an ice bath, and 5.70 ml (8.89 mmol) of a 1.56 mol/L
hexane solution of n-butyllithium was added dropwise. Subsequently,
the mixture was stirred at room temperature for 3 hours. The
resulting solution was cooled again to -40.degree. C., 2.22 g (7.39
mol) of a dehydrated tetrahydrofuran solution of
6,6-di(p-chlorophenyl)fulvene synthesized by the procedure of
Synthesis Example 2-2 (i) was added dropwise, and the mixture was
stirred at room temperature for 5 hours. Subsequently, the mixture
was quenched with a dilute aqueous solution of hydrochloric acid.
Then, 100 ml of hexane was added to the reaction liquid to extract
the soluble fraction. This organic layer was washed with a
saturated solution of sodium hydrogen carbonate, water and
saturated brine, and dried over magnesium sulfate. Thereafter,
magnesium sulfate was separated by filtration, and the filtrate was
subjected to distillation under reduced pressure using a rotary
evaporator to remove the solvent. Subsequently, the residue was
washed with hexane and methanol to obtain a target product (yield
3.20 g (54%)). The target product was identified by .sup.1H-NMR,
FD-MS spectroscopy. The target product was identified by
.sup.1H-NMR, FD-MS spectroscopy.
[1729] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.2 (s,
18H), 2.9 (s, 2H), 5.2 (s, 1H), 6.0 (d, 1H), 6.2 (d, 1H), 6.3 (s,
1H), 6.6 (s, 2H), 6.9 (s, 10H), 7.2-7.4 (m+s, 8H), 7.6 (s, 2H).
[1730] MS (FD): M/z 729 (M.sup.+).
(iv) Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butyl-
-fluorenyl)zirconium dichloride
[1731] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 1.00 g (1.37 mmol) of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butyl-
-fluorenyl) and 60 ml of dehydrated diethyl ether were added, and
the mixture was stirred. This solution was cooled in a dry
ice/methanol bath, 1.80 ml (2.81 mmol) of a 1.56 mol/L hexane
solution of n-butyllithium was added dropwise, and the mixture was
stirred at room temperature for 20 hours. Subsequently, the mixture
was cooled to -60.degree. C. in a dry ice/methanol bath. Then, 0.37
g (1.59 mmol) of zirconium tetrachloride was added, and the mixture
was stirred at room temperature for 20 hours. This solution was
subjected to distillation under reduced pressure to remove the
organic solvent. Subsequently, the residue was extracted with
dehydrated hexane and dehydrated dichloromethane, and
recrystallized from the respective solutions to obtain a target
product (yield 0.47 g (38%)). The target product was identified by
.sup.1H-NMR.
[1732] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.2 (s,
18H), 5.4 (m, 2H), 5.8 (s, 2H), 6.3 (m, 2H), 7-7.2 (s+m+m, 6H),
7.5-7.7 (m, 12H), 8.3 (s, 2H).
Synthesis Example 2-5
Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butyl-
-fluorenyl)zirconium dichloride
(i) Synthesis of 2,7-dimethyl-3,6-di-t-butyl-fluorene
[1733] Under a nitrogen stream, a 300-ml three-necked flask was
charged with 5.03 g (11.5 mmol) of
2,7-dibromo-3,6-di-t-butyl-fluorene synthesized by the procedure of
Synthesis Example 2-4(i) and 0.196 g (0.24 mmol) of
PdCl.sub.2(dppf).CH.sub.2Cl.sub.2, and further charged with 100 mL
of dehydrated t-butylmethylether. The mixture was stirred at room
temperature for 20 minutes. This solution was cooled in an ice
bath, and 19.2 mL (57.6 mmol) of a 3.0 mol/L ether solution of
methylmagnesium bromide was added dropwise over 15 minutes.
Subsequently, a slurry solution obtained by heating to reflux for 5
days was left to be naturally cooled, and then quenched with cold 1
N hydrochloric acid in an ice bath. Subsequently, ether was added
to extract the soluble fraction, and this organic layer was washed
with a saturated aqueous solution of sodium hydrogen carbonate,
water and saturated brine, and then dried over magnesium sulfate.
Magnesium sulfate was separated by filtration, and the filtrate was
subjected to distillation under reduced pressure using a rotary
evaporator to remove the solvent. The residue was purified by
column chromatography to obtain a target product (yield 2.07 g
(63%)). The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1734] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.5 (s,
18H), 2.5 (s, 6H), 3.7 (s, 2H), 7.2 (d, 2H), 7.7 (s, 2H).
[1735] MS (FD): M/z 306 (M.sup.+).
(ii) Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butyl-
-fluorenyl)
[1736] Under a nitrogen atmosphere, a 200-ml three-necked flask was
charged with 2.60 g (8.49 mmol) of
2,7-dimethyl-3,6-di-t-butyl-fluorene and 100 mL of dehydrated
tetrahydrofuran, and the mixture was stirred. This mixed solution
was cooled in an ice bath, and 5.70 ml (8.89 mmol) of a 1.56 mol/L
hexane solution of n-butyllithium was added dropwise. The mixture
was stirred at room temperature for 3 hours. Subsequently, the
resulting solution was cooled to -40.degree. C. in a dry
ice/methanol bath, and 60 ml of a tetrahydrofuran solution in which
2.78 g (9.33 mmol) of 6,6-di(p-chlorophenyl)fulvene synthesized by
the procedure of Synthesis Example 2-2(i) was dissolved was added
dropwise. Subsequently, the mixture was stirred for 1 hour while
gradually warming to room temperature. Then, 100 ml of 1 N
hydrochloric acid and 100 ml of hexane was sequentially added to
the reaction solution to extract the soluble fraction. This organic
layer was washed with water and saturated brine, and then dried
over magnesium sulfate. Then, magnesium sulfate was separated by
filtration, and the filtrate was subjected to distillation under
reduced pressure using a rotary evaporator to remove the solvent.
The residue was recrystallized from hexane to obtain a target
product (yield 4.40 g (86%)). The target product was identified by
.sup.1H-NMR and FD-MS spectroscopy.
[1737] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.3 (s,
18H), 2.3 (s, 6H), 3.0 (s, 2H), 5.2 (s, 2H), 6.1-6.3 (s, 4H), 6.7
(s, 2H), 7.0 (s, 6H), 7.4 (s, 2H)
[1738] MS (FD): M/z 604 (M.sup.+).
(iii) Synthesis of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butyl-
-fluorenyl)zirconium dichloride
[1739] Under a nitrogen atmosphere, a 100-ml Schlenk flask was
charged with 1.00 g (1.65 mmol) of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butyl-
-fluorenyl) and 50 ml of dehydrated diethyl ether, and the mixture
was stirred. This mixed slurry solution was cooled to -40.degree.
C. in a dry ice/methanol bath, and 2.20 ml (3.43 mmol) of a 1.56
mol/L hexane solution of n-butyllithium was added. The mixture was
stirred for 22 hours while gradually warming to room temperature.
This reaction liquid was cooled in a dry ice/methanol bath, and
0.38 g (1.65 mmol) of zirconium tetrachloride was added.
Subsequently, the mixture was stirred for 20 hours while gradually
warming to room temperature.
[1740] The solvent was removed by distillation under reduced
pressure. Subsequently, about 30 ml of dehydrated hexane was added,
and the mixture was stirred. Then, the insolubles were removed by
separation by filtration and were dissolved in dehydrated methylene
chloride. The insolubles were removed by separation by filtration.
The hexane solution and the methylene chloride solution obtained by
filtration were combined and concentrated, and then a powder
precipitated with dehydrated hexane was separated by filtration.
Finally, the powder was washed with dehydrated hexane and
dehydrated pentane to obtain a target product (yield 0.122 g
(10%)). The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1741] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.5 (s,
18H), 2.3 (s, 6H), 5.6 (m, 2H), 6.0 (m, 2H), 6.3 (m, 2H), 7.3 (dd,
2H), 7.4 (dd, 2H), 7.7 (dd, 2H), 7.8 (dd, 2H), 8.1 (s, 2H)
[1742] MS (FD): M/z 764 (M.sup.+).
Synthesis Example 2-6
Synthesis of
(m-chlorophenyl)(phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodi-
benzofluorenyl)zirconium dichloride
(i) Synthesis of 6,6-(m-chlorophenyl)(phenyl)fulvene
[1743] To a 500-ml three-necked flask which was thoroughly purged
with nitrogen, and equipped with a three-way cock, a dropping
funnel and a magnetic stirrer, 6.48 g (29.9 mmol) of
(m-chlorophenyl)(phenyl)ketone and 100 ml of dehydrated
tetrahydrofuran were added, and the mixture was stirred. To this
solution, 22.5 ml (45 mmol) of a 2.0 M tetrahydrofuran solution of
sodium cyclopentadienide was added dropwise from the dropping
funnel, and the mixture was stirred for 4 hours at 0.degree. C.
Then, the reaction was terminated with dilute hydrochloric acid.
Thereafter, 50 ml of diethyl ether was added, and the organic phase
was collected by separation using a separatory funnel. The aqueous
phase was subjected to extraction with 30 ml of diethyl ether. The
organic phases were combined, and washed two times with 50 ml of a
saturated aqueous solution of sodium hydrogen carbonate, once with
50 ml of saturated brine, and the organic phase was dried over
magnesium sulfate. Then, magnesium sulfate was separated by
filtration, and the filtrate was subjected to distillation under
reduced pressure using a rotary evaporator to remove the solvent.
The residue was purified by column chromatography to obtain a
target product (yield 4.85 g (61%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1744] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 6.2 (m
Cp 2H), 6.6 (m, Cp, 2H), 7.1-7.4 (m, Ph, 9H).
[1745] MS (FD): M/z 264 (M.sup.+).
(ii) Synthesis of
(m-chlorophenyl)(phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodi-
benzofluorenyl)
[1746] To a 500-ml three-necked flask which was thoroughly purged
with nitrogen, and equipped with a three-way cock, a dropping
funnel and a magnetic stirrer, 6.73 g (17.4 mmol) of
octamethyloctahydrodibenzofluorene synthesized by the method
described in Synthesis Example 2-1(i) and 150 ml of dehydrated
tetrahydrofuran were added, and the mixture was stirred. The
mixture was cooled to 0.degree. C., and 12.6 ml (20.1 mmol) of a
1.60 mol/L hexane solution of n-butyllithium was added. The
resulting mixture was stirred for 4 hours at room temperature. The
reaction liquid was cooled to -78.degree. C., and then a solution
prepared by dissolving 4.85 g (18.4 mmol) of
6,6-(m-chlorophenyl)(phenyl)fulvene in 30 ml of dehydrated
tetrahydrofuran was added over 15 minutes. This mixture was stirred
at -78.degree. C. for 2 hours. This solution was quenched with a
dilute aqueous solution of hydrochloric acid, and the soluble
fraction was extracted with 50 ml of diethyl ether. The organic
phase was collected, and washed two times with 50 ml of a saturated
aqueous solution of sodium hydrogen carbonate and once with 50 mL
of saturated brine. Then, magnesium sulfate was separated by
filtration, and the filtrate was subjected to distillation under
reduced pressure using a rotary evaporator to remove the solvent.
The residue was subjected to column chromatography to obtain a
target product (yield 3.10 g (26%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1747] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.9-1.5
(m, 24H), 1.6 (s+s, 8H), 3.0 (br, 2H), 5.4 (s+s, 1H), 6.2-6.5
(m(br), 3H), 7.0-7.4 (br+s, 13H)
[1748] MS (FD): M/z 650 (M.sup.+).
(iii) Synthesis of
(m-chlorophenyl)(phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodi-
benzofluorenyl)zirconium dichloride
[1749] To a 30-ml Schlenk flask which was thoroughly purged with
nitrogen and equipped with a dropping funnel and a magnetic
stirrer, 1.31 g (2.02 mmol) of
di(m-chloro)phenylmethylene(cyclopentadienyl)(octamethyloctahydr-
odibenzofluorenyl) and 30 ml of dehydrated diethyl ether were
added. The mixture was stirred with a magnetic stirrer, and then
cooled to -78.degree. C. To this mixture, 2.60 ml (4.20 mmol) of a
1.60 mmol/L hexane solution of n-butyllithium was added. Then, the
mixture was gradually warmed to room temperature and stirred at
room temperature for 22 hours. This slurry was cooled again to
-78.degree. C. Subsequently, 0.45 g (1.90 mmol) of zirconium
tetrachloride was added, and the mixture was stirred at room
temperature for 19 hours. The volatile fraction of this slurry was
removed by distillation under reduced pressure. The residue was
washed with 40 ml of dehydrated hexane, and the insolubles were
separated by filtration. The solution obtained by filtration was
subjected to recrystallization to obtain a target product (yield
0.12 g (7%)). The target product was identified by .sup.1H-NMR and
FD-MS spectroscopy.
[1750] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.8 (s,
6H), 0.9 (s, 6H), 1.4 (s, 6H), 1.5 (s, 6H), 1.6-1.7 (m, 8H), 5.6
(dd, 2H), 6.2 (s, 2H), 6.3 (dd, 2H), 7.2-7.5 (m, 5H), 7.9 (d, 2H),
8.0 (d, 2H), 8.1 (s, 2H).
[1751] MS (FD): M/z 811 (M.sup.+).
Synthesis Example 2-7
Synthesis of
di(2-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluor-
enyl)zirconium dichloride
(i) Synthesis of 6,6-di-2-naphthylfulvene
[1752] A 200-ml two-necked flask equipped with a magnetic stirrer
and a three-way cock was thoroughly purged with nitrogen, and
sequentially charged with 1.55 g (5.48 mmol) of di-2-naphthyl
ketone produced by the method described in Heterocycles, vol. 40,
No. 1, 79-83 (1995) and 40 ml of tetrahydrofuran. Then, 5.50 ml
(11.0 mmol) of a 2.0 mol/l cyclopentadienyl sodium/tetrahydrofuran
solution was gradually added while cooling the mixture in an ice
water bath, and then the mixture was stirred at room temperature
for 65 hours under a nitrogen atmosphere. Subsequently, 100 ml of 3
N hydrochloric acid and 100 ml of diethyl ether were gradually
added. The two-layered solution thus obtained was transferred to a
300-ml separatory funnel and the funnel was shaken several times.
The aqueous layer was then removed. This aqueous layer was
subjected to extraction with 30 ml of diethyl ether once, and the
extract was combined with the organic layer obtained previously.
Subsequently, the organic layer obtained was washed 3 times with
100 ml of water and once with 100 ml of saturated brine, and dried
over anhydrous magnesium sulfate for 2 hours. The solids were
separated by filtration, and the solvent was distilled off to
obtain solids. The solids were purified by separation using silica
gel chromatography to obtain a target product (yield 1.21 g (67%)).
The target product was identified by .sup.1H-NMR spectroscopy.
[1753] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 6.3-6.5
(m, Cp, 2H), 6.6-6.7 (m, Cp, 2H), 7.3-7.5 (m, Ar, 2H), 7.5-7.6 (m,
Ar, 4H), 7.7-7.9 (m, Ar, 8H).
(ii) Synthesis of
di-2-naphthyl(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)metha-
ne
[1754] A 200-ml two-necked flask equipped with a magnetic stirrer,
a three-way cock and a 100-ml dropping funnel was thoroughly purged
with nitrogen, and sequentially charged with 1.35 g (3.48 mmol) of
octamethyloctahydrodibenzofluorene and 40 mL of tetrahydrofuran.
Then, 2.30 ml (3.60 mmol) of a 1.58 mol/l n-butyllithium/hexane
solution was gradually added while cooling the mixture in an ice
water bath, and then the mixture was stirred at room temperature
for 20 hours under a nitrogen atmosphere. Subsequently, 1.18 g
(3.57 mmol) of 6,6-di-2-naphthylfulvene dissolved in 30 ml of
tetrahydrofuran in advance was gradually added over 30 minutes
while cooling the mixture in a methanol/dry ice bath. The mixture
was gradually warmed to room temperature, and stirred for 20 hours
at room temperature under a nitrogen atmosphere. Then, 100 ml of 1
N hydrochloric acid was gradually added, and subsequently 100 ml of
diethyl ether was added. The two-layered solution thus obtained was
transferred to a 300-ml separatory funnel and the funnel was shaken
several times. The aqueous layer was then removed. Subsequently,
the organic layer obtained was washed 2 times with 100 ml of water
and once with 100 ml of saturated brine, and dried over anhydrous
magnesium sulfate for 3 hours. The solids were separated by
filtration, and the solvent was distilled off. The residue was
purified by separation using silica gel chromatography to obtain a
target product (yield 1.28 g (51%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1755] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 1.1-1.3
(m, Me(OMOHDBFlu), 24H), 1.4-1.7 (br, CH.sub.2(OMOHDBFlu), 8H),
2.8-3.2 (br, CH.sub.2(Cp), 1H), 5.56 (s, CH(9-OMOHDBFlu), 1H),
6.1-6.5 (br, Cp, 4H), 7.1-8.0 (br, Ar(OMOHDBFlu) & Ar(Nap),
18H)
[1756] MS (FD): M/z 716 (M.sup.+).
(iii) Synthesis of
di(2-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluor-
enyl)zirconium dichloride
[1757] A 100-ml gilder flask equipped with a magnetic stirrer was
thoroughly purged with nitrogen, and sequentially charged with 0.50
g (0.70 mmol) of
di(2-naphthyl)(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)meth-
ane and 40 ml of diethyl ether. Then, 0.92 ml (1.5 mmol) of a 1.58
mol/l n-butyllithium/hexane solution was gradually added while
cooling the mixture in an ice water bath, and the mixture was
stirred at room temperature for 24 hours under a nitrogen
atmosphere. Thereafter, 0.25 g (0.67 mmol) of a zirconium
tetrachloride.tetrahydrofuran complex (1:2) was added while
maintaining the mixture cool in a methanol/dry ice bath.
Subsequently, the mixture was gradually warmed to room temperature,
and stirred at room temperature for 24 hours under a nitrogen
atmosphere. The solid obtained by distilling off the solvent under
reduced pressure was subjected to extraction with pentane under a
nitrogen atmosphere, and the extract was again left to stand at
-18.degree. C. for one day. White solids precipitated were
separated by filtration, and the filtrate was left to stand for
another day at -18.degree. C. White solids precipitated were again
separated by filtration, the filtrate obtained was subjected to
distillation under reduced pressure to remove the solvent, thereby
obtaining a target product as a red peach-colored solid (yield 0.35
g (58%)). The target product was identified by .sup.1H-NMR and
FD-MS spectroscopy.
[1758] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.6-1.8
(m, Me(OMOHDBFlu) & CH.sub.2(OMOHDBFlu), 32H), 5.5-6.4 (m, Cp,
4H), 7.3-8.6 (m, Ar, 18H).
[1759] MS (FD): M/z 876 (M.sup.+).
Synthesis Example 2-8
Synthesis of
bis(4-biphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluo-
renyl)zirconium dichloride
(i) Synthesis of 6,6-bis(4-biphenyl)fulvene
[1760] A reaction vessel thoroughly purged with nitrogen was
charged with tetrahydrofuran (60 ml) and cyclopentadiene 2.47 ml
(29.9 mmol). Then, 19.6 ml (30.8 mmol) of 1.57 mol/l
n-butyllithium/hexane solution was added while cooling this
solution in a dry ice/methanol bath and the mixture was stirred
overnight while gradually warming to room temperature. A solution
prepared by dissolving 10 g (29.9 mmol) of
4,4'-diphenylbenzophenone in tetrahydrofuran (50 ml) was slowly
added dropwise using a dropping funnel while cooling the reaction
solution to 0.degree. C., and then the mixture was stirred at room
temperature for 3 days. This reaction liquid was subjected to
extraction with diethyl ether. The organic layer was washed with a
saturated aqueous solution of ammonium chloride, water and
saturated brine, and dried over magnesium sulfate. The solvent was
removed by distillation under reduced pressure. The residue was
purified by separation using silica gel chromatography to obtain a
target product (yield 0.80 g (7%)). The target product was
identified by .sup.1H-NMR spectrometry.
[1761] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 6.3-6.4
(m, 2H, Cp), 6.6-6.7 (m, 2H, Cp), 7.3-7.5 (m, 10H, Ar), 7.6-7.7 (m,
8H, Ar).
(ii) Synthesis of
bis(4-biphenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)metha-
ne
[1762] A reaction vessel was charged with t-butylmethylether (60
ml) and 2.09 g (5.41 mmol) of octamethyloctahydrodibenzofluorene
under a nitrogen atmosphere. Then, 3.90 ml (6.14 mmol) of a 1.58
mol/l n-butyllithium/hexane solution was slowly added dropwise
while cooling this solution to 0.degree. C. and the mixture was
stirred. Thereafter, 1.38 g (3.61 mmol) of solid
6,6-bis(4-biphenyl)fulvene was added while cooling this solution to
-78.degree. C., and the mixture was stirred for one day while
slowly warming to room temperature. This reaction liquid was
subjected to extraction with diethyl ether. The organic layer was
washed with 1 N hydrochloric acid, a saturated aqueous solution of
sodium hydrogen carbonate and saturated brine, and dried over
magnesium sulfate. The solvent was removed by distillation under
reduced pressure. The residue was purified by separation using a
silica gel column and recrystallized from n-hexane to obtain a
target product (yield 1.15 g (41%)). The target product was
identified by .sup.1H-NMR and FD-MS spectroscopy.
[1763] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.93 (b,
6H), 1.12 (b, 6H), 1.24 (s, 6H), 1.26 (s, 6H), 1.61 (b, 8H),
2.93-3.05 (b, 2H), 5.44 (s, 1H), 6.34 (b, 3H), 7.30-7.64 (m,
22H).
[1764] MS (FD): M/z 768 (M.sup.+).
(iii) Synthesis of
bis(4-biphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluo-
renyl)zirconium dichloride
[1765] Under a nitrogen atmosphere, 0.50 g (0.65 mmol) of
bis(4-biphenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)metha-
ne was added to a diethyl ether solvent (20 mL). Then, 0.91 ml
(1.43 mmol) of a 1.58 mol/l n-butyllithium/hexane solution was
slowly added dropwise while cooling this solution to 0.degree. C.,
and the mixture was stirred overnight. Subsequently, 0.23 g (0.62
mmol) of zirconium tetrachloride.tetrahydrofuran complex (1:2) was
added while cooling to -78.degree. C., and the mixture was stirred
overnight. The solids obtained by distilling off the solvent under
reduced pressure was dissolved in hexane under a nitrogen
atmosphere, the liquid was passed through a glass filter filled
with Celite and insolubles were washed with hexane, and
hexane-insolubles were washed with dichloromethane. The filtrate in
which dichloromethane-solubles were dissolved was concentrated. The
resultant was washed with diethyl ether and hexane, and dried to
obtain a target product (yield 0.14 g (24%)). The target product
was identified by .sup.1H-NMR and FD-MS spectroscopy.
[1766] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.84 (s,
6H), 0.97 (s, 6H), 1.43 (s, 6H), 1.50 (s, 6H), 1.60-1.71 (m, 8H),
5.62-5.64 (m, 2H), 6.27 (s, 2H), 6.31-6.33 (m, 2H), 7.26-7.47 (m,
6H), 7.56-7.61 (m, 6H), 7.71 (dd, 2H, J=1.89 Hz, 7.83 Hz), 7.97
(dd, 2H, J=2.16 Hz, 8.1 Hz), 8.05-8.09 (m, 4H).
[1767] MS (FD): M/z 928 (M.sup.+).
Synthesis Example 2-9
Synthesis of
bis(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl)(octame-
thyloctahydrodibenzofluorenyl)zirconium dichloride
(i) 6,6-bis(4-bromo)fulvene
[1768] Under a nitrogen stream, 80 ml of dried THF were added to
5.50 g (16.2 mmol) of 4,4'-dibromobenzophenone and the mixture was
stirred. At -78.degree. C., 9.70 ml (19.4 mmol) of a 2.0 mol/l
cyclopentadienyl sodium/tetrahydrofuran solution was gradually
added dropwise. The temperature of the mixture was warmed to
-10.degree. C. and the mixture was then stirred for 3 hours. When
completion of the reaction was checked, the reaction was terminated
with 1 N hydrochloric acid. Liquid-liquid phase separation was
performed, and the aqueous layer was subjected to extraction with
diethyl ether two times. The extract was combined with the organic
layer previously obtained, and the liquid was washed with a
saturated aqueous solution of sodium hydrogen carbonate, water and
saturated brine, and then dried over magnesium sulfate. The solvent
was distilled off, and the residue was subjected to separation by
silica gel chromatography to obtain a target product (yield 5.20 g
(83%)). The target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1769] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 6.22 (d,
2H), 6.63 (d, 2H), 7.14 (d, 4H), 7.54 (d, 4H).
[1770] MS (FD): M/z 386 (M.sup.+).
(ii) Synthesis of
6,6-bis(4-[p-trifluoromethylphenyl]-phenyl)fulvene
[1771] Under a nitrogen stream, 100 ml of methanol was added to
1.28 g (3.30 mmol) of 6,6-bis(4-bromo)fulvene, and the mixture was
stirred. Then, 1.68 g (8.80 mmol) of 4-(trifluoromethyl)phenylboric
acid, 0.21 g (0.165 mmol) of tetrakistriphenylphosphinepalladium
and 2.09 g (1.98 mmol) of sodium carbonate were added, and the
mixture was stirred at 65.degree. C. for 2 hours. Liquid-liquid
phase separation was performed using water and dichloromethane, and
the aqueous layer was subjected to extraction with dichloromethane
two times. The extract was washed with saturated brine and dried
over magnesium sulfate. The solvent was distilled off, and the
residue was subjected to separation by silica gel chromatography to
obtain a target product (yield 1.38 g (81%)). The target product
was identified by .sup.1H-NMR and FD-MS spectroscopy.
[1772] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 6.34 (d,
2H), 6.65 (d, 2H), 7.46 (d, 4H), 7.66 (d, 4H), 7.75 (t, 8H).
[1773] MS (FD): M/z 518 (M.sup.+).
(iii) Synthesis of
bis(4-[p-trifluoromethylphenyl]-phenyl)cyclopentadienyl(octamethyloctahyd-
rodibenzofluorenyl)methane
[1774] Under a nitrogen atmosphere, 0.81 g (2.20 mmol) of
octamethyloctahydrodibenzofluorene and 100 ml of dehydrated
tert-butyl methyl ether were added, and the mixture was stirred.
This solution was cooled to 0.degree. C., and 1.59 ml (2.42 mmol)
of a 1.52 mol/l hexane solution of n-butyllithium was added.
Subsequently, the mixture was stirred at room temperature for 24
hours. The resulting solution was cooled to -78.degree. C., and
1.04 g (2 mmol) of
6,6-bis(4-(p-trifluoromethylphenyl)-phenyl)fulvene was added. The
mixture was stirred at room temperature for 3 hours. When the
completion of reaction was checked, 1 N hydrochloric acid was added
to the reaction solution to perform liquid-liquid phase separation.
The aqueous layer was subjected to extraction with diethyl ether
two times, and the extract was combined with the organic layer
previously obtained. The liquid was washed with a saturated aqueous
solution of sodium hydrogen carbonate, water and saturated brine,
and dried over magnesium sulfate. The solvent was distilled off,
and the residue was subjected to separation by silica gel
chromatography to obtain a target product (yield 0.92 g (47%)). The
target product was identified by .sup.1H-NMR and FD-MS
spectroscopy.
[1775] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): .delta./ppm 0.8-1.7
(m, 24H), 2.1-2.4 (br, 8H), 2.7-3.1 (br, 1H), 5.2-5.4 (m, 1H),
5.8-6.5 (br, 4H), 6.7-7.5 (br, 8H), 7.29 (s, 2H).
[1776] MS (FD): M/z 904 (M.sup.+).
(iv) Synthesis of
bis(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl)(octame-
thyloctahydrodibenzofluorenyl)zirconium dichloride
[1777] Under a nitrogen atmosphere, 456 mg (0.50 mmol) of
bis(4-[p-trifluoromethylphenyl]-phenyl)cyclopentadienyl(octamethyloctahyd-
rodibenzofluorenyl)methane was added to 30 ml of diethyl ether, and
this solution was cooled to -78.degree. C. Then, 0.69 ml (1.05
mmol) of a 1.52 mol/L hexane solution of n-butyllithium was slowly
added dropwise. The mixture was stirred for 19 hours while
gradually warming to room temperature. Subsequently, the mixture
was cooled again to -78.degree. C., and 0.12 g (0.50 mmol) of
zirconium tetrachloride was added. The mixture was stirred for 19
hours while gradually warming to room temperature. This reaction
solution was concentrated, and dissolved in 30 mL of hexane under a
nitrogen stream. The liquid in which hexane-solubles were dissolved
was concentrated, and recrystallization from 10 ml of pentane was
performed. Impurities were removed to obtain a target product
(yield 0.08 g (15%)). The target product was identified by
.sup.1H-NMR and FD-MS spectroscopy.
[1778] .sup.1H-NMR (270 MHz, CDCl.sub.3, TMS): 8/ppm 0.84 (s, 6H),
0.97 (s, 6H), 1.43 (s, 6H), 1.50 (s, 6H), 1.60-1.71 (m, 8H),
5.62-5.64 (m, 2H), 6.27 (s, 2H), 6.31-6.33 (m, 2H), 7.26-7.47 (m,
6H), 7.56-7.61 (m, 4H), 7.71 (dd, 2H), 7.97 (dd, 2H), 8.05-8.09 (m,
4H).
[1779] MS (FD): M/z 1062 (M.sup.+).
Example 2-1
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1780] In a 2000-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 700 ml
of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
65.degree. C., and propylene was introduced to raise the pressure
in the system to 6.1 kg/cm.sup.2G, and then with ethylene to 6.2
kg/cm.sup.2G. Subsequently, the polymerization vessel was charged
with a toluene solution in which 0.002 mmol of
di[m-(trifluoromethyl)phenyl]methylene(cyclopentadienyl)(octamethyloctahy-
drodibenzofluorenyl)zirconium dichloride synthesized in Synthesis
Example 2-1 had been contacted with 0.6 mmol, in terms of aluminum,
of methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 15 minutes while maintaining
the internal temperature at 65.degree. C. and the ethylene pressure
at 6.2 kg/cm.sup.2G, and 20 ml of methanol was added to terminate
the polymerization. After depressurizing, the resulting polymer was
precipitated from the polymerization solution in 2 L of methanol,
and dried in a vacuum at 130.degree. C. for 12 hours. The amount of
the polymer obtained was 54.0 g, and the polymerization activity
was 108.0 kg-polymer/mmol-cathr. The polymer composition was 55.0
mol % of propylene content, 6.5 mol % of ethylene content, and 38.5
mol % of 1-butene content, and the intrinsic viscosity [.eta.] was
2.79 dl/g.
Example 2-2
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1781] In a 2000-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 700 ml
of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
65.degree. C., and propylene was introduced to raise the pressure
in the system to 6.1 kg/cm.sup.2G, and then with ethylene to 6.2
kg/cm.sup.2G. Subsequently, the polymerization vessel was charged
with a toluene solution in which 0.002 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride synthesized in Synthesis Example 2-2
had been contacted with 0.6 mmol, in terms of aluminum, of
methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 20 minutes while maintaining
the internal temperature at 65.degree. C. and the ethylene pressure
at 6.2 kg/cm.sup.2G, and 20 ml of methanol was added to terminate
the polymerization. After depressurizing, the resulting polymer was
precipitated from the polymerization solution in 2 L of methanol,
and dried in a vacuum at 130.degree. C. for 12 hours. The amount of
the polymer obtained was 72.8 g, and the polymerization activity
was 109.1 kg-polymer/mmol-cathr. The polymer composition was 53.0
mol % of propylene content, 10.0 mol % of ethylene content, and
37.0 mol % of 1-butene content, and the intrinsic viscosity [.eta.]
was 2.35 dl/g.
Example 2-3
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1782] In a 2000-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 700 ml
of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
65.degree. C., and propylene was introduced to raise the pressure
in the system to 6.1 kg/cm.sup.2G, and then with ethylene to 6.2
kg/cm.sup.2G. Subsequently, the polymerization vessel was charged
with a toluene solution in which 0.004 mmol of
di(m-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride synthesized in Synthesis Example 2-3
had been contacted with 1.2 mmol, in terms of aluminum, of
methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 35 minutes while maintaining
the internal temperature at 65.degree. C. and the ethylene pressure
at 6.2 kg/cm.sup.2G, and 20 ml of methanol was added to terminate
the polymerization. After depressurizing, the resulting polymer was
precipitated from the polymerization solution in 2 L of methanol,
and dried in a vacuum at 130.degree. C. for 12 hours. The amount of
the polymer obtained was 65.4 g, and the polymerization activity
was 28.0 kg-polymer/mmol-cathr. The polymer composition was 51.0
mol % of propylene content, 17.0 mol % of ethylene content, and
32.0 mol % of 1-butene content, and the intrinsic viscosity [.eta.]
was 2.48 dl/g.
Example 2-4
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1783] In a 2000-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 700 ml
of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
65.degree. C., and propylene was introduced to raise the pressure
to 6.1 kg/cm.sup.2G, and then with ethylene to 6.2 kg/cm.sup.2G.
Subsequently, the polymerization vessel was charged with a toluene
solution in which 0.002 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-t-butyl-
-fluorenyl)zirconium dichloride synthesized in Synthesis Example
2-4 had been contacted with 0.6 mmol, in terms of aluminum, of
methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 60 minutes while maintaining
the internal temperature at 65.degree. C. and the ethylene pressure
at 6.2 kg/cm.sup.2G, and 20 ml of methanol was added to terminate
the polymerization. After depressurizing, the resulting polymer was
precipitated from the polymerization solution in 2 L of methanol,
and dried in a vacuum at 130.degree. C. for 12 hours. The amount of
the polymer obtained was 8.1 g, and the polymerization activity was
4.1 kg-polymer/mmol-cathr. The polymer composition was 61.0 mol %
of propylene content, 2.0 mol % of ethylene content, and 37.0 mol %
of 1-butene content, and the intrinsic viscosity [.eta.] was 2.42
dl/g.
Example 2-5
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1784] In a 2000-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 700 ml
of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
65.degree. C., and propylene was introduced to raise the pressure
in the system to 6.1 kg/cm.sup.2G, and then with ethylene to 6.2
kg/cm.sup.2G. Subsequently, the polymerization vessel was charged
with a toluene solution in which 0.002 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(2,7-dimethyl-3,6-di-t-butyl-
-fluorenyl)zirconium dichloride synthesized in Synthesis Example
2-5 had been contacted with 0.6 mmol, in terms of aluminum, of
methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 60 minutes while maintaining
the internal temperature at 65.degree. C. and the ethylene pressure
at 6.2 kg/cm.sup.2G, and 20 ml of methanol was added to terminate
the polymerization. After depressurizing, the resulting polymer was
precipitated from the polymerization solution in 2 L of methanol,
and dried in a vacuum at 130.degree. C. for 12 hours. The amount of
the polymer obtained was 22.6 g, and the polymerization activity
was 11.3 kg-polymer/mmol-cat hr. The polymer composition was 51.0
mol % of propylene content, 8.0 mol % of ethylene content, and 41.0
mol % of 1-butene content, and the intrinsic viscosity [.eta.] was
2.10 dl/g.
Example 2-6
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1785] In a 2000-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 700 ml
of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
65.degree. C., and propylene was introduced to raise the pressure
in the system to 6.1 kg/cm.sup.2G, and then with ethylene to 6.2
kg/cm.sup.2G. Subsequently, the polymerization vessel was charged
with a toluene solution in which 0.002 mmol of
(m-chlorophenyl)(phenyl)methylene(cyclopentadienyl)(octamethyloctahydrodi-
benzofluorenyl)zirconium dichloride synthesized in Synthesis
Example 2-6 had been contacted with 0.6 mmol, in terms of aluminum,
of methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 15 minutes while maintaining
the internal temperature at 65.degree. C. and the ethylene pressure
at 6.2 kg/cm.sup.2G, and 20 ml of methanol was added to terminate
the polymerization. After depressurizing, the resulting polymer was
precipitated from the polymerization solution in 2 L of methanol,
and dried in a vacuum at 130.degree. C. for 12 hours. The amount of
the polymer obtained was 30.4 g, and the polymerization activity
was 26.1 kg-polymer/mmol-cathr. The polymer composition was 58.0
mol % of propylene content, 5.0 mol % of ethylene content, and 37.0
mol % of 1-butene content, and the intrinsic viscosity [.eta.] was
2.29 dl/g.
Example 2-7
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1786] In a 2000-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 700 ml
of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
65.degree. C., and propylene was introduced to raise the pressure
in the system to 6.1 kg/cm.sup.2G, and then with ethylene to 6.2
kg/cm.sup.2G. Subsequently, the polymerization vessel was charged
with a toluene solution in which 0.002 mmol of
di(2-naphthyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluor-
enyl) irconium dichloride synthesized in Synthesis Example 2-7 had
been contacted with 0.6 mmol, in terms of aluminum, of
methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 12 minutes while maintaining
the internal temperature at 65.degree. C. and the ethylene pressure
at 6.2 kg/cm.sup.2G, and 20 ml of methanol was added to terminate
the polymerization. After depressurizing, the resulting polymer was
precipitated from the polymerization solution in 2 L of methanol,
and dried in a vacuum at 130.degree. C. for 12 hours. The amount of
the polymer obtained was 25.8 g, and the polymerization activity
was 64.6 kg-polymer/mmol-cathr. The polymer composition was 56.5
mol % of propylene content, 7.0 mol % of ethylene content, and 36.5
mol % of 1-butene content, and the intrinsic viscosity [.eta.] was
2.73 dl/g.
Example 2-8
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1787] In a 2000-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 700 ml
of dry hexane, 120 g of 1-butene and triisobutylaluminum (1.0 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
65.degree. C., and propylene was introduced to raise the pressure
in the system to 6.1 kg/cm.sup.2G, and then with ethylene to 6.2
kg/cm.sup.2G.
[1788] Subsequently, the polymerization vessel was charged with a
toluene solution in which 0.002 mmol of
bis(4-biphenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzofluo-
renyl)zirconium dichloride synthesized in Synthesis Example 2-8 had
been contacted with 0.6 mmol, in terms of aluminum, of
methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 30 minutes while maintaining
the internal temperature at 65.degree. C. and the ethylene pressure
at 6.2 kg/cm.sup.2G, and 20 ml of methanol was added to terminate
the polymerization. After depressurizing, the resulting polymer was
precipitated from the polymerization solution in 2 L of methanol,
and dried in a vacuum at 130.degree. C. for 12 hours. The amount of
the polymer obtained was 40.1 g, and the polymerization activity
was 40.1 kg-polymer/mmol-cathr. The polymer composition was 54.5
mol % of propylene content, 13.0 mol % of ethylene content, and
32.5 mol % of 1-butene content, and the intrinsic viscosity [.eta.]
was 2.44 dl/g.
Example 2-9
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1789] In a 1500-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 525 ml
of dry hexane, 90 g of 1-butene and triisobutylaluminum (0.75 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
65.degree. C., and propylene was introduced to raise the pressure
in the system to 6.1 kg/cm.sup.2G, and then with ethylene to 6.2
kg/cm.sup.2G.
[1790] Subsequently, the polymerization vessel was charged with a
toluene solution in which 0.0015 mmol of
bis(4-[p-trifluoromethylphenyl]-phenyl)methylene(cyclopentadienyl)(octame-
thyloctahydrodibenzofluorenyl)zirconium dichloride synthesized in
Synthesis Example 2-9 had been contacted with 0.45 mmol, in terms
of aluminum, of methylaluminoxane (manufactured by Tosoh Finechem
Corporation). Polymerization was then performed for 30 minutes
while maintaining the internal temperature at 65.degree. C. and the
ethylene pressure at 6.2 kg/cm.sup.2G, and 20 ml of methanol was
added to terminate the polymerization. After depressurizing, the
resulting polymer was precipitated from the polymerization solution
in 2 L of methanol, and dried in a vacuum at 130.degree. C. for 12
hours. The amount of the polymer obtained was 16.9 g, and the
polymerization activity was 22.5 kg-polymer/mmol-cathr. The polymer
composition was 56.5 mol % of propylene content, 9.0 mol % of
ethylene content, and 34.5 mol % of 1-butene content, and the
intrinsic viscosity [.eta.] was 2.48 dl/g.
Comparative Example 2-1
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1791] In a 2000-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 100 ml
of dry hexane, 480 g of 1-butene and triisobutylaluminum (1.0 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
35.degree. C., and propylene was introduced to raise the pressure
in the system to 6.0 kg/cm.sup.2G, and then with ethylene to 6.2
kg/cm.sup.2G. Subsequently, the polymerization vessel was charged
with a toluene solution in which 0.005 mmol of
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride
had been contacted with 1.5 mmol, in terms of aluminum, of
methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 5 minutes while maintaining
the internal temperature at 35.degree. C. and the ethylene pressure
at 6.2 kg/cm.sup.2G, and 20 ml of methanol was added to terminate
the polymerization. After depressurizing, the resulting polymer was
precipitated from the polymerization solution in 2 L of methanol,
and dried in a vacuum at 130.degree. C. for 12 hours. The amount of
the polymer obtained was 36.1 g, and the polymerization activity
was 86.7 kg-polymer/mmol-cathr. The polymer composition was 58.2
mol % of propylene content, 4.1 mol % of ethylene content, and 37.7
mol % of 1-butene content, and the intrinsic viscosity [.eta.] was
2.69 dl/g.
Comparative Example 2-2
Synthesis of Syndiotactic Propylene-Butene-Ethylene-Based
Copolymer
[1792] In a 2000-ml polymerization apparatus which had been dried
under reduced pressure and thoroughly purged with nitrogen, 100 ml
of dry hexane, 240 g of 1-butene and triisobutylaluminum (1.0 mmol)
were placed at normal temperature. Subsequently, the internal
temperature of the polymerization apparatus was raised to
65.degree. C., and propylene was introduced to raise the pressure
in the system to 6.0 kg/cm.sup.2G, and then with ethylene to 6.2
kg/cm.sup.2G. Subsequently, the polymerization vessel was charged
with a toluene solution in which 0.004 mmol of
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride
had been contacted with 1.2 mmol, in terms of aluminum, of
methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 15 minutes while maintaining
the internal temperature at 65.degree. C. and the ethylene pressure
at 6.2 kg/cm.sup.2G, and 20 ml of methanol was added to terminate
the polymerization. After depressurizing, the resulting polymer was
precipitated from the polymerization solution in 2 L of methanol,
and dried in a vacuum at 130.degree. C. for 12 hours. The amount of
the polymer obtained was 82.6 g, and the polymerization activity
was 82.6 kg-polymer/mmol-cathr. The polymer composition was 51.0
mol % of propylene content, 14.0 mol % of ethylene content, and
34.0 mol % of 1-butene content, and the intrinsic viscosity [.eta.]
was 1.60 dl/g.
Example III
[1793] Hereinafter, the present invention (3) will be described in
more detail based on Examples, but the present invention is not
intended to be limited to these Examples. The respective properties
in Examples were measured in the following manner.
[1794] Intrinsic viscosity [.eta.]
[1795] Intrinsic viscosity [.eta.] was a value measured at
135.degree. C. using a decalin solvent. Specifically, about 20 mg
of a polymerization powder, a pellet or a resin lump was dissolved
in 15 ml of decalin, and the specific viscosity .eta..sub.sp was
measured in an oil bath at 135.degree. C. Thereafter, 5 ml of the
decalin solvent was added to this decalin solution for dilution,
and than the specific viscosity .eta..sub.sp was measured in the
same manner. This dilution operation was additionally repeated two
times, and the value of .eta..sub.sp/C of when the concentration
(C) was extrapolated to 0 was determined as the intrinsic viscosity
(see the following equation).
[.eta.]=lim(.eta..sub.sp/C)(C.fwdarw.0)
[1796] Amount of n-Decane-Soluble Fraction
[1797] 200 ml of n-decane was added to 5 g of a syndiotactic
propylene polymer sample, and the polymer was heated at 145.degree.
C. for 30 minutes to be dissolved. The resulting solution was
cooled to 20.degree. C. over about 3 hours, and left to stand for
30 minutes. Subsequently, the precipitate (n-decane-insoluble
fraction) was separated by filtration. The filtrate was poured to
acetone of about 3-fold volume, and the components dissolved in
n-decane were precipitated. The precipitate was separated by
filtration from acetone, and then dried. On the other hand,
although the filtrate was concentrated and dried, no residue was
observed. The amount of the n-decane-soluble fraction was
determined by the following equation:
Amount of n-Decane-soluble fraction (wt %)=[weight of
precipitate/weight of sample].times.100
[1798] Molecular Weight Distribution (Mw/Mn)
[1799] The molecular weight distribution (Mw/Mn) was measured in
the following manner using gel permeation chromatograph Alliance
GPC-2000 type manufactured by Waters Corp. The separation columns
used were two TSKgel GNH6-HT columns and two TSKgel GNH6-HTL
columns, and all of the columns had a size of 7.5 mm in diameter
and 300 mm in length. The column temperature was set at 140.degree.
C., the mobile phase was o-dichlorobenzene (Wako Pure Chemical
Industries, Ltd.) containing 0.025 wt % of BHT (Takeda Yakuhin Co.,
Ltd.) as an antioxidant, moving at a rate of 1.0 ml/min. The sample
concentration was 15 mg/10 mL, the injection volume of a sample was
500 microliters, and a differential refractometer was used as the
detector. For the standard polystyrene, a product by Tosoh Finechem
Corporation was used for the molecular weight Mw<1000 and
Mw>4.times.10.sup.6, and a product by Pressure Chemical Company
was used for the molecular weight
1000.ltoreq.Mw.ltoreq.4.times.10.sup.6.
[1800] Contents of Ethylene, Propylene and .alpha.-Olefin in
Polymer
[1801] Quantification of the contents of ethylene, propylene and
.alpha.-olefin was determined as follows using a JNM GX-500 type
NMR measuring apparatus manufactured by JEOL, Ltd. 0.35 g of a
sample was dissolved in 2.0 ml of hexachlorobutadiene while
heating. This solution was filtered through a glass filter (G2).
Subsequently, 0.5 ml of deuterated benzene was added, and the
mixture was placed in an NMR tube having an internal diameter of 10
mm. .sup.13C-NMR measurement was performed at 120.degree. C. The
accumulation times were 10,000 or more. The composition of
ethylene, propylene and .alpha.-olefin was quantified using the
.sup.13C-NMR spectrum obtained.
[1802] Melting Point (Tm), Heat of Fusion (.DELTA.H)
[1803] Using DSCPyris1 or DSC7 manufactured by PerkinElmer Inc.,
about 5 mg of a sample was heated to 200.degree. C., maintained for
10 minutes, and then cooled to 30.degree. C. at 10.degree. C./min,
under a nitrogen atmosphere (20 ml/min). The temperature was
maintained at 30.degree. C. for 5 minutes and then heated to
200.degree. C. at 10.degree. C./min. The melting point was
calculated from the apex of the crystal melting peak, and the heat
of fusion was calculated from the integrated value of the peak.
[1804] When two peaks were observed for the propylene-based polymer
described in the Examples of the present invention, in the case
that the peak on the lower temperature side was designated as
Tm.sub.1 and the peak on the higher temperature side was designated
as Tm.sub.2, Tm.sub.2 was considered as the Tm defined in the
requirement [2] of Claim 1 of the present invention.
[1805] Half-Crystallization Time (t.sub.1/2)
[1806] About 5 mg of a sample was placed in an aluminum pan for
exclusive use, and a DSC curve was obtained by heating the sample
from 30.degree. C. to 200.degree. C. at a rate of 320.degree.
C./min, maintaining at 200.degree. C. for 5 minutes, cooling from
200.degree. C. to the isothermal crystallization temperature
110.degree. C. at a rate of 320.degree. C./min, maintaining at the
respective isothermal crystallization temperature, using DSCPyris1
or DSC7 manufactured by PerkinElmer, Inc. From the DSC curve thus
obtained, the half-crystallization time (t.sub.1/2) was obtained.
Here, the half-crystallization time (t.sub.1/2) was determined from
the initial time of the isothermal crystallization process (the
time to reach the isothermal crystallization temperature from
200.degree. C.) as t=0. For the composition of the present
invention, t.sub.1/2 was determined as described above. However,
when crystallization did not occur at an isothermal crystallization
temperature, for example, at 110.degree. C., measurement was taken
for convenience at several points in the range of not more than
110.degree. C. of an isothermal crystallization temperature, and
the half crystallization time (t.sub.1/2) was determined from the
extrapolated value.
[1807] MFR
[1808] MFR was measured at 230.degree. C. under a load of 2.16 kgf,
according to JIS K-6721.
[1809] Method for Producing Press Sheet for Various
Measurements
[1810] Using a hydraulic hot press machine which was set at
200.degree. C. and which was manufactured by Shinto Metal
Industries, Ltd., sheet forming was performed at a pressure of 10
MPa. In the case of a sheet having a thickness of 0.5 to 3 mm
(spacer shaped; four sheets of 80.times.80.times.0.5 to 3 mm were
obtained from a plate of 240.times.240.times.2 mm), preheating was
carried out for about 5 minutes to 7 minutes, and a pressure of 10
MPa was applied for 1 to 2 minutes. Subsequently, the sheet was
compressed at 10 MPa using another hydraulic hot press machine
which was set at 20.degree. C. and which was manufactured by Shinto
Metal Industries, Ltd., and the sheet was then cooled for about 5
minutes to produce a specimen for measurement. Here, a brass plate
having a thickness of 5 mm was used for the thermal plate. The
samples produced by the method described above were supplied as the
specimens for various property evaluations.
[1811] Tensile Modulus
[1812] A press sheet having a thickness of 1 mm was punched using
an O-dumbbell for No. JIS3 dumbbell according to JIS K6301, and the
specimen was provided as evaluation sample. The measurement was
performed at 23.degree. C. under the condition that the span
interval was 30 mm and the tensile rate was 30 mm/min.
[1813] Izod Impact Strength
[1814] According to ASTM D-256, a specimen of 12.7 mm
(width).times.3.2 mm (thickness).times.64 mm (length) was punched
out from a press sheet having a thickness of 3 mm, and a notch was
inserted by machine processing. The Izod impact strength was
measured at 0.degree. C.
[1815] Softening Temperature from TMA Measurement
[1816] According to JIS K7196, using a specimen having a thickness
of 1 mm, the measurement was performed under the condition that
pressure applied to a planar indenter of 1.8 mmm was 2 kgf/cm.sup.2
and heating rate was 5.degree. C./min. The softening temperature
(.degree. C.) was determined from the TMA curve.
[1817] Method for Producing Sample for Internal Haze
Measurement
[1818] In the case of a 1-mm thickness press sheet, a test sample
was produced according to the method for producing a press sheet
for various measurements described above. In the case of a 2-mm
thickness injection molded specimen, molding was performed using an
injection molding machine IS-55 manufactured by Toshiba Corp. to
produce a specimen having a shape of angular plate with a size of 2
mm in thickness.times.120 mm in length.times.130 mm in width. The
conditions of the molding were that resin temperature was
200.degree. C., injection pressure was 1000 kgf/cm.sup.2, and mold
temperature was 40.degree. C.
[1819] Internal Haze (%)
[1820] The internal haze (%) was measured using a press sheet
having a thickness of 1 mm as the specimen, and using a digital
turbidimeter "NDH-20D" manufactured by Nippon Denshoku Industries
Co., Ltd.
[1821] Evaluation of Injection Moldability
[1822] The evaluation was performed using a 55-ton injection
molding machine manufactured by Toshiba Corp. under the condition
that resin temperature was 200.degree. C., mold temperature was
40.degree. C. and cool time was one of the 2 conditions, 20 seconds
(condition 1) or 1 second (condition 1). Moldability was rated as
follows. When injection molding was performed 5 times, the sample
was peeled off from the mold with ejector pins and continuous
operation was possible: .largecircle., the sample was not peeled
off from the mold all times: .DELTA., and the sample was not peeled
off from the mold and continuous operation was impossible: x.
Catalyst Synthesis Example
[1823]
Dibenzylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirco-
nium dichloride was produced by the method described in Synthesis
Example 3 of JP-A No. 2004-189668.
[1824]
Dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfl-
uorenyl)zirconium dichloride was produced in the same manner as in
Synthesis Example [1-1].
Polymerization Example 3-1
Synthesis of Syndiotactic Propylene Polymer (A-1)
[1825] In a thoroughly nitrogen purged reaction bath having an
internal volume of 3 m.sup.3, 1000 L of n-heptane was placed, and
610 mL (0.93 mol) of a toluene solution of methylaluminoxane
(Al=1.53 mol/l) was added dropwise at normal temperature.
Meanwhile, in a thoroughly nitrogen purged side arm flask having an
internal volume of 5 L, a magnetic stirrer was placed, and the
flask was sequentially charged with 610 mL (0.93 mol) of a toluene
solution of methylaluminoxane (Al=1.53 mol/l) and a toluene
solution of 1.30 g (1.86 mmol) of
dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride. The mixture was stirred for 20 minutes. This solution
was introduced into the reaction bath, and then 3200 NL of hydrogen
was supplied at 19 Nm.sup.3/h over 10 minutes. Subsequently,
polymerization was initiated while supplying propylene at 65 kg/h
and supplying hydrogen at such a rate that the gas phase
concentration inside the reaction bath would be 53 mol %. Propylene
was continuously supplied at a rate of 65 kg/h while maintaining
the gas phase concentration of hydrogen inside the reaction bath at
53 mol %, and polymerization was performed for 4 hours at
25.degree. C. Then, a small amount of diethylene glycol
monoisopropyl ether was added to terminate the polymerization. The
polymer obtained was washed with 1.8 m.sup.3 of heptane, and dried
under reduced pressure at 80.degree. C. for 15 hours to obtain a
polymer in an amount of 100 kg. The polymerization activity was
13.4 kg-PP/mmol-Zrhr, the polymer obtained had [.eta.]=1.90 dl/g,
Tm.sub.1=152.degree. C., Tm.sub.2=158 C, and rrrr fraction=94%.
Polymerization Example 3-2
Synthesis of Syndiotactic Propylene Polymer (A-2)
[1826] In a thoroughly nitrogen purged glass autoclave having an
internal volume of 500 ml was charged with 250 ml of toluene and
then charged with propylene at a rate of 150 liters/hr, which was
maintained at 25.degree. C. for 20 minutes. Meanwhile, a magnetic
stirrer was placed in a thoroughly nitrogen purged side arm flask
having an internal volume of 30 ml, and the flask was sequentially
charged with 5.00 mmol of a toluene solution of methylaluminoxane
(Al=1.53 mol/l) and 5.0 .mu.mol of a toluene solution of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride. The mixture was stirred for 20 minutes.
This solution was added to the toluene in the glass autoclave which
had been charged with propylene, and polymerization was initiated.
Propylene gas was continuously supplied at a rate of 150 liters/hr,
polymerization was performed at 25.degree. C. for 10 minutes under
normal pressure. Thereafter, a small amount of methanol was added
to terminate the polymerization. The polymer solution was added to
an excess of methanol to precipitate a polymer. The polymer was
then dried under reduced pressure at 80.degree. C. for 12 hours to
obtain a polymer in an amount of 6.95 g. The polymerization
activity was 7.58 kg-PP/mmol-Zrhr, the polymer obtained had
[.eta.]=2.90 dl/g, Tm.sub.1=157.degree. C., Tm.sub.2=162.degree.
C., and rrrr fraction=95%.
Polymerization Example 3-3
Synthesis of Syndiotactic Propylene Polymer (A-3)
[1827] A thoroughly dried and nitrogen purged SUS autoclave having
an internal volume of 2.0 L was charged with 1.0 L of heptane, and
subsequently charged with propylene gas to 0.3 MPaG while stirring
to be purged. This process was repeated three times. Meanwhile, in
a thoroughly nitrogen purged side arm flask having an internal
volume of 50 ml, a magnetic stirrer was placed, and the flask was
sequentially charged with 1.80 mmol of a toluene solution of
methylaluminoxane (Al=1.53 mol/l) and 1.8 .mu.mol of a toluene
solution of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride. The mixture was stirred for 15 minutes.
This solution was added to the heptane contained in the SUS
autoclave which had been charged with propylene, and polymerization
was initiated. Propylene gas was continuously supplied such that
the pressure in the system was maintained at 0.2 MPaG, and
polymerization was performed at 25.degree. C. for 60 minutes.
Thereafter, a small amount of methanol was added to terminate the
polymerization. The resulting polymer was recovered from the
heptane slurry by filtration, and dried under reduced pressure at
80.degree. C. for 6 hours to obtain a polymer in an amount of 75.4
g. Polymerization activity was 42.0 kg-PP/mmol-Zrhr, the polymer
obtained had [.eta.]=2.4 dl/g, Tm=161.degree. C., and rrrr
fraction=97%.
Example 3-1
[1828] 100 parts by weight of the syndiotactic polypropylene
polymer obtained in Polymerization Example 3-1 was blended with,
based on 100 parts by weight of the polymer, 0.1 part by weight of
Tris(2,4-di-tert-butylphenyl)phosphate as a secondary antioxidant,
0.1 part by weight of Benzenepropanoic acid,
3,5-bis(1,1-dimethylethyl)-4-hydroxy-,
2,2-bis[[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]meth-
yl]-1,3-propandiyl ester as a heat stabilizer, and 0.1 part by
weight of calcium stearate as a neutralizer. Then, using a
Laboplast Mill (twin screw batch type melt kneading apparatus)
manufactured by Toyo Seiki Co., Ltd., and the composition was melt
kneaded for 5 minutes under the conditions of set temperature of
200.degree. C., amount of resin of 40 g (apparatus batch volume=60
cm.sup.3) and 50 rpm. Subsequently, the composition was removed and
molded into a sheet with a cold press set at 20.degree. C., and the
sheet was used as a sample for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the sample, and the properties thereof were measured. The
results of various property tests are presented in Table 3-2.
Besides, an equal amount of the additives were added to the
polymer, and using a twin screw extruder BT-30 (30 mmm, L/D=46,
co-rotation, four kneading zones) manufactured by Prabo Co., Ltd.,
the polymer was granulated under the conditions of set temperature
of 230.degree. C., extrusion amount of resin of 50 g/min, and 200
rpm. The granules were used in the injection molding evaluation
test. The results are presented in Table 3-3. Compared to the
products of Comparative Examples, the composition had excellent
moldability and heat resistance, as well as an excellent balance
between transparency, mechanical properties and strength.
Example 3-2
[1829] 100 parts by weight of the syndiotactic polypropylene
polymer obtained in Polymerization Example 3-2 was blended with,
based on 100 parts by weight of the polymer, the same amounts of
additives used in Example 1. Then, using a Laboplast Mill (twin
screw batch type melt kneading apparatus) manufactured by Toyo
Seiki Co., Ltd., the composition was melt kneaded for 5 minutes
under the conditions of set temperature of 200.degree. C., amount
of resin of 40 g (apparatus batch volume=60 cm.sup.3) and 50 rpm.
Subsequently, the composition was removed and molded into a sheet
with a cold press set at 20.degree. C. The sheet was used as a
sample for measurement after cutting into an appropriate size, or
the like. Also, a press sheet was produced from the specimen, and
the properties thereof were measured. The results of various
property tests are presented in Table 3-2. Compared to the products
of Comparative Examples, the composition had excellent moldability
and heat resistance, as well as an excellent balance between
transparency, mechanical properties and strength.
Example 3-3
[1830] 100 parts by weight of the syndiotactic polypropylene
polymer (A-3) obtained in Polymerization Example 3-3 was blended
with, based on 100 parts by weight the polymer, the same amounts of
additives used in Example 3-1. Then, using a Laboplast Mill (twin
screw batch type melt kneading apparatus) manufactured by Toyo
Seiki Co., Ltd., the composition was melt kneaded for 5 minutes
under the conditions of set temperature of 200.degree. C., amount
of resin of 40 g (apparatus batch volume=60 cm.sup.3) and 50 rpm.
Subsequently, the composition was removed and molded into a sheet
with a cold press set at 20.degree. C. The sheet was used as a
sample for measurement after cutting into an appropriate size, or
the like. Also, a press sheet was produced from the sample, and the
properties thereof were measured. The results of various property
tests are presented in Table 3-2. Compared to the products of
Comparative Examples, the composition had excellent moldability and
heat resistance, as well as an excellent balance between
transparency, mechanical properties and strength.
Comparative Example 3-1
[1831] A press sheet was produced using polypropylene 1471 pellets
manufactured by TOTAL Corp., and the properties thereof were
measured. The results of various property tests are presented in
Table 3-2. The pellets were used in the injection molding
evaluation test. The results are presented in Table 3-3. Compared
to the products of Examples, the polymer had inferior moldability
and heat resistance, as well as an inferior balance between
mechanical properties and strength.
Comparative Example 3-2
[1832] A press sheet was produced using polypropylene F327 pellets
manufactured by Prime Polymer Co., Ltd., and the properties thereof
were measured. The results of various property tests are presented
in Table 3-2. The pellets were used in the injection molding
evaluation test. The results are presented in Table 3-3. Compared
to the products of Examples, the polymer had inferior heat
resistance, as well as an inferior balance between transparency,
mechanical properties and strength.
TABLE-US-00005 TABLE 3-1 Comparative Examples Examples 3-1 3-2 3-3
3-1 3-2 Melting point (Tm) (.degree. C.) 152/158 157/162 161
113/125 137/145 Crystallization (.degree. C.) 104 110 111 66 99
temperature (Tc) .DELTA.H (mJ/mg) 60 59 68 33 66 t.sub.1/2
(110.degree. C.) (sec) 138 98 86 22730 299 r.r.r.r. (%) 94 95 97 69
-- Amount of decane- (%) <0.5 <0.5 <0.5 25 <0.5 soluble
fraction [.eta.] (dL/g) 1.9 2.9 2.4 1.6 2.2 Density (g/cm.sup.3)
0.882 0.883 0.881 0.877 0.898 Mw/Mn 2.0 2.0 2.0 2.0 --
TABLE-US-00006 TABLE 3-2 Comparative Examples Examples 3-1 3-2 3-3
3-1 3-2 Tensile modulus (MPa) 827 858 822 558 814 Tensile break
strength (MPa) 36 39 36 18 25 Elongation (%) 577 592 512 535 1092
Needle penetration (.degree. C.) 155 158 162 121 137 temperature
Internal Haze, 1 mmt (%) 24 20 20 23 71
TABLE-US-00007 TABLE 3-3 Mold release characteristics test
Condition 1 Condition 2 Example 3-1 .largecircle. .largecircle.
Example 3-2 -- -- Comparative Example 3-1 X X Comparative Example
3-2 .largecircle. .largecircle.
Example IV
[1833] Hereinafter, the present invention (4) will be described in
more detail based on Examples, but the present invention is not
intended to be limited to these Examples. In the Examples, the
respective properties were measured as follows.
[1834] Methods for Property Measurement
[1835] [Intrinsic Viscosity [.eta.]]
[1836] Intrinsic viscosity [n] was measured by the same method as
in Example III.
[1837] [Amount of n-Decane-Soluble Fraction]
[1838] Amount of n-decane-soluble fraction was measured by the same
method as in Example III.
[1839] [Molecular Weight Distribution (Mw/Mn)]
[1840] Molecular weight distribution (Mw/Mn) was measured by the
same method as in Example III.
[1841] [Contents of Ethylene, Propylene and .alpha.-Olefin in
Polymer]
[1842] Quantification of the contents of ethylene, propylene and
.alpha.-olefin was determined as follows using a JNM GX-400 type
NMR measuring apparatus manufactured by JEOL, Ltd. 0.35 g of a
sample was dissolved while heating in 2.0 ml of
hexachlorobutadiene, and this solution was filtered through a glass
filter (G2). Subsequently, 0.5 ml of deuterated benzene was added
and the mixture was placed in an NMR tube having an internal
diameter of 10 mm. .sup.13C-NMR measurement was performed at
120.degree. C. The accumulation times were 8,000 or more. The
composition of ethylene, propylene and .alpha.-olefin was
quantified using the .sup.13C-NMR spectrum obtained.
[1843] [Melting Point (Tm) and Heat of Fusion (.DELTA.H) of
Component (AA)]
[1844] Melting point (Tm) and heat of fusion (.DELTA.H) of
component (AA) were measured by the same method as in Example
III.
[1845] [Half-Crystallization Time (t.sub.1/2)]
[1846] Half-crystallization time (t.sub.1/2) was measured by the
same method as in Example III.
[1847] [Glass Transition Temperature (Tg) and Melting Point (Tm) of
Component (B2)]
[1848] About 5 mg of a sample was placed in an aluminum pan for
measurement, and, using a DSC manufactured by Seiko Instruments,
Inc., the sample was heated to 200.degree. C. at a rate of
100.degree. C./min, maintained at 200.degree. C. for 5 minutes,
cooled to -150.degree. C. at a rate of 10.degree. C./min, and then
heated to 200.degree. C. at a rate 10.degree. C./min to obtain an
endothermal curve. The glass transition temperature (Tg) and
melting point (Tm) of component (B2) were determined from the
endothermal curve thus obtained.
[1849] [MFR] The MFR of the syndiotactic propylene polymer (AA) and
propylene..alpha.-olefin copolymer (B3) were measured at
230.degree. C. under a load of 2.16 kg, according to JIS
K-6721.
[1850] The MFR of the ethylene.butene copolymer (C0) was measured
at 190.degree. C. under a load of 2.16 kg, according to JIS
K-6721.
[1851] [Method for Producing Press Sheet for Various
Measurements]
[1852] A press sheet for various measurements was produced by the
same method as in Example III.
[1853] [Tensile Modulus]
[1854] Tensile modulus was measured by the same method as in
Example III.
[1855] [Izod Impact Strength]
[1856] Izod impact strength was measured by the same method as in
Example III.
[1857] [Softening Temperature from TMA Measurement]
[1858] Softening temperature from TMA measurement was measured by
the same method as in Example III.
[1859] [Internal Haze (%)]
[1860] The internal haze was measured using a specimen having a
thickness of 1 mm, and using a digital turbidimeter "NDH-20D"
manufactured by Nippon Denshoku Industries Co., Ltd.
[1861] [Gloss Change Rate (%) after Gakushin Abrasion]
[1862] The Gakushin abrasion testing machine manufactured by Toyo
Seiki Co., Ltd., and a specimen having a thickness of 2 mm was
used. The tip of a 45R SUS abrasion indenter 470 g was covered with
a cotton fabric #10, and the sample was abraded under the
conditions of 23.degree. C., shuttling number of 100 times,
shuttling rate of 33 times/min, and a stroke of 100 mm. The gloss
change rate before and after the abrasion, .DELTA.Gloss, was
determined as follows.
.DELTA.Gloss=(Gloss before abrasion-Gloss after abrasion)/gloss
before abrasion.times.100
[1863] [Permanent Set (%) after 200% Stretching]
[1864] A dumbbell specimen having a shape of length: 50 mm
(L.sub.0), length between marks: 15 mm, and width: 5 mm, and a
thickness of 1 mmt, was mounted on a jig with a chuck interval of
30 mm, and 200% deformation (chuck interval: up to 90 mm) was
applied at a stress rate of 30 mm/min, and then the length (L)
resulting in zero stress during the process of unloading at the
stress rate was measured. Permanent set (%)=L/L.sub.0.times.100
[1865] [Evaluation of film formability]
[1866] Under the conditions of using a single screw extruder with
20 mm.PHI.L/D=28, a die of 25 mmm, lip width of 250 mm, and
processing temperature of 210.degree. C., granulated pellets of the
composition as a sample was extruded at a roll temperature of
40.degree. C. and at a winding rate of 0.63 m/min to form a film
having a thickness of 250 .mu.m. The formability was rated as
follows. No winding on the roll was occurred and continuous
operation for 1 hour was possible: .largecircle., some winding on
the roll was occurred but operation was possible: .DELTA., and
winding on the roll was occurred and continuous operation was
impossible: x. The results are presented in Table 4-2.
Catalyst Synthesis Example
Synthesis Example 4-1
[1867]
Dibenzylmethylene(cyclopentadienyl)(3,6-ditert-butylfluorenyl)zirco-
nium dichloride was produced by the method described in Synthesis
Example 3 of JP-A No. 2004-189666.
Synthesis Example 4-2
[1868]
Dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-ditert-butylfl-
uorenyl)zirconium dichloride was produced by the same method as in
[Synthesis Example 1-1].
Synthesis Example 4-3
[1869]
Di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodi-
benzofluorenyl)zirconium dichloride was produced by the same method
as in Synthesis Example [2-2].
Synthesis Example 4-4
Synthesis of
diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)zirconium dichloride
(i) Synthesis of 1-ethyl-3-tert-butylcyclopentadiene
[1870] Under a nitrogen atmosphere, a 300 ml three-neck flask
equipped with a magnetic stirrer chip and a three-way cock was
charged with 200 ml of dehydrated diethyl ether and 52 ml (154
mmol) of diethyl ether solution of 3.0 Methyl magnesium bromide. In
an ice-water bath, 17.8 g (129 mmol) of 3-tert-butylcyclopentenone
was added dropwise over 1 hour and the resultant solution was
further stirred at room temperature for 20 hours. Then, the
reaction solution was poured into 100 ml of 2N hydrochloric acid.
The organic layer was separated, and the aqueous layer was
subjected to extraction with 50 ml of ether twice. The organic
layers obtained were combined with the organic layer previously
obtained, and the liquid was washed two times with a saturated
aqueous solution of sodium hydrogencarbonate, two times with water,
and once with saturated brine, and dried over magnesium sulfate.
The solvent was distilled off, and then the residue was purified by
column chromatography to obtain 20.2 g of a pale yellowy clear
solution (75% GC purity). The yield was 78%. Identification was
done by .sup.1H-NMR spectrum. The measurement results are shown as
follows.
[1871] .sup.1H-NMR spectrum (270 MHz, CDCl.sub.3, TMS standard):
.delta./ppm 6.19+6.05+5.81+5.77 (m+m+m+m, 2H), 2.91+2.85 (m+m, 2H),
2.48-2.27 (m, 2H), 1.15-1.08 (s+s+m, 12H)
(ii) Synthesis of 3-tert-butyl-1-ethyl-6,6-diphenylfulvene
[1872] Under a nitrogen atmosphere, a 300 ml three-neck flask
equipped with a magnetic stirrer chip and a three-way cock was
charged with 5.11 g (23.9 mmol) of
1-ethyl-3-tert-butylcyclopentadiene (75% GC purity) and 150 ml of
THF. In the dry ice/methanol bath, 16 ml (25.2 mmol) of 1.56M
n-butyllithium hexane solution was gradually added dropwise and the
mixture was then stirred at room temperature for 20 hours. Then,
3.1 ml (28.8 mmol) of 1,3-dimethyl-2-imidazolidinone and 5.3 g
(28.8 mmol) of benzophenone were sequentially added to the reaction
solution obtained, and the solution was stirred for 48 hours under
reflux. The reaction solution was poured into 100 ml of 2N
hydrochloric acid. The organic layer was separated, and the aqueous
layer was subjected to extraction with 50 ml of hexane twice. The
organic layers obtained were combined with the organic layer
previously obtained. The liquid was washed with a saturated aqueous
solution of sodium hydrogencarbonate, water, and a saturated
aqueous solution of sodium chloride, and dried over magnesium
sulfate. The solvent was distilled off, and the residue was
purified by column chromatography to obtain 4.2 g of an orange
solid. The yield was 56%. Identification was done by .sup.1H-NMR
spectrum. The measurement results are shown as follows.
[1873] .sup.1H-NMR spectrum (270 MHz, CDCl.sub.3, TMS standard):
.delta./ppm 7.2-7.4 (m, 10H), 6.3 (m, 1H), 5.7 (m, 1H), 1.70+1.85
(q, 2H), 1.15 (s, 9H), 0.85 (t, 3H).
(iii) Synthesis of
diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)
[1874] A 200 ml three-neck flask equipped with a magnetic stirrer
chip and a three-way cock was thoroughly purged with nitrogen, and
3.8 g of 2,7-di-tert-butylfluorene (13.7 mmol) was dissolved in 80
ml of dehydrated diethyl ether under a nitrogen atmosphere. In an
ice-water bath, 9.2 ml of n-butyl lithium/hexane solution (1.56M:
14.3 mmol) was slowly added dropwise to the solution, and the
mixture was then stirred at room temperature for 100 hours. To the
reaction solution, 4.5 g of
3-tert-butyl-1-ethyl-6,6-diphenylfulvene (14.3 mmol) was added, and
the mixture was then stirred under reflux for 30 hours. The
reaction solution was poured into 100 ml of aqueous solution of 2N
hydrochloric acid in an ice bath. Then, diethylether was added to
separate the organic layer. The aqueous layer was subjected to
extraction with 50 ml of diethyl ether twice. The organic layers
were combined with the organic layer previously obtained, and the
liquid was washed with a saturated aqueous solution of sodium
hydrogencarbonate, water, and a saturated aqueous solution of
sodium chloride, and then dried over magnesium sulfate. The solvent
was distilled off, and the residue was purified by column
chromatography to obtain 4.2 g of a white solid. The yield was 53%.
Identification was done by FD-mass analysis spectrum (FD-MS). The
measurement results are shown as follows.
[1875] FD-MS: m/z-592 (M.sup.+)
(iv) Synthesis of
diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)zirconium dichloride
[1876] A 100 ml Schlenk flask equipped with a magnetic stirrer chip
and a three-way cock was thoroughly purged with nitrogen, and 1.0 g
of
diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl) (1.68 mmol) was dissolved in 40 ml of dehydrated
diethylether under a nitrogen atmosphere. In an ice bath, 2.2 ml
(3.4 mmol) of 1.56M n-butyllithium hexane solution was gradually
added dropwise to this solution, and then stirred at room
temperature for 28 hours. This reaction solution was thoroughly
cooled in a dry ice/methanol bath, and then 0.39 g of zirconium
tetrachloride (1.68 mmol) was added. The solution was stirred for
48 hours while gradually warming to room temperature. Then, the
solvent was distilled off under reduced pressure. The resulting
product was reslurred in hexane, and the slurry was filtered with
use of a diatomite-filled glass filter. A brown solid on the filter
was separated through extraction with a small amount of
dichloromethane. For the hexane solution and dichloromethane
solution obtained, each solvent was distilled off under reduced
pressure. The dark orange solids were each washed with a small
amount of pentane and diethylether, and then dried under reduced
pressure to obtain 140 mg (0.186 mmol) of a target compound as an
orange solid. Identification was done by .sup.1H-NMR spectrum and
FD-mass analysis spectrum. The measurement results are shown as
follows.
[1877] .sup.1H-NMR spectrum (270 MHz, CDCl.sub.3, TMS standard):
.delta./ppm 7.90-8.07 (m, 5H), 7.75 (m, 1H), 7.15-7.60 (m, 8H),
6.93 (m, 1H), 6.15-6.25 (m, 2H), 5.6 (d, 1H), 2.05+2.25 (q, 2H),
0.95-1.15 (s+t+s, 30H)
[1878] FD-MS: m/z-752 (M.sup.+)
Polymerization Examples
Polymerization Example 4A-1
Synthesis of Syndiotactic Propylene Polymer (4A-1)
[1879] A thoroughly nitrogen purged glass autoclave having the
internal volume of 500 ml was charged with 250 ml of toluene, and
then charged with propylene at a rate of 150 liter/hour, which was
kept at 25.degree. C. for 20 minutes. Meanwhile, a magnetic stirrer
was placed in a thoroughly nitrogen purged side arm flask having an
internal volume of 30 ml, and the flask was sequentially charged
with 5.00 mmol of a toluene solution of methylaluminoxane (Al=1.53
mol/l) and 5.0 .mu.mol of a toluene solution of
dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride. The mixture was stirred for 20 minutes. This solution
was then added to toluene in the glass autoclave which had been
charged with propylene, and the polymerization was initiated.
Propylene gas was continuously supplied at a rate of 150
liter/hour, and the polymerization was performed at 25.degree. C.
for 45 minutes under normal pressure. Thereafter, a small amount of
methanol was added to terminate the polymerization. The polymer
solution was added to an excessive amount of methanol to
precipitate a polymer. The polymer was then dried under reduced
pressure at 80.degree. C. for 12 hours to obtain a polymer in an
amount of 2.38 g. The polymerization activity was 0.63
kg-PP/mmol-Zrhr. The polymer obtained had [.eta.]=1.9 dl/g,
Tm.sub.1=152.degree. C., Tm2=158.degree. C., rrrr=93.5%, and
Mw/Mn=2.0. This procedure was repeated to obtain a required amount
of the polymer, which was then used in Examples. In addition, for
the evaluation of the film formability, a sample used was a polymer
having the same TMA softening temperature, rrrr fraction, [.eta.],
and Mw/Mn as that of the above-mentioned polymer. The polymer was
produced in accordance with the above-mentioned production process,
but in a larger scale.
Polymerization Example 4A-2
Synthesis of Syndiotactic Propylene Polymer (4A-2)
[1880] A thoroughly nitrogen purged glass autoclave having an
internal volume of 500 ml was charged with 250 ml of toluene, and
then charged with propylene at a rate of 150 liter/hour, which kept
at 25.degree. C. for 20 minutes. Meanwhile, a magnetic stirrer was
placed in a thoroughly nitrogen purged side arm flask having an
internal volume of 30 ml, the flask was sequentially charged with
5.00 mmol of a toluene solution of methylaluminoxane (Al=1.53
mol/l) and 5.0 mol of a toluene solution of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluoren-
yl)zirconium dichloride. The mixture was stirred for 20 minutes.
This solution was then added to toluene in the glass autoclave
which had been charged with propylene, and the polymerization was
initiated. Propylene gas was continuously supplied at a rate of 150
liter/hour, and the polymerization was performed at 25.degree. C.
for 10 minutes under normal pressure. Thereafter, a small amount of
methanol was added to terminate the polymerization. The polymer
solution was added to an excessive amount of methanol to
precipitate a polymer. The polymer was then dried under reduced
pressure at 80.degree. C. for 12 hours to obtain a polymer in an
amount of 6.95 g. The polymerization activity was 7.58
kg-PP/mmol-Zrhr. The polymer obtained had [.eta.]=2.9 dl/g,
Tm=162.0.degree. C., and rrrr fraction=95.3%. This procedure was
repeated to obtain a required amount of the polymer, which was then
used in Examples.
Syndiotactic Propylene Polymer (4A-3)
[1881] Syndiotactic polypropylene (Trade Name: Finaplas 1471,
MFR=5.0 g/10 min) produced by Total, Inc. was used in Examples. The
properties are shown in Table 4-1.
Polymerization Example 4A-4
Synthesis of Syndiotactic Propylene Polymer (4A-4)
[1882] The syndiotactic propylene polymer (4A-4) (propylene
homopolymer) was produced in accordance with the production process
in Polymerization Example 4A-1, except that hydrogen was introduced
(in other words, hydrogen was further supplied in the
polymerization system). The polymer obtained had the same TMA
softening temperature, rrrr fraction, and Mw/Mn as those of the
polymer (4A-1), and had [r] of 1.4 dl/g. The properties of the
polymer (4A-4) are shown in Table 4-4.
Polymerization Example 4A-5
Synthesis of Syndiotactic Propylene Polymer (4A-5)
[1883] The syndiotactic propylene polymer (4A-5) (propylene
homopolymer) was produced in accordance with the production process
in Polymerization Example 4A-1, except that hydrogen was introduced
(in other words, hydrogen was further supplied in the
polymerization system). The polymer obtained had the same TMA
softening temperature, rrrr fraction, and Mw/Mn as those of the
polymer (4A-1), and had [.eta.] of 1.2 dl/g. The properties of the
polymer (4A-5) are shown in Table 4-4.
Syndiotactic Propylene Polymer (4A-6)
[1884] Syndiotactic polypropylene (Trade Name: Finaplas 1571,
MFR=9.1 g/10 min) produced by Total, Inc. was used in Examples. The
properties are shown in Table 4-4.
Polymerization Example 4B-1
Synthesis of Propylene..alpha.-Olefin Copolymer (4B-1)
[1885] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane and
triisobutylaluminum (1.0 mmol) at normal temperature. Subsequently,
the internal temperature of the polymerization apparatus was raised
to 70.degree. C., and propylene was introduced to raise the
pressure in the system to 0.66 MPa, and ethylene was then
introduced to adjust the pressure in the system to 1.36 MPa.
Subsequently, the polymerization vessel was charged with a toluene
solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 15
minutes while maintaining the internal temperature at 70.degree. C.
and the pressure in the system at 1.36 MPa with ethylene, and 20 ml
of methanol was added to the terminate polymerization. After
depressurizing, the resulting polymer was precipitated from the
polymerization solution in 4 L of methanol, and dried in a vacuum
at 130.degree. C. for 12 hours. The amount of the polymer obtained
was 105 g, MFR was 0.7 (g/10 min), and [.eta.] measured at
135.degree. C. in decalin was 2.5 (dL/g). The polymer properties
measured are shown in Table 4-1. The rr.sub.1 value was 78%.
Polymerization Example 4B-2
Propylene..alpha.-Olefin Copolymer (4B-2)
[1886] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane and
triisobutylaluminum (1.0 mmol) at normal temperature. Subsequently,
the internal temperature of the polymerization apparatus was raised
to 70.degree. C., and propylene was introduced to raise the
pressure in the system to 0.64 MPa, and ethylene was then
introduced to adjust the pressure in the system to 1.34 MPa.
Subsequently, the polymerization vessel was charged with a toluene
solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 15
minutes while maintaining the internal temperature at 70.degree. C.
and the pressure in the system at 1.34 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After
depressurizing, the resulting polymer was precipitated from the
polymerization solution in 4 L of methanol, and dried in a vacuum
at 130.degree. C. for 12 hours. The amount of the polymer obtained
was 109 g, MFR was 0.6 (g/10 min), and [.eta.] measured at
135.degree. C. in decalin was 2.6 (dL/g). The polymer properties
measured are shown in Table 4-1. The rr.sub.1 value was 76%. This
procedure was repeated to obtain a required amount of the polymer,
which was then used in Examples. In addition, the polymer used in
the evaluation of the film formability was produced in accordance
with the above-mentioned production process, but in a large scale.
The polymer had the same ethylene content, rr fraction, [.eta.],
and Mw/Mn as those of the above-mentioned polymer.
Polymerization Example 4B-3
Propylene..alpha.-Olefin Copolymer (4B-3)
[1887] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane and
triisobutylaluminum (1.0 mmol) at normal temperature. Subsequently,
the internal temperature of the polymerization apparatus was raised
to 70.degree. C., and propylene was introduced to raise the
pressure in the system to 0.67 MPa, and ethylene was then
introduced to adjust the pressure in the system to 1.37 MPa.
Subsequently, the polymerization vessel was charged with a toluene
solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 10
minutes while maintaining the internal temperature at 70.degree. C.
and the pressure in the system at 1.37 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After
depressurizing, the resulting polymer was precipitated from the
polymerization solution in 4 L of methanol, and dried in a vacuum
at 130.degree. C. for 12 hours. The amount of the polymer obtained
was 90 g, MFR was 1.0 (g/10 min), and [.eta.] measured at
135.degree. C. in decalin was 2.3 (dL/g). The rr.sub.1 value was
75%. The polymer properties measured are shown in Table 4-1.
Polymerization Example 4B-4
Synthesis of Propylene..alpha.-Olefin Copolymer (4B-4)
[1888] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane, 20 g of 1-butene,
and triisobutylaluminum (1.0 mmol) at normal temperature.
Subsequently, the internal temperature of the polymerization
apparatus was raised to 70.degree. C., and propylene was introduced
to raise the pressure in the system to 0.63 MPa, and ethylene was
then introduced to adjust the pressure in the system to 1.33 MPa.
Subsequently, the polymerization vessel was charged with a toluene
solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had contacted with 0.3 mmol, in terms
of aluminum, of methylaluminoxane (manufactured by Tosoh Finechem
Corporation). Polymerization was then performed for 10 minutes
while maintaining the internal temperature at 70.degree. C. and the
pressure in the system at 1.33 MPa with ethylene, and 20 ml of
methanol was added to terminate the polymerization. After
depressurizing, the resulting polymer was precipitated from the
polymerization solution in 4 L of methanol, and dried in a vacuum
at 130.degree. C. for 12 hours. The amount of the resulting polymer
was 102 g, MFR was 1.0 (g/10 min), and [.eta.] measured at
135.degree. C. in decalin was 2.3 (dL/g). The polymer properties
measured are shown in Table 4-1. The rr.sub.1 value was 75%.
Polymerization Example 4B-5
Synthesis of Propylene..alpha.-Olefin Copolymer (4B-5)
[1889] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane and
triisobutylaluminum (1.0 mmol) at normal temperature. Subsequently,
the internal temperature of the polymerization apparatus was raised
to 50.degree. C., and propylene was introduced to raise the
pressure in the system to 0.67 MPa, and ethylene was then
introduced to adjust the pressure in the system to 1.37 MPa.
Subsequently, the polymerization vessel was charged with a toluene
solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 10
minutes while maintaining the internal temperature at 50.degree. C.
and the pressure in the system at 1.37 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After
depressurizing, the resulting polymer was precipitated from the
polymerization solution in 4 L of methanol, and dried in a vacuum
at 130.degree. C. for 12 hours. The amount of the resulting polymer
was 78 g, [.eta.] measured at 135.degree. C. in decalin was 3.5
(dL/g), and an ethylene content measured by .sup.13C-NMR was 18 mol
%. The polymer properties measured are shown in Table 4-4.
[1890] Details of the ethylene.butene copolymer (4C) and propylene
polymers (4D-1) to (4D-8) are as follows.
[1891] (Ethylene.Butene Copolymer (4C))
[1892] Described in Table 4-1, MFR=4.0 g/10 min
[1893] (Propylene Polymer (4D-1))
[1894] PP produced by Prime Polymer Co., Ltd. (Trade Name: F102W,
MFR=2.1 g/10 min)
[1895] (Propylene Polymer (4D-2))
[1896] PP produced by Prime Polymer Co., Ltd. (Trade Name: J104W,
MFR=5.2 g/10 min)
[1897] (Propylene Polymer (4D-3))
[1898] PP produced by Prime Polymer Co., Ltd. (Trade Name: B101,
MFR=0.7 g/10 min)
[1899] (Propylene Polymer (4D-4))
[1900] PP produced by Prime Polymer Co., Ltd. (Trade Name: J106G,
MFR=15.0 g/10 min)
[1901] (Propylene Polymer (4D-5))
[1902] PP produced by Prime Polymer Co., Ltd. (Trade Name: J107G,
MFR=30.0 g/10 min)
[1903] (Propylene Polymer (4D-6))
[1904] PP produced by Prime Polymer Co., Ltd. (Trade Name: J108M,
MFR=45.0 g/10 min)
[1905] (Propylene Polymer (4D-7))
[1906] (Synthesis of Propylene.Ethylene.Butene Copolymer)
[1907] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane, 110 g of 1-butene,
and triisobutylaluminum (1.0 mmol) at normal temperature.
Subsequently, the internal temperature of the polymerization
apparatus was raised to 55.degree. C., and propylene was introduced
to raise the pressure in the system to 0.58 MPa, and ethylene was
then introduced to adjust the pressure in the system to 0.75 MPa.
Subsequently, the polymerization vessel was charged with a toluene
solution in which 0.001 mmol of
diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)zirconium dichloride synthesized in Synthesize Example
4-4 had been contacted with 0.3 mmol, in terms of aluminum, of
methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 25 minutes while maintaining
the internal temperature at 55.degree. C. and the pressure in the
system at 0.75 MPa with ethylene, and 20 ml of methanol was added
to terminate the polymerization. After depressurizing, the
resulting polymer was precipitated from the polymerization solution
in 4 L of methanol, and dried in a vacuum at 130.degree. C. for 12
hours. The amount of the resulting polymer was 120.2 g and MFR was
0.7 (g/10 min). The polymer properties measured are shown in Table
4-5.
[1908] (Propylene Polymer (4D-8))
[1909] The polymer (4D-8) was produced in accordance with the
process condition of producing the polymer 4D-7, except that the
polymerization temperature was changed to 40.degree. C. The polymer
had the same ethylene content and butene content as those of the
polymer (4D-7), and had [(] of 4.0 dl/g and Mw/Mn of 2.1. The
properties of the polymer obtained are shown in Table 4-5.
[1910] The properties of the propylene polymers (4D-1) to (4D-8)
are shown in Table 4-5.
[1911] FIG. 3 shows a graph in which MFR and [.eta.] are plotted
with respect to the isotactic propylene polymers (4D-1) to (4D-8)
and of the polymers (4B-1) to (4B-5), (4A-1), (4A-3), (4A-4),
(4A-5) and (4A-6) used in the present invention (4). The graph
shows the polymers used in the present invention (4) are
distinguished from the isotactic propylene-based polymers (4D-1) to
(4d-8) by the requirement (b-2).
TABLE-US-00008 TABLE 4-1 Syndiotactic propylene
Propylene.cndot..alpha.-olefin Ethylene.cndot.Butene polymer (AA)
copolymer (B2) copolymer (4A-1) (4A-2) (4A-3) (4B-1) (4B-2) (4B-3)
(4B-4) (4C) Compo- (a) Propylene content (mol %) 100 100 100 77 72
82 68 0 sition (b) Ethylene content (mol %) 0 0 0 23 28 18 27 88
(c) .alpha.-olefin content (mol %) 0 0 0 0 0 0 5 12 Melting point
(Tm) (.degree. C.) 152/158 157/162 113/125 -- -- -- -- 72 rrrr (%)
94 95 69 -- -- -- -- -- r.r (%) -- -- -- 82.9 84.6 83.5 82.1 -- MFR
(g/10 min) 2.4 -- 5.0 0.7 0.6 1.0 1.0 4.0 [.eta.] (dL/g) 1.9 2.9
1.6 2.5 2.6 2.3 2.3 1.5 Density (g/cm.sup.3) 0.882 0.883 0.877
0.852 0.852 0.852 0.853 0.888 .DELTA.H (mJ/mg) 62 59 33 -- -- -- --
63 Tg (.degree. C.) -5.7 -5.8 -6.5 -30.1 -34.9 -26.8 -35.4 -52.8
Mw/Mn 2.0 2.0 2.0 2.0 2.0 2.0 2.0 -- t.sub.1/2 (110.degree. C.)
(sec) 138 98 22730 Amount of Decane- (%) <0.5 <0.5 25 soluble
fraction
Example 4-1
[1912] A composition of 80 parts by weight of the syndiotactic
polypropylene (4A-1) obtained in [Polymerization Example (4A-1)]
and 20 parts by weight of the propylene-ethylene copolymer (4B-2)
obtained in [Polymerization Example (4B-2)] was blended with, based
on 100 parts by weight of the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C. The sheet was used as
a specimen for measurement after cutting into an appropriate size,
or the like. Also, a press sheet was produced from the specimen,
and the properties thereof were measured. The results of various
property tests are presented in Table 4-2. The composition has
excellent moldability and heat resistance, as well as excellent
transparency, impact resistance, and scratch resistance.
Example 4-2
[1913] A composition of 70 parts by weight of the syndiotactic
polypropylene (4A-1) obtained in [Polymerization Example (4A-1)]
and 30 parts by weight of the propylene-ethylene copolymer (4B-2)
obtained in [Polymerization Example (4B-2)] was blended with, based
on 100 parts by weight of the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C. The sheet was used as
a specimen for measurement after cutting into an appropriate size,
or the like. Also, a press sheet was produce from the specimen, and
the properties thereof were measured. The results of various
property tests are presented in Table 4-2. The composition has
excellent moldability and heat resistance, as well as excellent
transparency, impact resistance, and scratch resistance.
Example 4-3
[1914] A composition of 60 parts by weight of the syndiotactic
polypropylene (4A-1) obtained in [Polymerization Example (4A-1)]
and 40 parts by weight of the propylene-ethylene copolymer (4B-2)
obtained in [Polymerization Example (4B-2)] was blended with, based
on 100 parts by weight of the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C. The sheet was used as
a specimen for measurement after cutting into an appropriate size,
or the like. Also, a press sheet was produced from the specimen,
and the properties thereof were measured. The results of various
property tests are presented in Table 4-2. The composition has
excellent moldability and heat resistance, as well as excellent
transparency, impact resistance, and scratch resistance.
Example 4-4
[1915] A composition of 60 parts by weight of the syndiotactic
polypropylene (4A-1) obtained in [Polymerization Example (4A-1)]
and 40 parts by weight of the propylene-ethylene copolymer (4B-1)
obtained in [Polymerization Example (4B-1)] was blended with, based
on 100 parts by weight of the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C. The sheet was used as
a specimen for measurement after cutting into an appropriate size,
or the like. Also, a press sheet was produced from the specimen,
and the properties thereof were measured. The results of various
property tests are presented in Table 4-2. The composition has
excellent moldability and heat resistance, as well as excellent
transparency, impact resistance, and scratch resistance.
Example 4-5
[1916] A composition of 60 parts by weight of the syndiotactic
polypropylene (4A-1) obtained in [Polymerization Example (4A-1)]
and 40 parts by weight of the propylene-ethylene copolymer (4B-4)
obtained in [Polymerization Example (4B-4)] was blended with, based
on 100 parts by weight of the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C. The sheet was used as
a specimen for measurement after cutting into an appropriate size,
or the like. Also, a press sheet was produced from the specimen,
and the properties thereof were measured. The results of various
property tests are presented in Table 4-2. The composition has
excellent moldability and heat resistance, as well as excellent
transparency, impact resistance, and scratch resistance.
Comparative Example 4-1
[1917] A composition of 60 parts by weight of the syndiotactic
polypropylene (4A-3) (trade name: Finaplas1471, MFR=5.0 g/10 min,
rrrr fraction=69%) manufactured by Total Corp., and 40 parts by
weight of the propylene-ethylene copolymer (4B-2) obtained in
[Polymerization Example 4A-4] was blended with, based on 100 parts
by weight of the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C. The sheet was used as
a specimen for measurement after cutting into an appropriate size,
or the like. Also, a press sheet was produced from the specimen,
and the properties thereof were measured. The results of various
property tests are presented in Table 4-2. Compared to the products
of Examples 4-1 to 4-5, the composition has inferior moldability
and heat resistance.
TABLE-US-00009 TABLE 4-2 Comparative Example Example 4-1 4-2 4-3
4-4 4-5 4-1 Polymer (AA) 4A-1 4A-1 4A-1 4A-1 4A-1 4A-3 Copolymer
(B2) 4B-2 4B-2 4B-2 4B-1 4B-4 4B-2 Composition ratio (AA)/(B2)
80/20 70/30 60/40 60/40 60/40 60/40 (parts by weight) Softening
temperature (TMA) (.degree. C.) 155 154 156 155 155 121 t.sub.1/2
(110.degree. C.) (sec) 170 205 225 210 205 8850 Cloudiness (Haze)
(%) 31 34 43 27 32 25 Internal Haze (%) 27 29 36 25 28 21 Tensile
modulus (MPa) 450 328 250 230 230 170 Izod (0.degree. C.) (J/m) 720
880 890 860 850 660 Gloss change rate (%) 8 12 14 11 7 17 Film
formability .smallcircle. -- .smallcircle. -- -- x Amount of
decane- (wt %) 21 21 41 41 41 58 soluble fraction at R.T. r.r.r.r.
of decane- (%) 94 94 94 94 94 69 insoluble fraction at R.T. Tm of
decane- (.degree. C.) 152/158 152/158 152/158 152/158 152/158
113/125 insoluble fraction at R.T. Compo- (a) Propylene content
(mol %) 94.0 91.0 88.2 90.4 86.6 88.2 sition (b) Ethylene content
(mol %) 6.0 9.0 11.8 9.6 11.3 11.8 (c) .alpha.-olefin content (mol
%) 0.0 0.0 0.0 0.0 2.1 0.0 -- indicates non-measured category
Example 4-6
[1918] A composition of 20 parts by weight of the syndiotactic
polypropylene (4A-1) obtained in [Polymerization Example (4A-1)]
and 80 parts by weight of the propylene-ethylene copolymer (4B-3)
obtained in [Polymerization Example (4B-3)] was blended with, based
on 100 parts by weight of the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 4-3. The
composition has excellent moldability and heat resistance, as well
as excellent transparency, flexibility, and scratch resistance.
Example 4-7
[1919] A composition of 30 parts by weight of the syndiotactic
polypropylene (4A-1) obtained in [Polymerization Example (4A-1)]
and 70 parts by weight of the propylene-ethylene copolymer (4B-3)
obtained in [Polymerization Example (4B-3)] was blended with, based
on 100 parts by weight of the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 4-3. The
composition has excellent moldability and heat resistance, as well
as excellent transparency, flexibility, and scratch resistance.
Example 4-8
[1920] A composition of 20 parts by weight of the syndiotactic
polypropylene (4A-2) obtained in [Polymerization Example (4A-2)]
and 80 parts by weight of the propylene-ethylene copolymer (4B-3)
obtained in [Polymerization Example (4B-3)] was blended with, based
on 100 parts by weight of the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 4-3. The
composition has excellent moldability and heat resistance, as well
as excellent transparency, impact resistance, and scratch
resistance.
Comparative Example 4-2
[1921] A composition of 20 parts by weight of the syndiotactic
polypropylene (4A-3) (trade name: Finaplas1471, MFR=5.0 g/10 min)
manufactured by Total Corp., and 80 parts by weight of the
propylene.ethylene copolymer (4B-3) obtained in [Polymerization
Example (4B-3)] was blended with, based on 100 parts by weight of
the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 4-3.
Compared to the products of Examples 4-6 and 4-7, the composition
has inferior moldability and heat resistance.
Comparative Example 4-3
[1922] A composition of 30 parts by weight of the syndiotactic
polypropylene (4A-3) (trade name: Finaplas1471, MFR=5.0 g/10 min)
manufactured by Total Corp., and 70 parts by weight of the
ethylene.butene copolymer (C) was blended with, based on 100 parts
by weight of the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 4-3.
Compared to the products of Examples 4-6 and 4-7, the composition
has inferior moldability and heat resistance, as well as inferior
transparency and scratch resistance.
TABLE-US-00010 TABLE 4-3 Comparative Example Example 4-6 4-7 4-8
4-2 4-3 Polymer (AA) 4A-1 4A-1 4A-2 4A-3 4A-3 Copolymer (B2) or (C)
4B-3 4B-3 4B-3 4B-3 4C Composition ratio (AA)/(B2) or (C) 20/80
30/70 20/80 20/80 30/70 (parts by weight) Softening temperature
(TMA) (.degree. C.) 131 156 135 108 56 t.sub.1/2 (110.degree. C.)
(sec) 230 215 178 9910 11800 Cloudiness (Haze) (%) 5 10 7 8 90
Internal Haze (%) 3 8 5 5 89 Tensile modulus (MPa) 21 68 27 46 70
Gloss change rate (%) 18 21 17 30 95 Permanent set (%) 32 37 28 47
87 Amount of decane- (wt %) 81 71 80 86 79 soluble fraction at R.T.
r.r.r.r. of decane- (%) 94 94 95 69 69 insoluble fraction at R.T.
Tm of decane- (.degree. C.) 152/158 152/158 157/162 113/125 113/125
insoluble fraction at R.T. Compo- (a) Propylene content (mol %)
82.0 87.1 82.0 82.0 24.2 sition (b) Ethylene content (mol %) 18.0
12.9 18.0 18.0 66.7 (c) .alpha.-olefin content (mol %) 0.0 0.0 0.0
0.0 9.1
TABLE-US-00011 TABLE 4-4 Syndiotactic propylene
Propylene.cndot..alpha.-olefin polymer (AA) copolymer (B2) (4A-4)
(4A-5) (4A-6) (4B-5) r.r. (%) -- -- -- 75 MFR (g/10 min) 16.8 20.3
9.1 0.1 [.eta.] (dL/g) 1.4 1.2 1.3 3.5
TABLE-US-00012 TABLE 4-5 Propylene polymer (4D) (4D-1) (4D-2)
(4D-3) (4D-4) (4D-5) (4D-6) (4D-7) (4D-8) MFR (g/10 min) 2.1 5.2
0.7 15.0 30.0 45.0 0.7 0.2 [.eta.] (dL/g) 2.7 2.4 3.2 1.9 1.7 1.4
2.9 4.0 mmmm (%) -- -- -- 96 -- 96 -- --
Example V
[1923] Hereinafter, the present invention (5) will be described in
more detail based on Examples, but the present invention is not
intended to be limited to these Examples. In these Examples, the
respective properties were measured as follows.
[1924] Methods for Measuring Properties
[1925] [Intrinsic Viscosity [.eta.]]
[1926] Intrinsic viscosity [.eta.] was measured by the same method
as in Example IV.
[1927] [Amount of n-Decane-Soluble Fraction]
[1928] Amount of n-decane-soluble fraction was measured by the same
method as in Example IV.
[1929] [Molecular Weight Distribution (Mw/Mn)]
[1930] Molecular weight distribution (Mw/Mn) was measured by the
same method as in Example IV.
[1931] [Contents of Ethylene, Propylene and .alpha.-Olefin in
Polymer]
[1932] Contents of ethylene, propylene and .alpha.-olefin in
polymer were measured by the same method as in Example IV.
[1933] [Melting Point (Tm) and Heat of Fusion (.DELTA.H)]
[1934] Using a DSC7 manufactured by PerkinElmer, Inc., under a
nitrogen atmosphere (20 ml/min), about 5 mg of a sample was heated
to 200.degree. C., maintained for 10 minutes, and then cooled to
30.degree. C. at 10.degree. C./min. Subsequently, the temperature
was maintained at 30.degree. C. for 5 minutes and raised to
200.degree. C. at 10.degree. C./min. The melting point was
calculated from the peak top of the crystal melting peak, and the
heat of fusion was calculated from the integrated value of the
peak.
[1935] [Half-Crystallization Time (t.sub.1/2)]
[1936] Half-crystallization time (t.sub.1/2) was measured by the
same method as in Example IV.
[1937] [Glass Transition Temperature (Tg)]
[1938] Glass transition temperature (Tg) was measured by the same
method as in Example IV.
[1939] [MFR]
[1940] MFR was measured by the same method as in Example IV.
[1941] [Method for Producing Press Sheet for Various
Measurements]
[1942] A press sheet for various measurements was produced by the
same method as in Example IV.
[1943] [Tensile Modulus]
[1944] Tensile modulus was measured by the same method as in
Example IV.
[1945] [Izod Impact Strength]
[1946] Izod impact strength was measured by the same method as in
Example IV.
[1947] [Softening Temperature from TMA Measurement]
[1948] Softening temperature from TMA measurement was measured by
the same method as in Example IV.
[1949] [Internal Haze (%)]
[1950] Internal haze (%) was measured by the same method as in
Example IV.
[1951] Polymer
[1952] Here are details of the syndiotactic polypropylenes (5A-1)
to (5A-6), propylene..alpha.-olefin copolymers (5B-1) to (5B-5),
ethylene.butene copolymer (C), and propylene polymers (D-1) to
(D-8).
Syndiotactic Polypropylenes (5A-1) to (5A-6)
[1953] Syndiotactic polypropylenes (4A-1), (4A-2), (4A-3), (4A-4),
(4A-5) and (4A-6) of Example IV were used as syndiotactic
polypropylenes (5A-1), (5A-2), (5A-3), (5A-4), (5A-5) and (5A-6),
respectively.
[1954] (Propylene..alpha.-Olefin Copolymers (5B-1) to (5B-5))
[1955] Propylene..alpha.-olefin copolymers (4B-1), (4B-2), (4B-3),
(4B-4) and (4B-5) of Example IV were used as
propylene..alpha.-olefin copolymers (5B-1), (5B-2), (5B-3), (5B-4)
and (5B-5), respectively.
[1956] (Ethylene.Butene Copolymers (5C-1) to (5C-3))
[1957] Properties of ethylene.butene-1 random copolymers (5C-1) to
(5C-3) are presented in Table 5-1.
[1958] (Propylene Polymers (5D-1) to (5D-8))
[1959] Propylene polymers (4D-1), (4D-2), (4D-3), (4D-4), (4D-5),
(4D-6), (4D-7) and (4D-8) of Example IV were used as propylene
polymers (5D-1), (5D-2), (5D-3), (5D-4), (5D-5), (5D-6), (5D-7) and
(5D-8), respectively.
[1960] Properties of the propylene polymers (5D-1) to (5D-8),
namely, the propylene polymers (4D-1) to (4D-8), are presented in
Table 4-5.
[1961] FIG. 4-2 shows a plotted graph of MFR and [1] of the
isotactic propylene polymers (5D-1) to (5D-8) (namely, the polymers
(4D-1) to (4D-8)) and the polymers (5B-1) to (5B-5), (5A-1),
(5A-3), (5A-4), (5A-5) and (5A-6) used in the present invention (5)
(namely, the polymers (4B-1) to (4B-5), (4A-1), (4A-3), (4A-4),
(4A-5) and (4A-6)).
[1962] That shows the isotactic polymer and the polymers used in
the present invention (5) are distinguished by the requirement
(b-2).
TABLE-US-00013 TABLE 5-1 Syndiotactic propylene
Propylene.cndot..alpha.-olefin Ethylene.cndot..alpha.-olefin
copolymer (AA) copolymer (B2) copolymer (5A-1) (5A-2) (5A-3) (5B-1)
(5B-2) (5B-3) (5B-4) (5C-1) (5C-2) (5C-3) Compo- (a) Propylene
content (mol %) 100 100 100 77 72 82 68 0 0 0 sition (b) Ethylene
content (mol %) 0 0 0 23 28 18 27 88 88 85 (c) .alpha.-olefin
content (mol %) 0 0 0 0 0 0 5 12 12 15 Melting point (Tm) (.degree.
C.) 152/158 157/162 113/125 -- -- -- -- 72 69 56 rrrr (%) 94 95 69
-- -- -- -- -- -- -- Rr (%) -- -- -- 82.9 84.6 83.5 82.1 -- -- --
[.eta.] (dL/g) 1.9 2.9 1.6 -- -- -- -- 1.5 -- -- MFR (g/10 min) 2.4
-- 5.0 0.7 0.6 1.0 1.0 4.0 0.5 4.0 Density (g/cm.sup.3) 0.882 0.883
0.877 0.852 0.852 0.852 0.853 0.888 0.885 0.870 .DELTA.H (mJ/mg) 62
59 33 -- -- -- -- 63 60 37 Tg (.degree. C.) -5.7 -5.8 -6.5 -30.1
-34.9 -26.8 -35.4 -52.8 -52.1 -58.7 Mw/Mn 2.0 2.0 2.0 2.0 2.0 2.0
2.0 -- -- -- t.sub.1/2 (110.degree. C.) (sec) 138 98 22730 Amount
of Decane- (%) <0.5 <0.5 25 soluble fraction
Example 5-1
[1963] A composition of 100 parts by weight of the syndiotactic
polypropylene (5A-1) obtained in [Polymerization Example (5A-1)]
and 25 parts by weight of the ethylene.1-butene random copolymer
(5C-1) (MFR (190.degree. C.)=4.0, 1-butene content 12 mol %) was
blended with, based on the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C. The sheet was used as
a specimen for measurement after cutting into an appropriate size,
or the like. Also, a press sheet was produced from the specimen,
and the properties thereof were measured. The results of various
property tests are presented in Table 5-2. The composition has
excellent moldability and heat resistance, as well as excellent
transparency and low temperature impact resistance.
Example 5-2
[1964] A composition of 100 parts by weight of the syndiotactic
polypropylene (5A-1) obtained in [Polymerization Example (5A-1)]
and 66.7 parts by weight of the ethylene.1-butene random copolymer
(5C-1) (MFR (190.degree. C.)=4.0, 1-butene content 12 mol %) was
blended with, based on the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C. The sheet was used as
a specimen for measurement after cutting into an appropriate size,
or the like. Also, a press sheet was produced from the specimen,
and the properties thereof were measured. The results of various
property tests are presented in Table 5-2. The composition has
excellent moldability and heat resistance, as well as excellent
transparency, flexibility and low temperature impact
resistance.
Example 5-3
[1965] A composition of 75 parts by weight of the syndiotactic
polypropylene (5A-1) obtained in [Polymerization Example (5A-1)],
parts by weight of the propylene-ethylene copolymer (5B-1) obtained
in [Polymerization Example (5B-1)] and 25 parts by weight of the
ethylene.1-butene random copolymer (5C-3) (MFR (190.degree.
C.)=4.0, 1-butene content 15 mol %) was blended with, based on the
composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 5-2. The
composition has excellent moldability and heat resistance, as well
as excellent transparency, flexibility and low temperature impact
resistance.
Example 5-4
[1966] A composition of 66.7 parts by weight of the syndiotactic
polypropylene (5A-1) obtained in [Polymerization Example (5A-1)],
33.4 parts by weight of the propylene.ethylene copolymer (5B-3)
obtained from [Polymerization Example (5B-3)] and 66.7 parts by
weight of the ethylene.1-butene random copolymer (5C-2) (MFR
(190.degree. C.)=0.5, 1-butene content 12 mol %) was blended with,
based on the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 5-2. The
composition has excellent moldability and heat resistance, as well
as excellent transparency, flexibility and impact resistance.
Example 5-5
[1967] A composition of 50 parts by weight of the syndiotactic
polypropylene (5A-2) obtained in [Polymerization Example (5A-2)],
50 parts by weight of the propylene-ethylene copolymer (5B-4)
obtained in [Polymerization Example (5B-4)] and 25 parts by weight
of the ethylene.1-butene random copolymer (5C-3) (MFR (190.degree.
C.)=4.0, 1-butene content 15 mol %) was blended with, based on the
composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 5-2. The
composition has excellent moldability and heat resistance, as well
as excellent transparency, flexibility and impact resistance.
Reference Example 5-1
[1968] A composition of 100 parts by weight of the syndiotactic
polypropylene (5A-1) obtained in [Polymerization Example (5A-1)]
and 150 parts by weight of an ethylene.1-butene random copolymer
(5C-1) (MFR (190.degree. C.)=4.0, 1-butene content 12 mol %) was
blended with, based on the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 5-2.
Comparative Example 5-2
[1969] A composition of 100 parts by weight of the syndiotactic
polypropylene (5A-3) (trade name: Finaplas1471, MFR=5.0 g/10 min,
rrrr fraction=69%) manufactured by Total Corp., and 25 parts by
weight of the ethylene. 1-butene random copolymer (5C-1) (MFR
(190.degree. C.)=4.0, 1-butene content 12 mol %) was blended with,
based on the composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 5-2.
Compared to the products of Examples, the composition has inferior
moldability and heat resistance.
Comparative Example 5-3
[1970] A 60 parts by weight of the syndiotactic polypropylene
(5A-3) (trade name: Finaplas1471, MFR=5.0 g/10 min, rrrr
fraction=69%) manufactured by Total Corp., and 40 parts by weight
of the propylene.ethylene copolymer (5B-3) obtained in
[Polymerization Example (5B-3)] was blended with, based on the
composition, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 5-2.
Compared to the products of Examples, the composition has inferior
moldability, heat resistance, and impact resistance.
TABLE-US-00014 TABLE 5-2 Example Ref. Ex. Comp. Ex. Comp. Ex. 5-1
5-2 5-3 5-4 5-5 5-1 5-2 5-3 Polymer (AA) 5A-1 5A-1 5A-1 5A-1 5A-2
5A-1 5A-3 5A-3 Copolymer (B2) 5B-1 5B-3 5B-4 -- -- 5B-3 Copolymer
(C) 5C-1 5C-1 5C-3 5C-2 5C-3 5C-1 5C-1 -- Composition ratio
(AA)/(B2)/(C) 100/0/25 100/0/66.7 75/25/25 66.7/33.4/66.7 50/50/25
100/0/150 100/0/25 60/40 (parts by weight) Softening (.degree. C.)
155 156 154 154 155 67 125 124 temperature (TMA)
Half-crystallization (sec) 250 210 240 310 350 320 8190 8540 time
t.sub.1/2 Cloudiness (Haze) (%) 31 23 27 25 24 81 51 19 Internal
Haze (%) 27 20 25 21 21 77 47 17 Tensile modulus (MPa) 620 430 260
160 80 230 250 180 Izod (0.degree. C.) (J/m) 720 900 840 900
non-break non-break 320 28
TABLE-US-00015 TABLE 5-3 Syndiotactic propylene
Propylene.cndot..alpha.-olefin polymer (AA) copolymer (B2) (5A-4)
(5A-5) (5A-6) (5B-5) r.r. (%) -- -- -- 75 MFR (g/10 min) 16.8 20.3
9.1 0.1 [.eta.] (dL/g) 1.4 1.2 1.3 3.5
Example VI
[1971] Hereinafter, the present invention (6) will be described in
more detail based on Examples, but the present invention is not
intended to be limited to these Examples. In these Examples, the
respective properties were measured as follows.
[1972] Methods for Measuring Properties
[1973] [Intrinsic Viscosity [.eta.]]
[1974] Intrinsic viscosity [.eta.] was measured by the same method
as in Example III.
[1975] [Amount of n-Decane-Soluble Fraction]
[1976] Amount of n-decane-soluble fraction was measured by the same
method as in Example III.
[1977] [Molecular weight distribution (Mw/Mn)]
[1978] Molecular weight distribution (Mw/Mn) was measured by the
same method as in Example III.
[1979] [Contents of ethylene, propylene and .alpha.-olefin in
polymer]
[1980] Contents of ethylene, propylene and .alpha.-olefin in
polymer were measured by the same method as in Example IV.
[1981] [Melting Point (Tm) and Heat of Fusion (.DELTA.H) of
Component (AA)]
[1982] Melting point (Tm) and heat of fusion (.DELTA.H) of
component (AA) were measured by the same method as in Example
III.
[1983] [Half-Crystallization Time (t.sub.1/2)]
[1984] Half-crystallization time (t.sub.1/2) was measured by the
same method as in Example III.
[1985] [Glass Transition Temperature (Tg) and Melting Point (Tm) of
Component (B3)]
[1986] Glass transition temperature (Tg) and melting point (Tm) of
component (B3) were measured by the same method as in Example
IV.
[1987] [MFR]
[1988] The MFRs of the syndiotactic propylene polymer (AA) and
propylene..alpha.-olefin copolymer (B3) were measured at
230.degree. C. under a load of 2.16 kgf, according to JIS
K-6721.
[1989] The MFR of the ethylene.butene copolymer (C) was measured at
190.degree. C. under a load of 2.16 kgf, according to JIS
K-6721.
[1990] [Method for Producing Press Sheet for Various
Measurements]
[1991] A press sheet for various measurements was measured by the
same method as in Example III.
[1992] [Tensile Modulus]
[1993] Tensile modulus was measured by the same method as in
Example III.
[1994] [Izod Impact Strength]
[1995] Izod impact strength was measured by the same method as in
Example III.
[1996] [Softening Temperature from TMA Measurement]
[1997] Softening temperature from TMA measurement was measured by
the same method as in Example III.
[1998] [Internal Haze (%)]
[1999] Internal haze (%) was measured by the same method as in
Example IV.
[2000] [Gloss Change Rate (%) after Gakushin Abrasion]
[2001] Gloss change rate (%) after Gakushin abrasion was measured
by the same method as in Example IV.
[2002] [Rebound Resilience (%)]
[2003] According to the Lupke's type (Lupke's method) described in
JIS K6255, rebound resilience was measured using a specimen having
a thickness of 15 mm (formed by stacking five press sheets each
having a thickness of 3 mm), and using a rebound resilience tester
manufactured by Ueshima Seisakusho Co., Ltd.
Polymerization Example
Syndiotactic Propylene Polymer (6A-1) to (6A-5)
[2004] The syndiotactic propylene polymers (4A-1), (4A-3), (4A-4),
(4A-5) and (4A-6) of Example IV were used as syndiotactic propylene
polymers (6A-1), (6A-2), (6A-3), (6A-4) and (6A-5),
respectively.
Polymerization Example 6B-1
Synthesis of Propylene..alpha.-Olefin Copolymer (6B-1)
[2005] A 2000-mL polymerization apparatus thoroughly purged with
nitrogen was charged with 833 ml of dry hexane, 120 g of 1-butene
and triisobutylaluminum (1.0 mmol) at normal temperature.
Subsequently, the internal temperature of the polymerization
apparatus was raised to 60.degree. C., and propylene was introduced
to raise the pressure in the system to 0.33 MPa, and ethylene was
then introduced to adjust the pressure in the system to 0.62 MPa.
Subsequently, the polymerization vessel was charged with a toluene
solution in which 0.002 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.6 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 20
minutes while maintaining the internal temperature at 60.degree. C.
and the pressure in the system at 0.62 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After
depressurizing, the resulting polymer was precipitated from the
polymerization solution in 2 L of methanol, and dried in a vacuum
at 130.degree. C. for 12 hours. The amount of the polymer obtained
was 73 g, and [.eta.] measured in decalin at 135.degree. C. was 2.1
(dL/g). The properties measured using the polymer obtained are
presented in Table 6-1.
Polymerization Example 6B-2
Propylene..alpha.-Olefin Copolymer (6B-2)
[2006] A 2000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 833 ml of dry hexane, 120 g of 1-butene
and triisobutylaluminum (1.0 mmol) at normal temperature.
Subsequently, the internal temperature of the polymerization
apparatus was raised to 60.degree. C., and propylene was introduced
so that the pressure in the system was raised to 0.33 MPa, and
ethylene was then introduced to adjust the pressure in the system
to 0.63 MPa. Subsequently, the polymerization vessel was charged
with a toluene solution in which 0.002 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.6 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 20
minutes while maintaining the internal temperature at 60.degree. C.
and the pressure in the system at 0.63 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After
depressurizing, the resulting polymer was precipitated from the
polymerization solution in 2 L of methanol, and dried in a vacuum
at 130.degree. C. for 12 hours. The amount of the polymer obtained
was 97 g, and [g] measured in decalin at 135.degree. C. was 2.3
(dL/g). The properties measured using the polymer obtained are
presented in Table 6-1.
Polymerization Example 6B-3
Propylene..alpha.-Olefin Copolymer (6B-3)
[2007] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane and
triisobutylaluminum (1.0 mmol) at normal temperature. Subsequently,
the internal temperature of the polymerization apparatus was raised
to 70.degree. C., and propylene was introduced so that the pressure
in the system was raised to 0.67 MPa, and ethylene was then
introduced to adjust the pressure in the system to 1.37 MPa.
Subsequently, the polymerization vessel was charged with a toluene
solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 10
minutes while maintaining the internal temperature at 70.degree. C.
and the pressure in the system at 1.37 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After
depressurizing, the resulting polymer was precipitated from the
polymerization solution in 4 L of methanol, and dried in a vacuum
at 130.degree. C. for 12 hours. The amount of the polymer obtained
was 90 g, and [n] measured in decalin at 135.degree. C. was 2.2
(dL/g). The properties measured using the polymer obtained are
presented in Table 6-1.
Polymerization Example 6B-4
Synthesis of Propylene..alpha.-Olefin Copolymer (6B-4)
[2008] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane and
triisobutylaluminum (1.0 mmol) at normal temperature. Subsequently,
the internal temperature of the polymerization apparatus was raised
to 50.degree. C., and propylene was introduced to raise the
pressure in the system to 0.67 MPa, and ethylene was then
introduced to adjust the pressure in the system to 1.37 MPa.
Subsequently, the polymerization vessel was charged with a toluene
solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 10
minutes while maintaining the internal temperature at 50.degree. C.
and the pressure in the system at 1.37 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After
depressurizing, the resulting polymer was precipitated from the
polymerization solution in 4 L of methanol, and dried in a vacuum
at 130.degree. C. for 12 hours. The amount of the polymer obtained
was 78 g, [.eta.] measured in decalin at 135.degree. C. was 3.5
(dL/g), and the ethylene content measured by .sup.13C-NMR was 18
mol %. The properties measured using the polymer obtained are
presented in Table 6-4.
[2009] (Propylene..alpha.-Olefin Copolymers (6BB-1) to (6BB-4))
[2010] Propylene..alpha.-olefin copolymers (4B-1), (4B-2), (4B-3)
and (4B-4) of Example IV were used as propylene..alpha.-olefin
copolymers (6BB-1), (6BB-2), (6BB-3) and (6BB-4), respectively.
[2011] Details of other components are as follows.
[2012] Hydrocarbon resin (6C-1): Hydrogenated terpene resin P150
manufactured by Yasuhara Chemical Co., Ltd.
[2013] Thermoplastic elastomer (6C-2): Milastomer 7030B (MFR=25.0
g/10 min) manufactured by Mitsui Chemicals, Inc.
[2014] Ethylene-butene copolymer (6C-3): ethylene-butene copolymer
(6C) manufactured by Mitsui Chemicals, Inc. (trade name: Tafmer
A4070, MFR=4.0 g/10 min)
[2015] (Propylene Polymers (6D-1) to (6D-8))
[2016] Propylene polymers (4D-1), (4D-2), (4D-3), (4D-4), (4D-5),
(4D-6), (4D-7) and (4D-8) of Example IV were used as propylene
polymers (6D-1), (6D-2), (6D-3), (6D-4), (6D-5), (6D-6), (6D-7) and
(6D-8), respectively.
[2017] Properties of the propylene polymers (6D-1) to (6D-8),
namely, the propylene polymers (4D-1) to (4D-8), are presented in
Table 4-5.
[2018] FIG. 4 shows a plotted graph of MFR and [1] of the isotactic
propylene polymers (6D-1) to (6D-8) (namely, the polymers (4D-1) to
(4D-8)), (6B-1) to (6B-4), (6BB-1) to (6BB-4) (namely, the polymers
(4B-1) to (4B-4)), and (6A-1) to (6A-5) (the polymers (4A-1),
(4A-3), (4A-4), (4A-5) and (4A-6)). The graph shows the isotactic
polymers and the polymers used in the present invention are
distinguished by the requirement (b-2).
Example 6-1
[2019] A composition of 20 parts by weight of the syndiotactic
polypropylene (6A-1) obtained in [Polymerization Example (6A-1)]
and 80 parts by weight of the propylene-ethylene.1-butene random
copolymer (6B-1) (MFR (230.degree. C.)=1.2, [.eta.]=2.1, ethylene
content mol %, 1-butene content 29 mol %) was blended with, based
on 100 parts by weight of the sum, 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the sample, and the properties thereof were measured. The
results of various property tests are presented in Table 6-2. The
composition has excellent heat resistance, as well as excellent
transparency, abrasion resistance and rebound resilience.
Example 6-2
[2020] A composition of 20 parts by weight of the syndiotactic
polypropylene (6A-1) obtained in [Polymerization Example (6A-1)]
and 80 parts by weight of the propylene-ethylene.1-butene random
copolymer (6B-2) (MFR (230.degree. C.)=0.9, [.eta.]=2.3, ethylene
content mol %, 1-butene content 28 mol %) was blended with, based
on 100 parts by weight of the sum, 20 parts by weight of the resin
(6C-1), hydrogenated terpene resin P150 manufactured by Yasuhara
Chemical Co., Ltd., 0.1 part by weight of tri(2,
4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1 part
by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 6-2. The
composition has excellent heat resistance, as well as excellent
transparency and abrasion resistance, and, in particular, has more
excellent rebound resilience.
Example 6-3
[2021] A composition of 60 parts by weight of the syndiotactic
polypropylene (6A-1) obtained in [Polymerization Example (6A-1)]
and 40 parts by weight of the propylene.ethylene.1-butene random
copolymer (6B-2) above mentioned was blended with, based on 100
parts by weight of the sum, 20 parts by weight of the resin (6C-1)
(hydrogenated terpene resin P150 manufactured by Yasuhara Chemical
Co., Ltd.), 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., a sheet was produced in the same manner as
in Example 6-2, and the sheet was used as a specimen for
measurement after cutting into an appropriate size, or the like.
Also, a press sheet was produced from the specimen, and the
properties thereof were measured. The results of various property
tests are presented in Table 6-2.
Comparative Example 6-1
[2022] 20 parts by weight of the syndiotactic polypropylene (6A-2)
was used instead of the 20 parts by weight of the syndiotactic
polypropylene (6A-1) in Example 6-1, and 80 parts by weight of the
propylene.ethylene.1-butene random copolymer (6B-3) was used
instead of the 80 parts by weight of propylene-ethylene.1-butene
copolymer (6B-1) in Example 6-1. Those were blended with, based on
100 parts by weight of the sum of (6A-2) and (6B-3), 0.1 part by
weight of tri(2,4-di-t-butylphenyl)phosphate as a secondary
antioxidant, 0.1 part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., a sheet was produced in the same manner as
in Example 6-1, and the sheet was used as a specimen for
measurement after cutting into an appropriate size, or the like.
Also, a press sheet was produced from the specimen, and the
properties thereof were measured. The results of various property
tests are presented in Table 6-2.
Comparative Example 6-2
[2023] 20 parts by weight of the syndiotactic polypropylene (6A-2)
was used instead of the 20 parts by weight of the syndiotactic
polypropylene (6A-1) in Example 6-1, and 80 parts by weight of the
ethylene.1-butene random copolymer (6C-3) was used instead of the
80 parts by weight of propylene.ethylene.1-butene copolymer (6B-1)
in Example 6-1. Those were blended with, based on 100 parts by
weight of the sum of (6A-2) and (6C-3), 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., a sheet was produced in the same manner as
in Example 6-1, and the sheet was used as a specimen for
measurement by cutting into an appropriate size, or the like. Also,
a press sheet was produced from the sheet, and the properties
thereof were measured. The results of various property tests are
presented in Table 6-2.
Example 6-4
[2024] 20 parts by weight of the syndiotactic polypropylene (6A-1)
obtained in [Polymerization Example (6A-1)] and 80 parts by weight
of the propylene.ethylene.1-butene random copolymer (6B-1) (MFR
(230.degree. C.)=1.2, [.eta.]=2.1, ethylene content 5 mol %,
1-butene content 29 mol %) was blended with, based on 100 parts by
weight of the sum, 200 parts by weight of Milastomer.TM. (trade
name) 7030B manufactured by Mitsui Chemical Inc. as the
thermoplastic elastomer (6C-2), 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, 0.1
part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, using a Laboplast
Mill (twin screw batch type melt kneading apparatus) manufactured
by Toyo Seiki Co., Ltd., the composition was melt kneaded for 5
minutes under the conditions of set temperature of 200.degree. C.,
amount of resin of 40 g (apparatus batch volume=60 cm.sup.3), and
50 rpm. Subsequently, the composition was removed and molded into a
sheet with a cold press set at 20.degree. C., and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 6-2. The
composition has excellent heat resistance, impact strength,
abrasion resistance and the like.
Example 6-5
[2025] 20 parts by weight of the syndiotactic polypropylene (6A-1)
obtained in [Polymerization Example (6A-1)] and 80 parts by weight
of the propylene.ethylene.1-butene random copolymer (6B-2) obtained
in Polymerization Example (6B-2) (MFR=0.9 g/10 min, [.eta.]=2.3
dL/g, ethylene content 10 mol %, 1-butene content 28 mol %) was
blended with, based on 100 parts by weight of the sum, 100 parts by
weight of Milastomer.TM. (trade name) 7030B manufactured by Mitsui
Chemical Inc. as the thermoplastic elastomer (6C-2), 0.1 part by
weight of tri(2,4-di-t-butylphenyl)phosphate as a secondary
antioxidant, 0.1 part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, a sheet was
produced in the same manner as in Example 6-4, and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 6-3. The
composition has excellent heat resistance, impact strength,
abrasion resistance, and the like.
Comparative Example 6-3
[2026] The following compounds were blended. The compounds were 100
parts by weight of Milastomer.TM. (trade name) 7030B manufactured
by Mitsui Chemical Inc. as the thermoplastic elastomer (6C-2), 0.1
part by weight of tri(2,4-di-t-butylphenyl)phosphate as a secondary
antioxidant, 0.1 part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat resistant stabilizer, and 0.1 part by weight of calcium
stearate as a hydrochloric acid absorbent. Then, a sheet was
produced in the same manner as in Example 6-4, and the sheet was
used as a specimen for measurement after cutting into an
appropriate size, or the like. Also, a press sheet was produced
from the specimen, and the properties thereof were measured. The
results of various property tests are presented in Table 6-3.
TABLE-US-00016 TABLE 6-1 Syndiotactic propylene
Propylene.cndot..alpha.-olefin Polymer (AA) Copolymer (B3) resin
(6A-1) (6A-2) (6B-1) (6B-2) (6B-3) (6C-3) Compo- (a) Propylene
content (mol %) 100 100 66 62 82 sition (b) Ethylene content (mol
%) 0 0 5 10 18 85 (c) .alpha.-olefin content (mol %) 0 0 29 28 0 15
Melting point (Tm) (.degree. C.) 152/158 113/125 -- -- -- 56 rrrr
(%) 94 69 -- -- -- -- [.eta.] 1.9 1.6 2.1 2.3 2.2 -- MFR (g/10 min)
2.4 5.0 1.2 0.9 1.1 4.0 Density (g/cm.sup.3) 0.882 0.877 0.870
0.858 0.852 0.870 .DELTA.H (mJ/mg) 62 33 -- -- -- 37 Tg (.degree.
C.) -5.7 -6.5 -15.2 -23.7 -26.8 -58.7 Mw/Mn 2.0 2.0 2.0 2.0 2.0 --
t.sub.1/2 (110.degree. C.) (sec) 138 22730 Amount of decane- (%)
<0.5 25 soluble fraction
TABLE-US-00017 TABLE 6-2 Comparative Example Example 6-1 6-2 6-3
6-1 6-2 Polymer (AA) 6A-1 6A-1 6A-1 6A-2 6A-2 Copolymer (B3) 6B-1
6B-2 6B-2 6B-3 -- Copolymer (C) -- 6C-1 6C-1 -- 6C-3 Composition
ratio (A)/(B)/(C) 20/80/0 20/80/20 60/40/20 20/80/0 20/0/80 (parts
by weight) Softening (.degree. C.) 125 115 155 56 67 temperature
(TMA) Cloudiness (Haze) (%) 4 4 15 4 81 Internal Haze (%) 3 1 10 2
77 Tensile modulus (MPa) 55 33 125 16 70 Gloss change rate (%) 22
25 -- 56 95 Rebound resilience (%) 24 13 -- -- 65
TABLE-US-00018 TABLE 6-3 Comparative Example Example 6-4 6-5 6-3
Polymer (AA) 6A-1 6A-1 -- Copolymer (B3) 6B-1 6B-2 -- Copolymer (C)
6C-2 6C-2 6C-2 Composition ratio (AA)/(B3)/(C) 20/80/200 20/80/100
0/0/100 (Parts by weight) Softening temperature (.degree. C.) 160
160 160 (TMA) Tensile modulus (MPa) 31 21 11 Izod (0.degree. C.)
(J/m) >500 >500 >500 Gloss change rate (%) 41 28 85
TABLE-US-00019 TABLE 6-4 Syndiotactic propylene
Propylene.cndot..alpha.-olefin polymer (AA) copolymer (B3) (6A-3)
(6A-4) (6A-5) (6B-4) r.r. (%) -- -- -- 75 MFR (g/10 min) 16.8 20.3
9.1 0.1 [.eta.] (dL/g) 1.4 1.2 1.3 3.5
TABLE-US-00020 TABLE 6-5 Propylene.cndot..alpha.-olefin copolymer
(6BB-1) (6BB-2) (6BB-3) (6BB-4) Compo- (a) Propylene content (mol
%) 77 72 82 68 sition (b) Ethylene content (mol %) 23 28 18 27 (c)
.alpha.-olefin content (mol %) 0 0 0 5 Melting point (Tm) (.degree.
C.) -- -- -- -- r.r.r.r. (%) -- -- -- -- r.r. (%) 82.9 84.6 83.5
82.1 MFR (g/10 min) 0.7 0.6 1.0 1.0 [.eta.] (dL/g) 2.5 2.6 2.3 2.3
Density (g/cm.sup.3) 0.852 0.852 0.852 0.853 .DELTA.H (mJ/mg) -- --
-- -- Tg (.degree. C.) -30.1 -34.9 -26.8 -35.4 Mw/Mn 2.0 2.0 2.0
2.0
Example VII
[2027] Hereinafter, the present invention (7) will be described in
more detail based on Examples, but the present invention is not
intended to be limited to these Examples.
[2028] Measurement Methods for Properties
[2029] [1] Amount of n-Decane-Soluble Component (Dsol) Soluble in
n-Decane at Room Temperature
[2030] 200 ml of n-decane was added to a 20 cm.times.20 cm
monolayer film of the present invention, and the film was heated at
145.degree. C. for 30 minutes to be dissolved. The resulting
solution was cooled to 20.degree. C. in about 3 hours, and left to
stand for 30 minutes.
[2031] Subsequently, the precipitate (hereinafter, referred to as
`n-decane-insoluble component: Dinsol`) was separated by
filtration. The filtrate was poured to an about 3-fold volume of
acetone, and the components dissolved in n-decane were precipitated
(referred to as `Precipitate (A)`). Precipitate (A) was separated
by filtration from acetone, and then dried. On the other hand,
although the filtrate was concentrated and dried, no residue was
observed. The amount of the n-decane-soluble component was
determined by the following equation:
Amount of n-decane-soluble component (wt %)=[weight of Precipitate
(A)/weight of sample].times.100
[2032] [2] Mw/Mn Measurement (Mw: Weight Average Molecular Weight,
Mn: Number Average Molecular Weight)
[2033] The molecular weight distribution (Mw/Mn) was measured in
the following manner using gel permeation chromatograph Alliance
GPC-2000 manufactured by Waters Corp. The separation columns used
were two TSKgel GNH6-HT columns and two TSKgel GNH6-HTL columns,
which all had a size of 7.5 mm in diameter and 300 mm in length.
The column temperature was set at 140.degree. C., the mobile phase
was o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.)
containing 0.025 wt % of BHT (Takeda Yakuhin Co., Ltd.) as an
antioxidant, and the flow rate of the mobile phase was 1.0 ml/min.
The sample concentration was 15 mg/10 mL, the injection volume of
sample was 500 microliters, and a differential refractometer was
used as the detector. For the standard polystyrenes, products by
Tosoh Finechem Corporation were used for the molecular weight
Mw<1000 and Mw>4.times.10.sup.6, and products by Pressure
Chemical Company were used for the molecular weight 1000 S Mw S
4.times.10.sup.6.
[2034] [3] Melting Point (Tm)
[2035] Using DSC Pyris 1 or DSC7 manufactured by PerkinElmer Inc.,
about 5 mg of the sample was heated to 200.degree. C., maintained
for 10 minutes, and then cooled to 30.degree. C. at 10.degree.
C./min, under a nitrogen atmosphere (20 ml/min). The temperature
was maintained at 30.degree. C. for 5 minutes and then increased to
200.degree. C. at 10.degree. C./min. The melting point was
calculated from the apex of the crystal melting peak, and the heat
of fusion was calculated from the integrated value of the peak.
[2036] When a plurality of peaks were detected for the
propylene-based composition described in the present Example, the
highest temperature was defined as Tm.
[2037] [4] Intrinsic Viscosity [.eta.]
[2038] The intrinsic viscosity was a value measured at 135.degree.
C. using a decalin solvent. Specifically, about 20 mg of a polymer
resin in the form of powder, pellets or block was dissolved in 15
ml of decalin, and the specific viscosity .eta..sub.sp was measured
in an oil bath at 135.degree. C. Thereafter, 5 ml of the decalin
solvent was added to this decalin solution for dilution, and then
the specific viscosity .eta..sub.sp was measured in the same
manner. This diluting operation was additionally repeated two
times, and the value of .eta..sub.sp/C of when the concentration
(C) was extrapolated to 0 was determined as the intrinsic viscosity
(see the following equation):
[.eta.]=lim(.eta..sub.sp/C)(C.fwdarw.0)
[2039] [5] Concentration of Propylene Unit (Sp), Ethylene Unit
(SE), and .alpha.-Olefin Units of 4 to 10 Carbon Atoms
(S.alpha.)
[2040] Quantification of the contents of ethylene, propylene, and
.alpha.-olefin was performed as follows using a JNM GX-500 type NMR
measuring apparatus manufactured by JEOL, Ltd. 0.35 g of the sample
was dissolved in 2.0 ml of hexachlorobutadiene with heating. This
solution was filtered through a glass filter (G2).
[2041] Subsequently, 0.5 ml of deuterated benzene was added, and
the mixture was placed in an NMR tube having an internal diameter
of 10 mm. .sup.13C-NMR measurement was performed at 120.degree. C.
The number of scans was 10,000 or more. The composition of
ethylene, propylene, and .alpha.-olefin was quantified using the
13C-NMR spectrum obtained.
[2042] [6] MFR (Melt Flow Rate)
[2043] MFR was measured at 230.degree. C. under a load of 2.16 kgf,
according to JIS K-6721.
[2044] [7] Young's Modulus of Film (=Tensile Modulus)
[2045] The film was punched using a JIS No. 3 dumbbell according to
JIS K6301 to provide a specimen for evaluation. The specimen was
subjected to measurement under conditions of a span of 30 mm and a
tensile rate of 30 mm/min at 23.degree. C.
[2046] [8] Tensile Impact Strength of Film
[2047] Using Heat Seal Tester TP-701-B manufactured by Tester
Sangyo K.K., the molded film was subjected to heat sealing under
conditions of temperature (upper limit/lower limit) of 210.degree.
C./190.degree. C., pressure of 0.2 MPa, time of 5 seconds, and seal
width of 150 mm.times.20 mm, to give a sample for measurement.
[2048] The sample was cut to strips of 10 mmt in accordance with
JIS K-7160 to provide specimens. The tensile impact test was
performed using a No. 258 universal impact tester manufactured by
Yasuda Seiki seisakusho LTD., with Hammer 2J under conditions of a
hammer pendulum drop angle of 149.2.degree. and an impact speed of
3.0 (m/sec).
[2049] [9] Light Transmittance of Film
[2050] The measurement was carried out using benzyl alcohol as a
solvent according to JIS K-7136. Further, the film was subjected to
an annealing treatment in a pressure resistant oven with hot water
at 120.degree. C. for 30 minutes, and then the measurement was
carried out in the same manner to determine the rate of decrease in
light transmittance.
Catalyst Synthesis Examples
Synthesis Example 7-1
[2051]
Dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirc-
onium dichloride was produced by the method described in Synthesis
Example 3 of JP-A No. 2004-189666.
Synthesis Example 7-2
[2052]
Dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylf-
luorenyl)zirconium dichloride was produced as follows.
(i) Synthesis of 2,7-dibromo-3,6-di-tert-butyl-fluorene
[2053] Under a nitrogen atmosphere, 170 mL of propylene carbonate
was added to 15.22 g (54.7 mmol) of 3,6-di-tert-butylfluorene, and
the mixture was stirred. To this solution, 20.52 g (115 mmol) of
N-bromosuccinimide was added, and the mixture was heated and
stirred at 80.degree. C. for 5 hours. Subsequently, the mixture was
left to be naturally cooled. The reaction solution was added to 800
mL of water. The mixture was stirred at room temperature for 15
minutes, and filtered using a Kiriyama funnel. The whitish yellow
powder thus obtained was washed 5 times with 10 mL of ethanol.
Subsequently, a mixture solution of hexane and a small amount of
dichloromethane was added to the whitish yellow powder, and the
mixture was heated to 60.degree. C. to dissolve the powder
completely. The resultant solution was left to stand overnight at
-20.degree. C. Crystals precipitated were washed 3 times with 5 mL
of hexane to give a target product as a whitish yellow powder
(yield 21.16 g (76%)).
[2054] .sup.1H NMR (270 MHz, CDCl.sub.3): .delta. 1.60 (s,
tBu(Flu), 18H), 3.75 (s, Flu-9H, 2H), 7.73 (s, Flu, 2H), 7.81 (s,
Flu, 2H).
[2055] MS (FD): M/z 436 (M.sup.+).
(ii) Synthesis of 3,6-di-tert-butyl-2,7-diphenyl-fluorene
[2056] Under a nitrogen atmosphere, 120 mL of anhydrous DME was
added to 8.15 g (18.7 mmol) of
2,7-dibromo-3,6-di-tert-butylfluorene and 1.08 g (0.93 mmol) of
Pd(PPh.sub.3), and the mixture was stirred at room temperature for
20 minutes. To this solution, 20 mL of an ethanol solution in which
5.01 g (41.1 mmol) of phenylboric acid was dissolved was added. The
flask that had contained the phenylboric acid was washed two times
with 4 mL of ethanol, and this was also added to the solution. The
mixture was then stirred at room temperature for 20 minutes.
Thereafter, 37.4 mL (74.8 mmol) of a 2.0 mol/L aqueous solution of
sodium carbonate was added. Subsequently, the mixture was heated to
reflux for 18 hours, and left to be naturally cooled, and the
reaction was terminated with 1N hydrochloric acid in an ice bath.
Thereafter, ether was added to extract the soluble fraction, and
the aqueous layer was subjected to extraction with diethyl ether
twice. The resultant extract was then combined with the organic
layer obtained earlier. The resulting liquid was washed two times
with a saturated aqueous solution of sodium hydrogen carbonate, two
times with water, and once with saturated brine, and then dried
over magnesium sulfate. The solvent was distilled off, and the
residue was subjected to separation by silica gel chromatography.
To the thus obtained whitish yellow powder, a mixture solution of
hexane and a small amount of dichloromethane was added, and the
mixture was heated to 60.degree. C. to dissolve the powder
completely. The resultant solution was left to stand for 1 hour at
room temperature and then left to stand for 13 hours at -20.degree.
C. Crystals precipitated were washed 3 times with 10 mL of hexane
to give a target product as a white powder (yield 4.36 g
(54%)).
[2057] .sup.1H NMR (270 MHz, CDCl.sub.3): .delta. 1.29 (s,
tBu(Flu), 18H), 3.78 (s, Flu-9H, 2H), 7.16 (s, Flu, 2H), 7.34 (br,
PhFlu, 10H), 7.97 (s, Flu, 2H).
[2058] MS (FD): M/z 430 (M.sup.+).
(iii) Synthesis of 6,6-dibenzylfulvene
[2059] Under a nitrogen atmosphere, a 500-mL three-necked flask was
charged with 8.0 g (121.0 mmol) of cyclopentadiene and 100 mL of
dehydrated THF, and the mixture was stirred. This mixture solution
was cooled in an ice bath, and 80 mL (125.6 mmol) of a 1.57 mol/L
hexane solution of n-butyllithium was added. Thereafter, the
mixture was stirred at room temperature for 3 hours. The thus
obtained white slurry was cooled in an ice bath, and then a
solution prepared by dissolving 25.0 g (118.0 mmol) of
1,3-diphenyl-2-propanone in 50 mL of dehydrated THF was added.
Subsequently, the mixture was stirred at room temperature for 12
hours. The resulting yellow solution was quenched with a saturated
aqueous solution of NH.sub.4Cl. The soluble fraction was extracted
with 100 mL of hexane, and this organic phase was washed with water
and saturated brine, and then dried over magnesium sulfate. The
solvent was distilled off, and the residue was purified by column
chromatography to give a target product as a yellow solid (yield
3.7 g (12%)). 1H NMR (270 MHz, CDCl.sub.3): .delta. 3.69 (s,
PhCH.sub.2, 4H), 6.60-6.72 (m, Cp, 4H), 7.13-7.32 (m, PhCH.sub.2,
10H).
(iv) Synthesis of
(PhCH.sub.2).sub.2C(Cp)(3,6-tBu.sub.2-2,7-Ph.sub.2-Flu)
[2060] Under a nitrogen atmosphere, 40 mL of anhydrous THF was
added to 1.60 g (3.71 mmol) of
3,6-di-tert-butyl-2,7-diphenyl-fluorene, and the mixture was
stirred. This solution was cooled in an ice bath, and 2.65 mL (4.13
mmol) of a 1.56 M hexane solution of n-butyllithium was added. The
mixture was stirred at room temperature for 2 hours. The resulting
red solution was cooled to -78.degree. C. in a dry ice-methanol
bath, and a solution prepared by dissolving 1.06 g (4.10 mmol) of
6,6-dibenzylfulvene in 20 mL of THF was added dropwise in 20
minutes. Subsequently; the mixture was stirred for 18 hours while
the temperature was gradually increased to room temperature. To the
resulting red-black solution, 60 mL of 1 N hydrochloric acid was
added to terminate the reaction. 80 mL of ether was added to cause
liquid separation, and the soluble fraction was extracted. This
organic layer was washed two times with a saturated aqueous
solution of sodium hydrogen carbonate, two times with water, and
once with saturated brine, and then dried over magnesium sulfate.
The solvent was distilled off, and the residue was purified by
silica gel chromatography to give a target product as a whitish
yellow powder (yield 0.59 g (23%)).
[2061] .sup.1H NMR (270 MHz, CDCl.sub.3): .delta. 1.25 (s,
tBu(Flu), 18H), 2.66 (br, CpH, 1H), 3.22 (br, CH.sub.2Ph, 4H), 4.41
(br, Flu-9H, 1H), 5.85-6.51 (m, Cp, 4H), 6.82-7.40 (m, Ph(Flu) and
CH.sub.2Ph and Flu, 22H), 7.67 (s, Flu, 2H).
[2062] MS (FD): M/z 688 (M.sup.+).
(v) Synthesis of
(PhCH.sub.2).sub.2C(Cp)(3,6-tBu.sub.2-2,7-Ph.sub.2-Flu)ZrCl.sub.2
[2063] Under a nitrogen atmosphere, a 100-mL Schlenk flask was
charged with 0.59 g (0.855 mmol) of
(PhCH.sub.2).sub.2C(Cp)(3,6-tBu.sub.2-2,7-Ph.sub.2-Flu) and 40 mL
of anhydrous diethyl ether, and the mixture was stirred. This mixed
slurry solution was cooled in an ice bath, and 1.21 mL (1.88 mmol)
of a 1.56 mol/L hexane solution of n-butyllithium was added. The
mixture was stirred for 45 hours while the temperature was
gradually increased to room temperature. The resulting red reaction
liquid was cooled (-78.degree. C.) in a dry ice/methanol bath, and
then 0.200 g (0.858 mmol) of zirconium tetrachloride was added.
Subsequently, the mixture was stirred for 42 hours while the
temperature was gradually increased to room temperature to give a
red-orange suspension.
[2064] The solvent was dried under reduced pressure, then the
residue was dissolved in hexane in a glove box. The resultant
liquid was passed through a glass filter filled with Celite, and
the residue was washed with hexane. The orange colored powder
insoluble in hexane was extracted with dichloromethane. The solvent
in which the dichloromethane-solubles were dissolved was distilled
off. The residue was washed with diethyl ether/cold pentane and
dried to give a target product as an orange-colored powder (yield
515 mg (71%)).
[2065] .sup.1H NMR (270 MHz, CDCl.sub.3): .delta. 1.30 (s,
tBu(Flu), 18H), 3.82 (d, J=15.5 Hz, CH.sub.2Ph, 2H), 3.93 (d,
J=15.5 Hz, CH.sub.2Ph, 2H), 5.80 (t, J=2.6 Hz, Cp, 2H), 6.25 (t,
J=2.6 Hz, Cp, 2H), 6.97-7.34 (m, Ph(Flu) and CH.sub.2Ph, 20H), 7.37
(s, Flu, 2H), 8.32 (s, Flu, 2H).
[2066] MS (FD): M/z 848 (M.sup.+).
Synthesis Example 7-3
[2067]
Di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodi-
benzofluorenyl)zirconium dichloride was produced according to the
method described in [Synthesis Example 2-2].
Synthesis Example 7-4
[2068]
Diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-
-butylfluorenyl)zirconium dichloride was produced according to the
method described in [Synthesis Example 4-4].
Polymerization Example (7A-1)
Synthesis of Syndiotactic Propylene Polymer (7A-1)
[2069] In a thoroughly nitrogen purged reaction bath having an
internal volume of 3 m.sup.3, 1000 L of n-heptane was placed, and
610 mL (0.93 mol) of a toluene solution of methylaluminoxane
(Al=1.53 mol/l) was added dropwise at normal temperature.
Meanwhile, in a thoroughly nitrogen purged side arm flask having an
internal volume of 5 L, a magnetic stirrer was placed, and the
flask was sequentially charged with 610 mL (0.93 mol) of a toluene
solution of methylaluminoxane (Al=1.53 mol/l) and a toluene
solution of 1.30 g (1.86 mmol) of
dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride. The mixture was stirred for 20 minutes. This solution
was added into the reaction bath, and then 3200 NL of hydrogen was
supplied at 19 Nm.sup.3/h over 10 minutes. Subsequently,
polymerization was initiated while supplying propylene at 65 kg/h
and supplying hydrogen at such a rate that the gas phase
concentration inside the reaction bath would be 53 mol %. Propylene
was continuously supplied at a rate of 65 kg/h while maintaining
the gas phase concentration of hydrogen inside the reaction bath at
53 mol %, and polymerization was performed for 4 hours at
25.degree. C. Then, a small amount of diethylene glycol
monoisopropyl ether was added to terminate the polymerization. The
polymer obtained was washed with 1.8 m.sup.3 of heptane, and dried
under reduced pressure at 80.degree. C. for 15 hours to give a
polymer in an amount of 100 kg. The polymerization activity was
13.4 kg-PP/mmol-Zrhr, and the polymer obtained had [.eta.]=1.90
dl/g, Tm.sub.1=152.degree. C., Tm.sub.2=159.degree. C., and rrrr
fraction=94%. The properties are shown in Table 7-1.
Polymerization Example (7A-2)
[2070] Syndiotactic polypropylene (Trade Name: Finaplas 1471,
MFR=5.0 g/10 min) produced by Total, Inc. was used as the
syndiotactic propylene polymer (A-2). The properties are shown in
Table 7-1.
Polymerization Example (7AA-1)
Synthesis of Syndiotactic Propylene Polymer (7AA-1)
[2071] A thoroughly nitrogen purged glass autoclave having an
internal volume of 500 ml was charged with 250 ml of toluene, and
then continuously charged with propylene at a rate of 150
liter/hour for 20 minutes at 25.degree. C. Meanwhile, a magnetic
stirrer was placed in a thoroughly nitrogen purged side arm flask
having an internal volume of 30 ml, and the flask was sequentially
charged with 5.00 mmol of a toluene solution of methylaluminoxane
(Al=1.53 mol/l) and 5.0 .mu.mol of a toluene solution of
dibenzylmethylene(cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium
dichloride. The mixture was stirred for 20 minutes. This solution
was then added to the toluene in the glass autoclave which had been
charged with propylene, and thereby the polymerization was
initiated. Propylene gas was continuously supplied at a rate of 150
liter/hour, and the polymerization was performed at 25.degree. C.
for 45 minutes under normal pressure. Thereafter, a small amount of
methanol was added to terminate the polymerization. The polymer
solution was added to a large excess of methanol to precipitate the
polymer. The polymer was then dried under reduced pressure at
80.degree. C. for 12 hours to give a polymer in an amount of 2.38
g. The polymerization activity was 0.63 kg-PP/mmol-Zrhr. The
polymer obtained had [.eta.]=1.9 dl/g, Tm=158.degree. C.
(Tm.sub.1=152.degree. C., Tm.sub.2=158.degree. C.), rrrr=93.5%, and
Mw/Mn=2.0. The properties are shown in Table 7-3.
Polymerization Example (7AA-2)
Synthesis of Syndiotactic Propylene Polymer (7AA-2)
[2072] A thoroughly nitrogen purged glass autoclave having an
internal volume of 500 ml was charged with 250 ml of toluene, and
then continuously charged with propylene at a rate of 150
liter/hour for 20 minutes at 25.degree. C. Meanwhile, a magnetic
stirrer was placed in a thoroughly nitrogen purged side arm flask
having an internal volume of 30 ml, and the flask was sequentially
charged with 5.00 mmol of a toluene solution of methylaluminoxane
(Al=1.53 mol/l) and 5.0 .mu.mol of a toluene solution of
dibenzylmethylene(cyclopentadienyl)(2,7-diphenyl-3,6-di-ter
t-butylfluorenyl)zirconium dichloride. The mixture was stirred for
20 minutes. This solution was then added to the toluene in the
glass autoclave which had been charged with propylene, and thereby
the polymerization was initiated. Propylene gas was continuously
supplied at a rate of 150 liter/hour, and the polymerization was
performed at 25.degree. C. for 10 minutes under normal pressure.
Thereafter, a small amount of methanol was added to terminate the
polymerization. The polymer solution was added to a large excess of
methanol to precipitate the polymer. The polymer was then dried
under reduced pressure at 80.degree. C. for 12 hours to give a
polymer in an amount of 6.95 g. The polymerization activity was
7.58 kg-PP/mmol-Zrhr. The polymer obtained had [.eta.]=2.9 dl/g,
Tm=162.0.degree. C., and rrrr fraction=95.3%. The properties are
shown in Table 7-3.
[2073] [Syndiotactic polypropylene (7AA-3)]
[2074] The syndiotactic propylene polymer (7A-2) was used as the
syndiotactic polypropylene (7AA-3).
[2075] The properties are shown in Table 7-3.
Polymerization Example (7AA-4)
Synthesis of Syndiotactic Propylene Polymer (7AA-4)
[2076] The syndiotactic propylene polymer (7AA-4) (propylene
homopolymer) was produced according to the production process in
Polymerization Example A-1, except that hydrogen was introduced (in
other words, hydrogen was further supplied in the polymerization
system). The syndiotactic propylene polymer (7AA-4) had the same
rrrr fraction and Mw/Mn as those of the polymer (7A-1), and [i] of
1.4 dl/g. The properties of the polymer (7AA-4) are shown in Table
7-3.
Polymerization Example (7AA-5)
Synthesis of Syndiotactic Propylene Polymer (7AA-5)
[2077] The syndiotactic propylene polymer (7AA-5) (propylene
homopolymer) was produced according to the production process in
Polymerization Example 7A-1, except that hydrogen was introduced
(in other words, hydrogen was further supplied in the
polymerization system). The syndiotactic propylene polymer (7AA-5)
had the same rrrr fraction and Mw/Mn as those of the polymer
(7A-1), and [j] of 1.2 dl/g. The properties of the polymer (7AA-5)
are shown in Table 7-3.
[2078] [Syndiotactic Polypropylene (7AA-6)]
[2079] Syndiotactic polypropylene (Trade Name: Finaplas 1571,
MFR=9.1 g/10 min) produced by Total, Inc. was used as the
syndiotactic polypropylene (7AA-6). The properties are shown in
Table 7-3.
Polymerization Example (7B-1)
Synthesis of Propylene..alpha.-Olefin Copolymer (7B-1)
[2080] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane and
triisobutylaluminum (1.0 mmol) at normal temperature. Thereafter,
the internal temperature of the polymerization apparatus was raised
to 70.degree. C., and propylene was introduced to raise the
pressure in the system to 0.66 MPa, and ethylene was then
introduced to adjust the pressure in the system to 1.36 MPa.
Subsequently, the polymerization apparatus was charged with a
toluene solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 15
minutes while maintaining the internal temperature at 70.degree. C.
and the pressure in the system at 1.36 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After the
apparatus was depressurized, the resulting polymer was precipitated
from the polymerization solution in 4 L of methanol, and dried in
vacuum at 130.degree. C. for 12 hours. The amount of the polymer
obtained was 105 g, MFR was 0.7 (g/10 min), and [.eta.] measured at
135.degree. C. in decalin was 2.5 (dL/g). The polymer properties
measured are shown in Table 7-1. The rr.sub.1 value was 78%. The
above procedures were repeated to obtain a required amount of the
polymer, which was then melt-kneaded and used in Examples described
later.
Polymerization Example (7B-2)
Propylene..alpha.-Olefin Copolymer (7B-2)
[2081] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane and
triisobutylaluminum (1.0 mmol) at normal temperature. Thereafter,
the internal temperature of the polymerization apparatus was raised
to 70.degree. C., and propylene was introduced to raise the
pressure in the system to 0.67 MPa, and ethylene was then
introduced to adjust the pressure in the system to 1.37 MPa.
Subsequently, the polymerization apparatus was charged with a
toluene solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 10
minutes while maintaining the internal temperature at 70.degree. C.
and the pressure in the system at 1.37 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After the
apparatus was depressurized, the resulting polymer was precipitated
from the polymerization solution in 4 L of methanol, and dried in
vacuum at 130.degree. C. for 12 hours. The amount of the polymer
obtained was 90 g, MFR was 1.0 (g/10 min), and [.eta.] measured at
135.degree. C. in decalin was 2.3 (dL/g). The rr.sub.1 value was
75%. The polymer properties measured are shown in Table 7-1. The
above procedures were repeated to obtain a required amount of the
polymer, which was then melt-kneaded and used in Examples described
later.
Polymerization Example (7B-3)
Synthesis of Propylene..alpha.-Olefin Copolymer (7B-3)
[2082] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane, 20 g of 1-butene,
and triisobutylaluminum (1.0 mmol) at normal temperature.
Thereafter, the internal temperature of the polymerization
apparatus was raised to 70.degree. C., and propylene was introduced
to raise the pressure in the system to 0.63 MPa, and ethylene was
then introduced to adjust the pressure in the system to 1.33 MPa.
Subsequently, the polymerization apparatus was charged with a
toluene solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 10
minutes while maintaining the internal temperature at 70.degree. C.
and the pressure in the system at 1.30 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After the
apparatus was depressurized, the resulting polymer was precipitated
from the polymerization solution in 4 L of methanol, and dried in
vacuum at 130.degree. C. for 12 hours. The amount of the resulting
polymer was 107 g, MFR was 0.8 (g/10 min), and [.eta.] measured at
135.degree. C. in decalin was 2.4 (dL/g). The polymer properties
measured are shown in Table 7-1. The rr1 value was 79%. The above
procedures were repeated to obtain a required amount of the
polymer, which was then melt-kneaded and used in Examples described
later.
Polymerization Example (7BB-1)
[2083] The polymer was synthesized in the same manner as in
Polymerization Example 7B-1.
Polymerization Example (7BB-2)
Propylene..alpha.-Olefin Copolymer (7BB-2)
[2084] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane and
triisobutylaluminum (1.0 mmol) at normal temperature. Thereafter,
the internal temperature of the polymerization apparatus was raised
to 70.degree. C., and propylene was introduced to raise the
pressure in the system to 0.64 MPa, and ethylene was then
introduced to adjust the pressure in the system to 1.34 MPa.
Subsequently, the polymerization apparatus was charged with a
toluene solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 15
minutes while maintaining the internal temperature at 70.degree. C.
and the pressure in the system at 1.34 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After the
apparatus was depressurized, the resulting polymer was precipitated
from the polymerization solution in 4 L of methanol, and dried in
vacuum at 130.degree. C. for 12 hours. The amount of the polymer
obtained was 109 g, [i] measured at 135.degree. C. in decalin was
2.6 (dL/g), and MFR was 0.6 (g/10 min). The polymer properties
measured are shown in Table 7-1. The rr.sub.1 value was 76%. The
above procedures were repeated to obtain a required amount of the
polymer, which was then used in Examples. For use in the evaluation
of the film formability, a polymer was produced in accordance with
the above-mentioned production process in a larger scale, and the
polymer had the same ethylene content, rr fraction, [.eta.], and
Mw/Mn as those of the above-mentioned polymer.
Polymerization Example (7BB-3)
[2085] The polymer was synthesized in the same manner as in
Polymerization Example 7B-2.
Polymerization Example (7BB-4)
Synthesis of Propylene..alpha.-Olefin Copolymer (7BB-4)
[2086] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane, 20 g of 1-butene,
and triisobutylaluminum (1.0 mmol) at normal temperature.
Thereafter, the internal temperature of the polymerization
apparatus was raised to 70.degree. C., and propylene was introduced
to raise the pressure in the system to 0.63 MPa, and ethylene was
then introduced to adjust the pressure in the system to 1.33 MPa.
Subsequently, the polymerization apparatus was charged with a
toluene solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 10
minutes while maintaining the internal temperature at 70.degree. C.
and the pressure in the system at 1.33 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After the
apparatus was depressurized, the resulting polymer was precipitated
from the polymerization solution in 4 L of methanol, and dried in
vacuum at 130.degree. C. for 12 hours. The amount of the resulting
polymer was 102 g, [i] measured at 135.degree. C. in decalin was
2.3 (dL/g), and MFR was 1.0 (g/10 min). The polymer properties
measured are shown in Table 5-4. The rr.sub.1 value was 75%. The
properties are shown in Table 7-3.
Polymerization Example (7BB-5)
Synthesis of Propylene..alpha.-Olefin Copolymer (7B-5)
[2087] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane and
triisobutylaluminum (1.0 mmol) at normal temperature. Thereafter,
the internal temperature of the polymerization apparatus was raised
to 50.degree. C., and propylene was introduced to raise the
pressure in the system to 0.67 MPa, and ethylene was then
introduced to adjust the pressure in the system to 1.37 MPa.
Subsequently, the polymerization apparatus was charged with a
toluene solution in which 0.001 mmol of
di(p-chlorophenyl)methylene(cyclopentadienyl)(octamethyloctahydrodibenzof-
luorenyl)zirconium dichloride had been contacted with 0.3 mmol, in
terms of aluminum, of methylaluminoxane (manufactured by Tosoh
Finechem Corporation). Polymerization was then performed for 10
minutes while maintaining the internal temperature at 50.degree. C.
and the pressure in the system at 1.37 MPa with ethylene, and 20 ml
of methanol was added to terminate the polymerization. After the
apparatus was depressurized, the resulting polymer was precipitated
from the polymerization solution in 4 L of methanol, and dried in
vacuum at 130.degree. C. for 12 hours. The amount of the resulting
polymer was 78 g, [.eta.] measured at 135.degree. C. in decalin was
3.5 (dL/g), and the ethylene content measured by .sup.13C-NMR was
18 mol %. The polymer properties measured are shown in Table
7-4.
[2088] Propylene Polymers (7D-1) to (7D-8)
[2089] Propylene Polymer (7D-1)
[2090] PP produced by Prime Polymer Co., Ltd. (Trade Name: F102W,
MFR=2.1 g/10 min)
[2091] Propylene Polymer (7D-2)
[2092] PP produced by Prime Polymer Co., Ltd. (Trade Name: J104W,
MFR=5.2 g/10 min)
[2093] Propylene Polymer (7D-3)
[2094] PP produced by Prime Polymer Co., Ltd. (Trade Name: B101,
MFR=0.7 g/10 min)
[2095] Propylene Polymer (7D-4)
[2096] PP produced by Prime Polymer Co., Ltd. (Trade Name: J106G,
MFR=15.0 g/10 min)
[2097] Propylene Polymer (7D-5)
[2098] PP produced by Prime Polymer Co., Ltd. (Trade Name: J107G,
MFR=30.0 g/10 min)
[2099] Propylene Polymer (7D-6)
[2100] PP produced by Prime Polymer Co., Ltd. (Trade Name: J108M,
MFR=45.0 g/10 min)
[2101] Propylene Polymer (7D-7)
[2102] (Synthesis of Propylene.Ethylene.Butene Copolymer)
[2103] A 4000-ml polymerization apparatus thoroughly purged with
nitrogen was charged with 1834 ml of dry hexane, 110 g of 1-butene,
and triisobutylaluminum (1.0 mmol) at normal temperature.
Thereafter, the internal temperature of the polymerization
apparatus was raised to 55.degree. C., and propylene was introduced
to raise the pressure in the system to 0.58 MPa, and ethylene was
then introduced to adjust the pressure in the system to 0.75 MPa.
Subsequently, the polymerization apparatus was charged with a
toluene solution in which 0.001 mmol of
diphenylmethylene(3-tert-butyl-5-ethylcyclopentadienyl)(2,7-di-tert-butyl-
fluorenyl)zirconium dichloride synthesized in Synthesis Example 7-2
had been contacted with 0.3 mmol, in terms of aluminum, of
methylaluminoxane (manufactured by Tosoh Finechem Corporation).
Polymerization was then performed for 25 minutes while maintaining
the internal temperature at 55.degree. C. and the pressure in the
system at 0.75 MPa with ethylene, and 20 ml of methanol was added
to terminate the polymerization. After the apparatus was
depressurized, the resulting polymer was precipitated from the
polymerization solution in 4 L of methanol, and dried in vacuum at
130.degree. C. for 12 hours. The amount of the resulting polymer
was 120.2 g and MFR was 0.7 (g/10 min). The polymer properties
measured are shown in Table 7-3.
[2104] [Propylene Polymer (7D-8)]
[2105] The polymer (7D-8) was produced in accordance with the
process conditions for producing the propylene polymer (7D-7),
except that the polymerization temperature was changed to
40.degree. C. The polymer produced had the same ethylene content
and butene content as those of the polymer (7D-7), and had [r] of
4.0 and Mw/Mn of 2.1. The properties of the polymer obtained are
shown in Table 7-4.
[2106] FIG. 5 shows a graph in which MFR and [.eta.] are plotted
with respect to the isotactic propylene-based polymers (7D-1) to
(7D-8), (7BB-1) to (7BB-5), (7AA-1), (7AA-3), (7AA-4), (7AA-5), and
(7AA-6). The graph shows that the polymer (7B) used in a preferred
embodiment of the present invention is distinguished from the
isotactic propylene-based polymers (7D-1) to (7D-8) by Formula
(7b-2).
Example 7-1
[2107] 71 parts by weight of the syndiotactic polypropylene (7A-1)
obtained in [Polymerization Example (7A-1)], 29 parts by weight of
the propylene-ethylene copolymer (7B-2) obtained in [Polymerization
Example (7B-2)], 43 parts by weight of the ethylene..alpha.-olefin
copolymer (7C), 0.1 part by weight of
tri(2,4-di-t-butylphenyl)phosphate as a secondary antioxidant, and
0.1 part by weight of
n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a
heat stabilizer for the composition, were blended. The resulting
composition was granulated into pellets under the conditions of set
temperature of 230.degree. C., resin extrusion rate of 40 g/min and
200 rpm, using a twin screw extruder manufactured by Prabo Co.,
Ltd.
[2108] A T-die with a diameter 0 of 25 mm and a lip width of 250
mm.times.0.8 mm was attached to a single screw extruder having a
diameter 0 of 20 mm and L/D=28, manufactured by Thermo Co., Ltd.
The pellets obtained above were extruded into a 250 .mu.m thick
film at an extruder temperature of 210.degree. C., a roll
temperature of 40.degree. C. and a winding rate of 0.5 m/min. The
results are shown in Table 7-2.
Example 7-2
[2109] 40 parts by weight of the syndiotactic polypropylene (7A-1)
obtained in [Polymerization Example (7A-1)], 60 parts by weight of
the propylene-ethylene copolymer (7B-3) obtained in [Polymerization
Example (7B-3)], and as in Example 7-1, equal amounts of the
secondary antioxidant and the heat stabilizer for the composition,
were blended. With the use of the twin screw extruder manufactured
by Prabo Co., Ltd. and under the same extrusion and molding
conditions as in Example 7-1, pellets and a film were formed. The
results are shown in Table 7-2.
Example 7-3
[2110] 67 parts by weight of the syndiotactic polypropylene (7A-1)
obtained in [Polymerization Example (7A-1)], 33 parts by weight of
the propylene-ethylene copolymer (7B-1) obtained in [Polymerization
Example (7B-1)], 67 parts by weight of the ethylene..alpha.-olefin
copolymer (7C), and as in Example 7-1, equal amounts of the
secondary antioxidant and the heat stabilizer for the composition,
were blended. With the use of the twin screw extruder manufactured
by Prabo Co., Ltd. and under the same extrusion and molding
conditions as in Example 5-6, pellets and a film were formed. The
results are shown in Table 7-2.
Example 7-4
[2111] 50 parts by weight of the syndiotactic polypropylene (7A-1)
obtained in [Polymerization Example (7A-1)], 50 parts by weight of
the propylene-ethylene copolymer (7B-2) obtained in [Polymerization
Example (7B-2)], 67 parts by weight of the ethylene..alpha.-olefin
copolymer (7C), and as in Example 5-6, equal amounts of the
secondary antioxidant and the heat stabilizer for the composition,
were blended. With the use of the twin screw extruder manufactured
by Prabo Co., Ltd. and under the same extrusion and molding
conditions as in Example 7-1, pellets and a film were formed. The
results are shown in Table 7-2.
Comparative Example 7-1
[2112] 71 parts by weight of the syndiotactic polypropylene (7A-2)
(trade name: Finaplas1471, MFR=5.0 g/10 min) manufactured by Total
Corp., 29 parts by weight of the propylene-ethylene copolymer
(7B-2) obtained in [Polymerization Example (7B-2)], 43 parts by
weight of the ethylene..alpha.-olefin copolymer (7C), and as in
Example 7-1, equal amounts of the secondary antioxidant and the
heat stabilizer for the composition, were blended. With the use of
the twin screw extruder manufactured by Prabo Co., Ltd. and under
the same extrusion and molding conditions as in Example 7-1,
pellets and a film were formed. The results are shown in Table
7-2.
TABLE-US-00021 TABLE 7-1 Syndiotactic propylene
propylene.cndot..alpha.-olefin polymer (7A) copolymer (7B) (7A-1)
(7A-2) (7B-1) (7B-2) (7B-3) Compo- (a) propylene content (mol %)
100 100 77 82 90 sition (b) ethylene content (mol %) 0 0 23 18 10
(c) .alpha.-olefin content (mol %) 0 0 0 0 0 Melting Point (Tm)
(.degree. C.) 152/159 113/125 -- -- -- r.r.r.r. (%) 94 69 -- -- --
r.r. (%) -- -- 78 75 79 MFR (g/10 min) 2.4 5.0 0.7 1.0 0.8 [.eta.]
(dL/g) 1.9 1.6 2.5 2.3 2.4 Density (g/cm.sup.3) 0.882 0.887 0.852
0.852 0.860 .DELTA.H (mJ/mg) 62 33 -- -- -- Mw/Mn 2.0 2.0 2.0 2.0
2.0 t.sub.1/2 (110.degree. C.) (sec) 138 22730 Amount of decane-
(%) <0.5 25 soluble fraction
TABLE-US-00022 TABLE 7-2 Comparative Examples Example 7-1 7-2 7-3
7-4 7-1 Propylene polymer (7A) 7A-1 7A-1 7A-1 7A-1 7A-2
Propylene.cndot..alpha.-olefin copolymer (7B) 7B-2 7B-3 7B-1 7B-2
7B-2 Ethylene.cndot..alpha.-olefin copolymer (1C) 7C -- 7C 7C 7C
(7A)/(7B)/(7C) composition ratio 71/29/43 40/60/0 67/33/67 50/50/67
71/29/43 (parts by weight) Tm (.degree. C.) 155 154 156 155 125
Tensile modulus (MPa) 214 92 187 91 120 Tensile impact strength
(kJ/m.sup.2) 181 146 527 334 70 Light transmittance (%) 90 94 88 90
88 Light transmittance after (%) 90 90 91 89 72 heat treatment
Reduction rate (%) 0 4 3 1 18 Amount of fraction soluble in (wt %)
49 60 58 78 59 decane at room temperature [.eta.] of decane- 2.1
2.4 2.1 2.1 2.0 soluble fraction Compo- (a) propylene content (mol
%) 67.5 94.0 49.1 48.6 67.5 sition (b) ethylene content (mol %)
26.1 6.0 45.3 45.8 26.1 (c) .alpha.-olefin content (mol %) 6.4 0.0
5.6 5.6 6.4
TABLE-US-00023 TABLE 7-3 Syndiotactic propylene polymer (7AA)
Propylene.cndot..alpha.-olefin copolymer (7BB) (7AA-1) (7AA-2)
(7AA-3) (7AA-4) (7AA-5) (7AA-6) (7BB-1) (7BB-2) (7BB-3) (7BB-4)
(7BB-5) r.r. (%) -- -- -- -- -- -- 82.9 84.6 83.5 82.1 75 MFR (g/10
min) 2.4 5.0 16.8 20.3 9.1 0.7 0.6 1.0 1.0 0.1 [.eta.] (dL/g) 1.9
2.9 1.8 1.4 1.2 1.3 2.5 2.6 2.3 2.3 3.5
TABLE-US-00024 TABLE 7-4 Propylene polymer (7D) (7D-1) (7D-2)
(7D-3) (7D-4) (7D-5) (7D-6) (7D-7) (7D-8) MFR (g/10 min) 2.1 5.2
0.7 15.0 30.0 45.0 0.7 0.2 [.eta.] (dL/g) 2.7 2.4 3.2 1.9 1.7 1.4
2.9 4.0 mmmm (%) -- -- -- 96 -- 96 -- --
INDUSTRIAL APPLICABILITY
[2113] The catalyst (1) for olefin polymerization of the present
invention (1) has excellent polymerization activity and has a large
impact on the olefin polymerization industries.
[2114] The method for producing the propylene-based copolymer [B1]
of the present invention (2) is industrially useful since the
method is capable of polymerization at high temperatures and high
molecular weight propylene copolymer [B1] can be obtained
thereby.
[2115] The syndiotactic propylene polymer (A) of the present
invention (3) is a syndiotactic propylene polymer having improved
crystallization rate and crystallization temperature and excellent
moldability compared to existing polymers. Also, molded products
obtained from the polymer have an excellent balance between heat
resistance, transparency, and rigidity and strength, and thus
various new applications that could not be applied heretofore to
isotactic polypropylene, can be expected.
* * * * *