U.S. patent application number 10/072994 was filed with the patent office on 2002-08-22 for ethylene copolymer and aromatic vinyl graft copolymer and method for producing the same.
This patent application is currently assigned to IDEMITSU PETROCHEMICAL CO., LTD.. Invention is credited to Sera, Masanori, Teshima, Hideo.
Application Number | 20020115802 10/072994 |
Document ID | / |
Family ID | 26558952 |
Filed Date | 2002-08-22 |
United States Patent
Application |
20020115802 |
Kind Code |
A1 |
Teshima, Hideo ; et
al. |
August 22, 2002 |
Ethylene copolymer and aromatic vinyl graft copolymer and method
for producing the same
Abstract
The present invention provides resin materials endowed with
excellent heat resistance, solvent resistance, tensile elongation,
toughness, and transparency. Specifically, there are provided an
ethylene copolymer having a vinyl group attributed to a diene
monomer in the molecular chain and comprising an aromatic vinyl
monomer (A), ethylene (B) and a diene monomer (C), and an aromatic
vinyl graft copolymer which is a graft copolymerization product of
an aromatic vinyl monomer (H) and an ethylene copolymer macromer
(I).
Inventors: |
Teshima, Hideo; (Chiba,
JP) ; Sera, Masanori; (Chiba, JP) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
IDEMITSU PETROCHEMICAL CO.,
LTD.
Tokyo
JP
J
|
Family ID: |
26558952 |
Appl. No.: |
10/072994 |
Filed: |
February 12, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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|
10072994 |
Feb 12, 2002 |
|
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|
09177557 |
Oct 23, 1998 |
|
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6376614 |
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Current U.S.
Class: |
526/127 ;
526/160; 526/335; 526/346; 526/943 |
Current CPC
Class: |
C08F 10/00 20130101;
C08F 210/02 20130101; C08F 10/02 20130101; C08F 290/042 20130101;
C08F 10/00 20130101; C08F 4/65912 20130101; C08F 10/02 20130101;
C08F 4/6592 20130101; C08F 210/02 20130101; C08F 212/08 20130101;
C08F 212/36 20130101; C08F 2500/03 20130101; C08F 2500/17
20130101 |
Class at
Publication: |
526/127 ;
526/160; 526/335; 526/346; 526/943 |
International
Class: |
C08F 004/44 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 24, 1997 |
JP |
9-292348 |
Oct 24, 1997 |
JP |
9-292349 |
Claims
What is claimed is:
1. An ethylene copolymer comprising an aromatic vinyl monomer (A),
ethylene (B) and a diene monomer (C), and having in the molecular
chain a vinyl group attributed to a diene monomer, wherein
recurrent units attributed to aromatic vinyl monomer (A) is 1-98
mol %, recurrent units attributed to ethylene (B) is 1-98 mol % and
recurrent units attributed to diene monomer (C) is 0.001-10 mol
%.
2. An ethylene copolymer comprising an aromatic vinyl monomer (A),
ethylene (B), a diene monomer (C), and .alpha.-olefin (D), and
having in the molecular chain a vinyl group attributed to a diene
monomer, wherein recurrent units attributed to aromatic vinyl
monomer (A) is 1-98 mol %, recurrent units attributed to ethylene
(B) is 1-98 mol %, recurrent units attributed to diene monomer (C)
is 0.001-10 mol % and recurrent units attributed to .alpha.-olefin
(D) is 0-90 mol % (exclusive of 0).
3. The ethylene copolymer according to claim 1, wherein the diene
monomer (C) is a diene having a styrenic vinyl group.
4. The ethylene copolymer according to claim 2, wherein the diene
monomer (C) is a diene having a styrenic vinyl group.
5. A method for producing an ethylene copolymer recited in claim 1,
wherein the respective monomers are copolymerized through use of a
catalyst formed of the following components (E) and (F): (E) a
transition metal compound; and (F) an oxygen-containing compound
(i) represented by the following formula (1) or (2): 24wherein,
each of R.sup.1 through R.sup.5, which may be identical to or
different from one another, represents a C1-C8 alkyl group; each of
Y.sup.1 through Y.sup.3, which may be identical to or different
from one another, represents a Group 13 element; and a and b
independently represent numbers between 0 and 50 inclusive, with
the proviso that a+b is equal to or greater than 1; 25wherein, each
of R.sup.6 and R.sup.7, which may be identical to or different from
each other, represents a C1-C8 alkyl group; Y.sup.4 and Y.sup.5,
which may be identical to or different from each other, represents
a Group 13 element; and c and d independently represent numbers
between 0 and 50 inclusive, with the proviso that c+d is equal to
or greater than 1: and/or a compound (ii) capable of forming an
ionic complex through reaction with transition metal compound
(E).
6. A method for producing an ethylene copolymer recited in claim 2,
wherein the respective monomers are copolymerized through use of a
catalyst formed of the following components (E) and (F): (E) a
transition metal compound; and (F) an oxygen-containing compound
(i) represented by the following formula (1) or (2): 26wherein,
each of R.sup.1 through R.sup.5, which may be identical to or
different from one another, represents a C1-C8 alkyl group; each of
Y.sup.1 through Y3, which may be identical to or different from one
another, represents a Group 13 element; and a and b independently
represent numbers between 0 and 50 inclusive, with the proviso that
a+b is equal to or greater than 1; 27wherein, each of R.sup.6 and
R.sup.7, which may be identical to or different from each other,
represents a C1-C8 alkyl group; Y.sup.4 and Y.sup.5, which may be
identical to or different from each other, represents a Group 13
element; and c and d independently represent numbers between 0 and
50 inclusive, with the proviso that c+d is equal to or greater than
1: and/or a compound (ii) capable of forming an ionic complex
through reaction with transition metal compound (E).
7. A method for producing an ethylene copolymer recited in claim 3,
wherein the respective monomers are copolymerized through use of a
catalyst formed of the following components (E) and (F): (E) a
transition metal compound; and (F) an oxygen-containing compound
(i) represented by the following formula (1) or (2): 28wherein,
each of R.sup.1 through R.sup.5, which may be identical to or
different from one another, represents a C1-C8 alkyl group; each of
Y.sup.1 through Y.sup.3, which may be identical to or different
from one another, represents a Group 13 element; and a and b
independently represent numbers between 0 and 50 inclusive, with
the proviso that a+b is equal to or greater than 1; 29wherein, each
of R.sup.6 and R.sup.7, which may be identical to or different from
each other, represents a C1-C8 alkyl group; Y4 and Y.sup.5, which
may be identical to or different from each other, represents a
Group 13 element; and c and d independently represent numbers
between 0 and 50 inclusive, with the proviso that c+d is equal to
or greater than 1: and/or a compound (ii) capable of forming an
ionic complex through reaction with transition metal compound
(E).
8. A method for producing an ethylene copolymer recited in claim 4,
wherein the respective monomers are copolymerized through use of a
catalyst formed of the following components (E) and (F): (E) a
transition metal compound; and (F) an oxygen-containing compound
(i) represented by the following formula (1) or (2): 30wherein,
each of R.sup.1 through R.sup.5, which may be identical to or
different from one another, represents a C1-C8 alkyl group; each of
Y.sup.1 through Y.sup.3, which may be identical to or different
from one another, represents a Group 13 element; and a and b
independently represent numbers between 0 and 50 inclusive, with
the proviso that a+b is equal to or greater than 1; 31wherein, each
of R.sup.6 and R.sup.7, which may be identical to or different from
each other, represents a C1-C8 alkyl group; Y.sup.4 and Y.sup.5,
which may be identical to or different from each other, represents
a Group 13 element; and c and d independently represent numbers
between 0 and 50 inclusive, with the proviso that c+d is equal to
or greater than 1: and/or a compound (ii) capable of forming an
ionic complex through reaction with transition metal compound
(E).
9. A method for producing an ethylene copolymer recited in claim 1,
wherein the respective monomers are copolymerized through use of a
catalyst formed of the following components (E) and (F): (E) a
transition metal compound; and (F) an oxygen-containing compound
represented by the following formula (1): 32wherein, each of
R.sup.1 through R.sup.5, which may be identical to or different
from one another, represents a C1-C8 alkyl group; each of Y.sup.1
through Y3, which may be identical to or different from one
another, represents a Group 13 element; and a and b independently
represent numbers between 0 and 50 inclusive, with the proviso that
a+b is equal to or greater than 1.
10. A method for producing an ethylene copolymer recited in claim
1, wherein the respective monomers are copolymerized through use of
a catalyst formed of the following components (E) and (F): (E) a
transition metal compound; and (F) an oxygen-containing compound
represented by the following formula (2): 33wherein, each of
R.sup.6 and R.sup.7, which may be identical to or different from
each other, represents a C1-C8 alkyl group; Y.sup.4 and Y.sup.5,
which may be identical to or different from each other, represents
a Group 13 element; and c and d independently represent numbers
between 0 and 50 inclusive, with the proviso that c+d is equal to
or greater than 1.
11. A method for producing an ethylene copolymer recited in claim
1, wherein the respective monomers are copolymerized through use of
a catalyst formed of the following components (E) and (F): (E) a
transition metal compound; and (F) a compound capable of forming an
ionic complex through reaction with transition metal compound
(E).
12. A method for producing an ethylene copolymer recited in claim
1, wherein the respective monomers are copolymerized through use of
a catalyst formed of the following components (E), (F) and (G): (E)
a transition metal compound; (F) an oxygen-containing compound (i)
represented by the following formula (1) or (2): 34wherein, each of
R.sup.1 through R.sup.5, which may be identical to or different
from one another, represents a C1-C8 alkyl group; each of Y.sup.1
through Y.sup.3, which may be identical to or different from one
another, represents a Group 13 element; and a and b independently
represent numbers between 0 and 50 inclusive, with the proviso that
a+b is equal to or greater than 1; 35wherein, each of R.sup.6 and
R.sup.7, which may be identical to or different from each other,
represents a C1-C8 alkyl group; Y.sup.4 and Y.sup.5, which may be
identical to or different from each other, represents a Group 13
element; and c and d independently represent numbers between 0 and
50 inclusive, with the proviso that c+d is equal to or greater than
1: and/or a compound (ii) capable of forming an ionic complex
through reaction with transition metal compound (E): and (G) an
alkylating agent.
13. A method for producing an ethylene copolymer recited in claim
1, wherein the respective monomers are copolymerized through use of
a catalyst formed of the following components (E), (F) and (G): (E)
a transition metal compound; (F) an oxygen-containing compound
represented by the following formula (1): 36wherein, each of
R.sup.1 through R.sup.5, which may be identical to or different
from one another, represents a C1-C8 alkyl group; each of Y.sup.1
through Y.sup.3 which may be identical to or different from one
another, represents a Group 13 element; and a and b independently
represent numbers between 0 and 50 inclusive, with the proviso that
a+b is equal to or greater than 1: and (G) an alkylating agent.
14. A method for producing an ethylene copolymer recited in claim
1, wherein the respective monomers are copolymerized through use of
a catalyst formed of the following components (E), (F) and (G): (E)
a transition metal compound; (F) an oxygen-containing compound
represented by the following formula (2): 37wherein, each of
R.sup.6 and R.sup.7, which may be identical to or different from
each other, represents a C1-C8 alkyl group; Y.sup.4 and Y.sup.5,
which may be identical to or different from each other, represents
a Group 13 element; and c and d independently represent numbers
between 0 and 50 inclusive, with the proviso that c+d is equal to
or greater than 1: and (G) an alkylating agent.
15. A method for producing an ethylene copolymer recited in claim
1, wherein the respective monomers are copolymerized through use of
a catalyst formed of the following components (E), (F) and (G): (E)
a transition metal compound; (F) a compound capable of forming an
ionic complex through reaction with transition metal compound (E):
and (G) an alkylating agent.
16. The method for producing an ethylene copolymer according to
claim 5, wherein the transition metal compound (E) is represented
by the following formula (3): 38wherein M.sup.1 represents
titanium, zirconium, or hafnium; Cp represents a cyclopentadienyl
group or a substituted cyclopentadienyl group which is bonded to
M.sup.1 via a .eta..sup.5 bonding mode, an indenyl group, a
substituted indenyl group, a fluorenyl group, a substituted
fluorenyl group, a hexahydroazulenyl group, a substituted
hexahydroazulenyl group, a tetrahydroindenyl group, a substituted
tetrahydroindenyl group, a tetrahydrofluorenyl group, a substituted
tetrahydrofluorenyl group, an octahydrofluorenyl group, or a
substituted octahydrofluorenyl group; X.sup.1 represents a .sigma.
ligand; e represents 1 or 2; a plurality of X.sup.1 may be
identical to or different from one another and may be linked
together via an arbitrary group; Y.sup.6 represents O, S, NR, PR,
CR.sub.2, or a neutral two-electron donor selected from OR, SR,
NR.sub.2, or PR.sub.2; Z.sup.1 represents SiR.sub.2, CR.sub.2,
SiR.sub.2SiR.sub.2, CR.sub.2CR.sub.2, CR=CR, CRSiR.sub.2,
GeR.sub.2, BR, or BR.sub.2; R represents hydrogen, an alkyl group,
an aryl group, a silyl group, a haloalkyl group, a haloaryl group,
or a combination of at least two of the above groups selected so as
to have 20 or fewer non-hydrogen atoms; and two or more of the
above R may further form a condensed ring system with Z.sup.1 or
with Y.sup.6 and Z.sup.1.
17. An aromatic vinyl graft copolymer which is a graft
copolymerization product of an aromatic vinyl monomer (H) and
ethylene copolymer macromer (I) which has in the molecular chain a
vinyl group attributed to a diene monomer; the ethylene copolymer
(I) being obtained through copolymerization of an aromatic vinyl
monomer (A), ethylene (B) and a diene monomer (C), wherein
recurrent units attributed to aromatic vinyl monomer (A) is 1-98
mol %, recurrent units attributed to ethylene (B) is 1-98 mol %,
and recurrent units attributed to diene monomer (C) is 0.001-10 mol
%.
18. An aromatic vinyl graft copolymer which is a graft
copolymerization product of an aromatic vinyl monomer (H) and
ethylene copolymer macromer (I) and which has in the molecular
chain a vinyl group attributed to a diene monomer; the ethylene
copolymer (I) being obtained through copolymerization of an
aromatic vinyl monomer (A), ethylene (B), a diene monomer (C) and
.alpha.-olefin (D), wherein recurrent units attributed to aromatic
vinyl monomer (A) is 1-98 mol %, recurrent units attributed to
ethylene (B) is 1-98 mol %, recurrent units attributed to diene
monomer (C) is 0.001-10 mol % and recurrent units attributed to
.alpha.-olefin (D) is 0-90 mol % (exclusive of 0).
19. An aromatic vinyl graft copolymer according to claim 17,
wherein the diene monomer (C) is a diene having a styrenic vinyl
group.
20. An aromatic vinyl graft copolymer according to claim 18,
wherein the diene monomer (C) is a diene having a styrenic vinyl
group.
21. An aromatic vinyl graft copolymer according to claim 17,
wherein a chain attributed to aromatic vinyl monomer (A) has a
stereospecificity of highly syndiotactic structure.
22. An aromatic vinyl graft copolymer according to claim 17,
wherein a chain attributed to aromatic vinyl monomer (A) has a
stereospecificity of highly syndiotactic structure.
23. An aromatic vinyl graft copolymer according to claim 17,
wherein the ethylene copolymer macromer (I) is prepared by use of a
catalyst formed of the following components (E) and (F): (E) a
transition metal compound; (F) an oxygen-containing compound (i)
represented by the following formula (1) or (2): 39wherein, each of
R.sup.1 through R.sup.5, which may be identical to or different
from one another, represents a C1-C8 alkyl group; each of Y.sup.1
through Y.sup.3 which may be identical to or different from one
another, represents a Group 13 element; and a and b independently
represent numbers between 0 and 50 inclusive, with the proviso that
a+b is equal to or greater than 1; 40wherein, each of R.sup.6 and
R.sup.7, which may be identical to or different from each other,
represents a C1-C8 alkyl group; Y.sup.4 and Y.sup.5, which may be
identical to or different from each other, represents a Group 13
element; and c and d independently represent numbers between 0 and
50 inclusive, with the proviso that c+d is equal to or greater than
1; and/or a compound (ii) capable of forming an ionic complex
through reaction with transition metal compound (E).
24. An aromatic vinyl graft copolymer according to claim 17,
wherein the ethylene copolymer macromer (I) is prepared by use of a
catalyst formed of the following components (E), (F) and (G): (E) a
transition metal compound; (F) an oxygen-containing compound (i)
represented by the following formula (1) or (2): 41wherein, each of
R.sup.1 through R.sup.5, which may be identical to or different
from one another, represents a C1-C8 alkyl group; each of Y.sup.1
through Y.sup.3 which may be identical to or different from one
another, represents a Group 13 element; and a and b independently
represent numbers between 0 and 50 inclusive, with the proviso that
a+b is equal to or greater than 1; 42wherein, each of R.sup.6 and
R.sup.7, which may be identical to or different from each other,
represents a C1-C8 alkyl group; Y.sup.4 and Y.sup.5, which may be
identical to or different from each other, represents a Group 13
element; and c and d independently represent numbers between 0 and
50 inclusive, with the proviso that c+d is equal to or greater than
1; and/or a compound (ii) capable of forming an ionic complex
through reaction with transition metal compound (E): (G) an
alkylating agent.
25. The method for producing an ethylene copolymer according to
claim 23, wherein the transition metal compound (E) is represented
by the following formula (3): 43wherein M.sup.1 represents
titanium, zirconium, or hafnium; Cp represents a cyclopentadienyl
group or a substituted cyclopentadienyl group which is bonded to
M.sup.1 via a .eta..sup.5 bonding mode, an indenyl group, a
substituted indenyl group, a fluorenyl group, a substituted
fluorenyl group, a hexahydroazulenyl group, a substituted
hexahydroazulenyl group, a tetrahydroindenyl group, a substituted
tetrahydroindenyl group, a tetrahydrofluorenyl group, a substituted
tetrahydrofluorenyl group, an octahydrofluorenyl group, or a
substituted octahydrofluorenyl group; X.sup.1 represents a .sigma.
ligand; e represents 1 or 2; a plurality of X.sup.1 may be
identical to or different from one another and may be linked
together via an arbitrary group; Y.sup.6 represents O, S, NR, PR,
CR.sub.2, or a neutral two-electron donor selected from OR, SR,
NR.sub.2, or PR.sub.2; Z.sup.1 represents SiR.sub.2, CR.sub.2,
SiR.sub.2SiR.sub.2, CR.sub.2CR.sub.2, CR=CR, CRSiR.sub.2,
GeR.sub.2, BR, or BR.sub.2; R represents hydrogen, an alkyl group,
an aryl group, a silyl group, a haloalkyl group, a haloaryl group,
or a combination of at least two of the above groups selected so as
to have 20 or fewer non-hydrogen atoms; and two or more of the
above R may further form a condensed ring system with Z.sup.1 or
with Y.sup.6 and Z.sup.1.
26. The method for producing an ethylene copolymer according to
claim 24, wherein the transition metal compound (E) is represented
by the following formula (3): 44wherein M.sup.1 represents
titanium, zirconium, or hafnium; Cp represents a cyclopentadienyl
group or a substituted cyclopentadienyl group which is bonded to
M.sup.1 via a .eta..sup.5 bonding mode, an indenyl group, a
substituted indenyl group, a fluorenyl group, a substituted
fluorenyl group, a hexahydroazulenyl group, a substituted
hexahydroazulenyl group, a tetrahydroindenyl group, a substituted
tetrahydroindenyl group, a tetrahydrofluorenyl group, a substituted
tetrahydrofluorenyl group, an octahydrofluorenyl group, or a
substituted octahydrofluorenyl group; X.sup.1 represents a .sigma.
ligand; e represents 1 or 2; a plurality of X.sup.1 may be
identical to or different from one another and may be linked
together via an arbitrary group; Y.sup.6 represents O, S, NR, PR,
CR.sub.2, or a neutral two-electron donor selected from OR, SR,
NR.sub.2, or PR.sub.2; Z.sup.1 represents SiR.sub.2, CR.sub.2,
SiR.sub.2SiR.sub.2, CR.sub.2CR.sub.2, CR=CR, CRSiR.sub.2,
GeR.sub.2, BR, or BR.sub.2; R represents hydrogen, an alkyl group,
an aryl group, a silyl group, a haloalkyl group, a haloaryl group,
or a combination of at least two of the above groups selected so as
to have 20 or fewer non-hydrogen atoms; and two or more of the
above R may further form a condensed ring system with Z.sup.1 or
with Y.sup.1 and Z.sup.1.
27. The method for producing an aromatic vinyl graft copolymer
according to claims 17, wherein aromatic vinyl monomer (H) is
graft-copolymerized with ethylene copolymer macromer (I) through
use of a catalyst formed of the following components (E) and (F):
(E) a transition metal compound; and (F) an oxygen-containing
compound (i) represented by the following formula (1) or (2):
45wherein, each of R.sup.1 through R.sup.5, which may be identical
to or different from one another, represents a C1-C8 alkyl group;
each of Y.sup.1 through Y.sup.3, which may be identical to or
different from one another, represents a Group 13 element; and a
and b independently represent numbers between 0 and 50 inclusive,
with the proviso that a+b is equal to or greater than 1; 46wherein,
each of R.sup.6 and R.sup.7, which may be identical to or different
from each other, represents a C1-C8 alkyl group; Y.sup.4 and
Y.sup.5, which may be identical to or different from each other,
represents a Group 13 element; and c and d independently represent
numbers between 0 and 50 inclusive, with the proviso that c+d is
equal to or greater than 1: and/or a compound (ii) capable of
forming an ionic complex through reaction with transition metal
compound (E).
28. The method for producing an aromatic vinyl graft copolymer
according to claim 27, wherein the transition metal compound (E) is
represented by the following formula (16) or (17):
M.sup.10R.sup.26.sub.uR.sup.27.sub.vR-
.sup.28.sub.wR.sup.29.sub.4-(u+v+w) (16)
M.sup.11R.sup.30.sub.xR.sup.31.- sub.yR.sup.32.sub.3-(x+y) (17)
wherein each of M.sup.10 and M.sup.11 represents a metal that
belongs to Groups 3-6 or the lanthanum group; each of R.sup.26
through R.sup.32 represents an alkyl group, an alkoxy group, an
aryl group, an alkylaryl group, an arylalkyl group, an aryloxy
group, an acyloxy group, a cyclopentadienyl group, an alkylthio
group, an arylthio group, a substituted cyclopentadienyl group, an
indenyl group, a substituted indenyl group, fluorenyl group, an
amino group, an amide group, an acyloxy group, a phosphide group, a
halogen atom, or a chelating agent; R.sup.26 through R.sup.29, or
R.sup.30 through R.sup.32 may be identical to or different from
each other; each of u, v, and w is an integer between 0 and 4
inclusive; each of x and y is an integer of 0 and 3 inclusive; and
two of R.sup.26 through R.sup.29 or R.sup.30 through R.sup.32 may
be cross-linked by use of CH.sub.2 or Si(CH.sub.3).sub.2 to form a
complex.
29. The method for producing an aromatic vinyl graft copolymer
according to claim 27, wherein the transition metal compound (E) is
represented by the following formula (18): T i
R.sup.33X.sup.14Y.sup.10Z.sup.2 (18) wherein R.sup.33 represents a
cyclopentadienyl group, a substituted cyclopentadienyl group, an
indenyl group, a substituted indenyl group, or a fluorenyl group,
and each of X.sup.14, Y.sup.10, and Z.sup.2 represents a hydrogen
atom, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C6-C20 aryl
group, alkylaryl group, arylalkyl group, C6-C20 aryloxy group,
C1-C20 acyloxy group, C1-C50 amino group, amide group, phosphide
group, alkyl thio group, arylthio group, or a halogen atom:
compounds in which one of X.sup.14, Y.sup.10, and Z.sup.2 and
R.sup.33 are cross-linked with CH.sub.2, SiR.sub.2, etc..
30. The method for producing an aromatic vinyl graft copolymer
according to claim 27, wherein the transition metal compound (E) is
represented by the following formula (19): 47wherein each of
R.sup.34 and R.sup.35 represents a halogen atom, C1-c20 alkoxy
group, or an acyloxy group; and z is a number between 2 and 20
inclusive.
31. The method for producing an aromatic vinyl graft copolymer
according to claim 27, wherein the transition metal compound (E) is
represented by the following formula (20):
M.sup.12R.sup.36R.sup.37R.sup.38R.sup.39 (20) wherein M.sup.12
represents titanium, zirconium, or hafnium; each of R.sup.36 and
R.sup.37, which may be identical to or different from each other,
represents a cyclopentadienyl group, a substituted cyclopentadienyl
group, an indenyl group, or a fluorenyl group; and each of R.sup.38
and R.sup.39, which may be identical to or different from each
other, represents a hydrogen atom, a halogen atom, a C1-C20
hydrocarbon group, a C1-C20 alkoxy group, an amino group, or a
C1-C20 thioalkoxy group, wherein R.sup.38 and R.sup.39 may be
cross-linked by the mediation of a C1-C5 hydrocarbon group, a
C1-C20 alkylsilyl group having 1-5 silicon atoms, or a C1-C20
germanium-containing hydrocarbon group having 1-5 germanium
atoms.
32. The method for producing an aromatic vinyl graft copolymer
according to claim 27, wherein the transition metal compound (E) is
represented by the following formula (3): 48wherein M.sup.1
represents titanium, zirconium, or hafnium; Cp represents a
cyclopentadienyl group or a substituted cyclopentadienyl group
which is bonded to M.sup.1 via a .eta..sup.5 bonding mode, an
indenyl group, a substituted indenyl group, a fluorenyl group, a
substituted fluorenyl group, a hexahydroazulenyl group, a
substituted hexahydroazulenyl group, a tetrahydroindenyl group, a
substituted tetrahydroindenyl group, a tetrahydrofluorenyl group, a
substituted tetrahydrofluorenyl group, an octahydrofluorenyl group,
or a substituted octahydrofluorenyl group; X.sup.1 represents a
.sigma. ligand; e represents 1 or 2; a plurality of X.sup.1 may be
identical to or different from one another and may be linked
together via an arbitrary group; Y.sup.6 represents O, S, NR, PR,
CR.sub.2, or a neutral two-electron donor selected from OR, SR,
NR.sub.2, or PR.sub.2; Z.sup.1 represents SiR.sub.2, CR.sub.2,
SiR.sub.2SiR.sub.2, CR.sub.2CR.sub.2, CR=CR, CRSiR.sub.2,
GeR.sub.2, BR, or BR.sub.2; R represents hydrogen, an alkyl group,
an aryl group, a silyl group, a haloalkyl group, a haloaryl group,
or a combination of at least two of the above groups selected so as
to have 20 or fewer non-hydrogen atoms; and two or more of the
above R may further form a condensed ring system with Z.sup.1 or
with Y.sup.6 and Z.sup.1.
33. The method for producing an aromatic vinyl graft copolymer
according to claim 27, wherein the catalyst further contains an
alkylating agent (G).
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an ethylene copolymer and
an aromatic vinyl graft copolymer and a method for producing the
same. More particularly, the present invention relates to a novel
ethylene copolymer which has a vinyl group in the molecular chain,
which is endowed with excellent toughness and compatibility as well
as heat resistance and chemical resistance, and which is useful as
a heat-resistant elastomer and a raw material of a composite
material; to a syndiotactic aromatic vinyl copolymer containing a
macromer formed of the ethylene copolymer (hereinafter may be
simply referred to as ethylene copolymer macromer) as a graft
component; and to a method for producing the same effectively.
[0003] 2. Related Art
[0004] Previously, the present inventors successfully developed a
styrene polymer having a high syndiotacticity (Japanese Patent
Application Laid-Open (kokai) Nos. 62-10818 and 63-241009). The
styrene polymer having a syndiotactic structure is endowed with
excellent heat resistance and chemical resistance, but does not
exhibit sufficient toughness or elongation. In addition, it has
poor compatibility with other resins; therefore its use has
inevitably been limited.
[0005] In order to overcome this drawback, the present inventors
succeeded in endowing the aforementioned styrene polymer having a
syndiotactic structure with toughness by copolymerizing styrene
with an olefin (Japanese Patent Application Laid-Open (kokai) Nos.
3-7705, 4-130114, and 4-300904).
[0006] However, these polymers are not necessarily satisfactory in
terms of toughness, elongation, and compatibility with other
resins. Moreover, they sometimes suffer from deterioration of heat
resistance. Therefore, there has been demand for a technique which
further improves properties such as toughness which maintaining
excellent heat resistance.
[0007] Furthermore, there has been demand for a technique to
effectively improve toughness and elongation of fragile resins
having high glass transition temperature such as typical
polystyrene as well as polystyrene having a syndiotactic
structure.
[0008] The thus-obtained random or block copolymer of styrene and
an olefin suffers insufficient controllability of the
copolymerization composition as well as a low
copolymerization-modification ratio (i.e., percentage of modifier
olefins in the resultant copolymer), leading to insufficient
improvement in toughness, elongation, and compatibility with other
resins.
[0009] There have also been proposed graft copolymers in which a
styrene monomer is graft-copolymerized with a polymer having double
bonds in side chains, as well as block copolymers in which a
styrene monomer is block-copolymerized with a macromonomer having
polymerization-active terminal vinyl groups (Japanese Patent
Application Laid-Open (kokai) Nos. 05-247147 and 05-295056).
However, the copolymers disclosed in the above publications exhibit
an insufficient graft ratio, resulting in insufficient improvement
in physical properties thereof.
[0010] In view of the foregoing, the present invention is directed
to the provision of an ethylene copolymer which is remarkably
useful as a macromonomer for obtaining a syndiotactic polystyrene
graft copolymer having improved toughness, elongation, etc. or as a
material for obtaining a compatibility-enhancing agent for a
composition containing syndiotactic polystyrene and a rubber
component, or a composition of typical polystyrene and a rubber
component; the provision of a syndiotactic aromatic vinyl graft
copolymer which is endowed with excellent toughness, elongation,
and compatibility as well as heat resistance and chemical
resistance, and is useful for a heat-resistant elastomer and a raw
material of composite materials; and the provision of a method for
producing the same in an effective manner.
SUMMARY OF THE INVENTION
[0011] The present inventors carried out extensive studies, and as
a result, found that introduction of a styrenic vinyl group into
the ethylene chain may provide an effective comonomer for obtaining
a polystyrene graft copolymer, and that the polystyrene graft
copolymer may serve as a compatibility-enhancing agent for a
composition containing polystyrene and a rubber component.
[0012] The present inventors also found that a graft copolymer
which is obtained from an aromatic vinyl monomer and the
aforementioned ethylene copolymer serving as a macromer and which
contains an aromatic-vinyl-monomer-derived chain having a
stereospecificity of highly syndiotactic structure is endowed with
excellent toughness, elongation, and compatibility as well as heat
resistance and chemical resistance.
[0013] Furthermore, the present inventors found that ethylene
copolymers are effectively obtained by using a specific catalyst.
The present invention was accomplished based on these findings.
[0014] Specifically, the present invention provides:
[0015] (1) an ethylene copolymer comprising an aromatic vinyl
monomer (A), ethylene (B), and a diene monomer (C) and having in
the molecular chain a vinyl group attributed to a diene monomer,
wherein recurrent units attributed to aromatic vinyl monomer (A) is
1-98 mol %, recurrent units attributed to ethylene (B) is 1-98 mol
%, and recurrent units attributed to diene monomer (C) is 0.001-10
mol %.
[0016] (2) an ethylene copolymer comprising an aromatic vinyl
monomer (A), ethylene (B), a diene monomer (C), and .alpha.-olefin
(D), and having in the molecular chain a vinyl group attributed to
a diene monomer, wherein recurrent units attributed to aromatic
vinyl monomer (A) is 1-98 mol %, recurrent units attributed to
ethylene (B) is 1-98 mol %, recurrent units attributed to diene
monomer (C) is 0.001-10 mol % and recurrent units attributed to
.alpha.-olefin (D) is 0-90 mol % (exclusive of 0).
[0017] (3) the ethylene copolymer described in either one of the
above-described (1) or (2), wherein the diene monomer (C) is a
diene having a styrenic vinyl group.
[0018] (4) a method for producing an ethylene copolymer recited in
either one of the above-described (1) through (3), wherein the
respective monomers are copolymerized through use of a catalyst
formed of the following components (E) and (F):
[0019] (E) a transition metal compound; and
[0020] (F) an oxygen-containing compound (i) represented by the
following formula (1) or (2): 1
[0021] wherein, each of R.sup.1 through R.sup.5, which may be
identical to or different from one another, represents a C1-C8
alkyl group; each of Y.sup.1through Y.sup.3 which may be identical
to or different from one another, represents a Group 13 element;
and a and b independently represent numbers between 0 and 50
inclusive, with the proviso that a+b is equal to or greater than 1;
2
[0022] wherein, each of R.sup.6 and R.sup.7, which may be identical
to or different from each other, represents a C1-C8 alkyl group;
Y.sup.4 and Y.sup.5, which may be identical to or different from
each other, represents a Group 13 element; and c and d
independently represent numbers between 0 and 50 inclusive, with
the proviso that c+d is equal to or greater than 1: and/or a
compound (ii) capable of forming an ionic complex through reaction
with transition metal compound (E).
[0023] (5) a method for producing an ethylene copolymer recited in
either one of the above-described (1) through (3), wherein the
respective monomers are copolymerized through use of a catalyst
formed of the following components (E), (F) and (G):
[0024] (E) a transition metal compound;
[0025] (F) an oxygen-containing compound (i) represented by the
following formula (1) or (2): 3
[0026] wherein, each of R.sup.1 through R.sup.5, which may be
identical to or different from one another, represents a C1-C8
alkyl group; each of Y.sup.1 through Y.sup.3, which may be
identical to or different from one another, represents a Group 13
element; and a and b independently represent numbers between 0 and
50 inclusive, with the proviso that a+b is equal to or greater than
1; 4
[0027] wherein, each of R.sup.6 and R.sup.7, which may be identical
to or different from each other, represents a C1-C8 alkyl group;
Y.sup.4 and Y.sup.5, which may be identical to or different from
each other, represents a Group 13 element; and c and d
independently represent numbers between 0 and 50 inclusive, with
the proviso that c+d is equal to or greater than 1: and/or a
compound (ii) capable of forming an ionic complex through reaction
with transition metal compound (E): and
[0028] (G) an alkylating agent.
[0029] (6) a method for producing an ethylene copolymer recited in
either one of the above-described (1) through (3), wherein the
transition metal compound (E) is represented by the following
formula (3): 5
[0030] wherein M.sup.1 represents titanium, zirconium, or hafnium;
Cp represents a cyclopentadienyl group or a substituted
cyclopentadienyl group which is bonded to M.sup.1 via a .eta..sup.5
bonding mode, an indenyl group, a substituted indenyl group, a
fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl
group, a substituted hexahydroazulenyl group, a tetrahydroindenyl
group, a substituted tetrahydroindenyl group, a tetrahydrofluorenyl
group, a substituted tetrahydrofluorenyl group, an
octahydrofluorenyl group, or a substituted octahydrofluorenyl
group; X.sup.1 represents a .sigma. ligand; e represents 1 or 2; a
plurality of X.sup.1 may be identical to or different from one
another and may be linked together via an arbitrary group; Y.sup.6
represents O, S, NR, PR, CR.sub.2, or a neutral two-electron donor
selected from OR, SR, NR.sub.2, or PR.sub.2; Z.sup.1 represents
SiR.sub.2, CR.sub.2, SiR.sub.2SiR.sub.2, CR.sub.2CR.sub.2, CR=CR,
CRSiR.sub.2, GeR.sub.2, BR, or BR.sub.2; R represents hydrogen, an
alkyl group, an aryl group, a silyl group, a haloalkyl group, a
haloaryl group, or a combination of at least two of the above
groups selected so as to have 20 or fewer non-hydrogen atoms; and
two or more of the above R may further form a condensed ring system
with Z.sup.1 or with Y.sup.6 and Z.sup.1.
[0031] (7) An aromatic vinyl graft copolymer which is a graft
copolymerization product of an aromatic vinyl monomer (H) and
ethylene copolymer macromer (I) and which has in the molecular
chain a vinyl group attributed to a diene monomer; the ethylene
copolymer (I) being obtained through copolymerization of an
aromatic vinyl monomer (A), ethylene (B) and a diene monomer (C),
wherein recurrent units attributed to aromatic vinyl monomer (A) is
1-98 mol %, recurrent units attributed to ethylene (B) is 1-98 mol
%, and recurrent units attributed to diene monomer (C) is 0.001-10
mol %.
[0032] (8) an aromatic vinyl graft copolymer which is a graft
copolymerization product of an aromatic vinyl monomer (H) and
ethylene copolymer macromer (I) and which has in the molecular
chain a vinyl group attributed to a diene monomer; the ethylene
copolymer (I) being obtained through copolymerization of an
aromatic vinyl monomer (A), ethylene (B), a diene monomer (C) and
.alpha.-olefin (D), wherein recurrent units attributed to aromatic
vinyl monomer (A) is 1-98 mol %, recurrent units attributed to
ethylene (B) is 1-98 mol %, recurrent units attributed to diene
monomer (C) is 0.001-10 mol % and recurrent units attributed to
.alpha.-olefin (D) is 0-90 mol % (exclusive of 0).
[0033] (9) an aromatic vinyl graft copolymer described in either
one of the above-described (7) or (8), wherein the diene monomer
(C) is a diene having a styrenic vinyl group.
[0034] (10) an aromatic vinyl graft copolymer described in either
one of the above-described (7) through (9), wherein a chain
attributed to aromatic vinyl monomer (A) has a stereospecificity of
highly syndiotactic structure.
[0035] (11) an aromatic vinyl graft copolymer described in either
one of the above-described (7) through (10), wherein the ethylene
copolymer macromer (I) is prepared by use of a catalyst formed of
the following components (E) and (F):
[0036] (E) a transition metal compound;
[0037] (F) an oxygen-containing compound (i) represented by the
following formula (1) or (2): 6
[0038] wherein, each of R.sup.1 through R.sup.5, which may be
identical to or different from one another, represents a C1-C8
alkyl group; each of Y.sup.1 through Y.sup.3, which may be
identical to or different from one another, represents a Group 13
element; and a and b independently represent numbers between 0 and
50 inclusive, with the proviso that a+b is equal to or greater than
1; 7
[0039] wherein, each of R.sup.6 and R.sup.7, which may be identical
to or different from each other, represents a C1-C8 alkyl group;
Y.sup.4 and Y.sup.5, which may be identical to or different from
each other, represents a Group 13 element; and c and d
independently represent numbers between 0 and 50 inclusive, with
the proviso that c+d is equal to or greater than 1; and/or a
compound (ii) capable of forming an ionic complex through reaction
with transition metal compound (E).
[0040] (12) An aromatic vinyl graft copolymer described in either
one of the above-described (7) or (10), wherein the ethylene
copolymer macromer (I) is prepared by use of a catalyst formed of
the following components (E), (F) and (G):
[0041] (E) a transition metal compound;
[0042] (F) an oxygen-containing compound (i) represented by the
following formula (1) or (2): 8
[0043] wherein, each of R.sup.1 through R.sup.5, which may be
identical to or different from one another, represents a C1-C8
alkyl group; each of Y.sup.1 through Y.sup.3, which may be
identical to or different from one another, represents a Group 13
element; and a and b independently represent numbers between 0 and
50 inclusive, with the proviso that a+b is equal to or greater than
1; 9
[0044] wherein, each of R.sup.6 and R.sup.7, which may be identical
to or different from each other, represents a C1-C8 alkyl group;
Y.sup.4 and Y.sup.5, which may be identical to or different from
each other, represents a Group 13 element; and c and d
independently represent numbers between 0 and 50 inclusive, with
the proviso that c+d is equal to or greater than 1; and/or a
compound (ii) capable of forming an ionic complex through reaction
with transition metal compound (E):
[0045] (G) an alkylating agent.
[0046] (13) the method for producing an ethylene copolymer
described in either one of the above-described (9) or (12), wherein
the transition metal compound (E) is represented by the following
formula (3): 10
[0047] wherein M.sup.1 represents titanium, zirconium, or hafnium;
Cp represents a cyclopentadienyl group or a substituted
cyclopentadienyl group which is bonded to M.sup.1 via a .eta..sup.5
bonding mode, an indenyl group, a substituted indenyl group, a
fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl
group, a substituted hexahydroazulenyl group, a tetrahydroindenyl
group, a substituted tetrahydroindenyl group, a tetrahydrofluorenyl
group, a substituted tetrahydrofluorenyl group, an
octahydrofluorenyl group, or a substituted octahydrofluorenyl
group; X.sup.1 represents a .sigma. ligand; e represents 1 or 2; a
plurality of X.sup.1 may be identical to or different from one
another and may be linked together via an arbitrary group; Y6
represents O, S, NR, PR, CR.sub.2, or a neutral two-electron donor
selected from OR, SR, NR.sub.2, or PR.sub.2; Z.sup.1 represents
SiR.sub.2, CR.sub.2, SiR.sub.2SiR.sub.2, CR.sub.2CR.sub.2, CR=CR,
CRSiR.sub.2, GeR.sub.2, BR, or BR.sub.2; R represents hydrogen, an
alkyl group, an aryl group, a silyl group, a haloalkyl group, a
haloaryl group, or a combination of at least two of the above
groups selected so as to have 20 or fewer non-hydrogen atoms; and
two or more of the above R may further form a condensed ring system
with Z.sup.1 or with Y.sup.6 and Z.sup.1.
[0048] (14) the method for producing an aromatic vinyl graft
copolymer recited in either one of the above-described (9) or (13),
wherein aromatic vinyl monomer (H) is graft-copolymerized with
ethylene copolymer macromer (I) through use of a catalyst formed of
the following components (E) and (F):
[0049] (E) a transition metal compound; and
[0050] (F) an oxygen-containing compound (i) represented by the
following formula (1) or (2): 11
[0051] wherein, each of R.sup.1 through R.sup.5, which may be
identical to or different from one another, represents a C1-C8
alkyl group; each of Y.sup.1 through Y.sup.3 which may be identical
to or different from one another, represents a Group 13 element;
and a and b independently represent numbers between 0 and 50
inclusive, with the proviso that a+b is equal to or greater than 1;
12
[0052] wherein, each of R.sup.6 and R.sup.7, which may be identical
to or different from each other, represents a C1-C8 alkyl group;
Y.sup.4 and Y.sup.5, which may be identical to or different from
each other, represents a Group 13 element; and c and d
independently represent numbers between 0 and 50 inclusive, with
the proviso that c+d is equal to or greater than 1: and/or a
compound (ii) capable of forming an ionic complex through reaction
with transition metal compound (E).
[0053] (15) the method for producing an aromatic vinyl graft
copolymer described in the above-described (14), wherein the
transition metal compound (E) is represented by the following
formula (16) or (17):
M.sup.10R.sup.26.sub.uR.sup.27.sub.vR.sup.28.sub.wR.sup.29.sub.4-(u+v+w)
(16)
M.sup.11R.sup.30.sub.xR.sup.31.sub.yR.sup.32.sub.3-(x+y) (17)
[0054] wherein each of M.sup.10 and M.sup.11 represents a metal
that belongs to Groups 3-6 or the lanthanum group; each of R.sup.26
through R.sup.32 represents an alkyl group, an alkoxy group, an
aryl group, an alkylaryl group, an arylalkyl group, an aryloxy
group, an acyloxy group, a cyclopentadienyl group, an alkylthio
group, an arylthio group, a substituted cyclopentadienyl group, an
indenyl group, a substituted indenyl group, fluorenyl group, an
amino group, an amide group, an acyloxy group, a phosphide group, a
halogen atom, or a chelating agent; R.sup.26 through R.sup.29, or
R.sup.30 through R.sup.32 may be identical to or different from
each other and two of R.sup.26 through R.sup.29 or R.sup.30 through
R.sup.32 may be cross-linked by use of CH.sub.2 or
Si(CH.sub.3).sub.2 to form a complex; each of u, v, and w is an
integer between 0 and 4 inclusive; each of x and y is an integer of
0 and 3 inclusive.
[0055] (16) The method for producing an aromatic vinyl graft
copolymer described in the above-described (14), wherein the
transition metal compound (E) is represented by the following
formula (18):
TiR.sup.33X.sup.14Y.sup.10Z.sup.2 (18)
[0056] wherein R.sup.33 represents a cyclopentadienyl group, a
substituted cyclopentadienyl group, an indenyl group, a substituted
indenyl group, or a fluorenyl group, and each of x.sup.14,
Y.sup.10, and Z.sup.2 represents a hydrogen atom, a C1-C20 alkyl
group, a C1-C20 alkoxy group, a C6-C20 aryl group, alkylaryl group,
arylalkyl group, C6-C20 aryloxy group, C1-C20 acyloxy group, C1-C50
amino group, amide group, phosphide group, alkyl thio group,
arylthio group, or a halogen atom: compounds in which one of
X.sup.14, Y.sup.10, and Z.sup.2 and R.sup.33 are cross-linked with
CH.sub.2, SiR.sub.2, etc.
[0057] (16) the method for producing an aromatic vinyl graft
copolymer described in the above-described (14), wherein the
transition metal compound (E) is represented by the following
formula (19): 13
[0058] wherein each of R.sup.34 and R.sup.35 represents a halogen
atom, C1-c20 alkoxy group, or an acyloxy group; and z is a number
between 2 and 20 inclusive.
[0059] (18) the method for producing an aromatic vinyl graft
copolymer described in the above-described (14), wherein the
transition metal compound (E) is represented by the following
formula (20):
M.sup.12R.sup.36R.sup.37R.sup.38R.sup.39 (20)
[0060] wherein M.sup.12 represents titanium, zirconium, or hafnium;
each of R.sup.36 and R.sup.37, which may be identical to or
different from each other, represents a cyclopentadienyl group, a
substituted cyclopentadienyl group, an indenyl group, or a
fluorenyl group; and each of R.sup.38 and R.sup.39, which may be
identical to or different from each other, represents a hydrogen
atom, a halogen atom, a C1-C20 hydrocarbon group, a C1-C20 alkoxy
group, an amino group, or a C1-C20 thioalkoxy group, wherein
R.sup.38 and R.sup.39 may be cross-linked by the mediation of a
C1-C5 hydrocarbon group, a C1-C20 alkylsilyl group having 1-5
silicon atoms, or a C1-C20 germanium-containing hydrocarbon group
having 1-5 germanium atoms.
[0061] (19) the method for producing an aromatic vinyl graft
copolymer according to claims 20, wherein the transition metal
compound (E) is represented by the following formula (3): 14
[0062] wherein M.sup.1 represents titanium, zirconium, or hafnium;
Cp represents a cyclopentadienyl group or a substituted
cyclopentadienyl group which is bonded to M.sup.1 via a .eta..sup.5
bonding mode, an indenyl group, a substituted indenyl group, a
fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl
group, a substituted hexahydroazulenyl group, a tetrahydroindenyl
group, a substituted tetrahydroindenyl group, a tetrahydrofluorenyl
group, a substituted tetrahydrofluorenyl group, an
octahydrofluorenyl group, or a substituted octahydrofluorenyl
group; X.sup.1 represents a .sigma. ligand; e represents 1 or 2; a
plurality of X.sup.1 may be identical to or different from one
another and may be linked together via an arbitrary group; Y.sup.6
represents O, S, NR, PR, CR.sub.2, or a neutral two-electron donor
selected from OR, SR, NR.sub.2, or PR.sub.2; Z.sup.1 represents
SiR.sub.2, CR.sub.2, SiR.sub.2SiR.sub.2, CR.sub.2CR.sub.2, CR=CR,
CRSiR.sub.2, GeR.sub.2, BR, or BR.sub.2; R represents hydrogen, an
alkyl group, an aryl group, a silyl group, a haloalkyl group, a
haloaryl group, or a combination of at least two of the above
groups selected so as to have 20 or fewer non-hydrogen atoms; and
two or more of the above R may further form a condensed ring system
with Z.sup.1 or with Y.sup.6 and Z.sup.1.
[0063] (20) the method for producing an aromatic vinyl graft
copolymer described in either one of the above-described (14) to
(19), wherein the catalyst further contains an alkylating agent
(G).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0064] Embodiments of the present invention will next be
described.
[0065] 1. Ethylene copolymer
[0066] The ethylene copolymer according to the present invention is
a copolymer comprising an aromatic vinyl monomer (A), ethylene (B),
a diene monomer (C), and an optional .alpha.-olefin (D) and having
in the molecular chain of the copolymer a vinyl group attributed to
a diene monomer.
[0067] (1) Aromatic vinyl monomer (A)
[0068] The aromatic vinyl monomers of formula (A) are compounds
represented by the following formula (4): 15
[0069] wherein X.sup.2 represents a member which falls within the
following cases 1)-3): 1) a hydrogen atom, 2) a halogen atom, 3) a
substituent which contains at least one species selected from among
a carbon atom, a tin atom, or a silicon atom; f represents an
integer between 1 and 5 inclusive, wherein when f>2, X.sup.2 may
be identical to or different from one another. Specifically,
mention may be given of styrene; alkylstyrenes such as
p-methylstyrene, m-methylstyrene, o-methylstyrene,
2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene,
3,5-dimethylstyrene, p-ethylstyrene, m-ethylstryrene, and
p-tert-butylstyrene; halogenated styrenes such as p-chlorostyrene,
m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene,
o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene,
and o-methyl-p-fluorostyrene; alkoxystyrenes such as
methoxystyrene, ethoxystyrene, and t-butoxystyrene; vinylbiphenyls;
vinylphenylnaphthalenes; vinylphenylanthracenes;
halovinylbiphenyls; trialkylsilylvinylbiphenyls;
halogen-substituted alkylstyrenes; alkylsilylstyrenes;
phenyl-group-containing silylstyrenes; halosilylstyrenes; and
silyl-group-containing silylstyrenes. Mixtures of two or more of
these members are also usable. In addition, vinylnaphthalenes,
vinylanthracenes, and their substituents may also be used.
[0070] (2) Ethylene (B)
[0071] No particular limitation is imposed, and a hydrogen may be
substituted by a halogen, etc.
[0072] (3) Diene monomer (C)
[0073] As used herein, the diene monomer (C) is a monomer having
two or more C=C double bonds in the molecule. Mention may be given
of C4-C20 conjugated diene compounds such as butadiene, isoprene,
chloroprene, 1,3-hexadiene, 1,3-heptadiene; cyclodiene compounds
such as cyclopentadiene, 2,5-norbornadiene, 1,3-cyclohexadiene,
1,4-cyclohexadiene, 1,3-cyclooctadiene, and 1,5-cyclooctadiene; and
cycloolefins such as vinylnorbornene. Preferably, vinylstyrene
compounds having styrene vinyl groups, such as those represented by
the following formula (5) and (6), are used. 16
[0074] wherein each of X.sup.3 through X.sup.5 represents an
aromatic compound residue such as benzene, naphthalene, or
anthracene; an aromatic compound residue substituted by a C1-C20
alkyl group, such as toluene, xylene, or ethyl benzene; or a
halogen-substituted aromatic compound residue such as chlorobenzene
or bromobenzene; X.sup.4 and x.sup.5 may be identical to or
different from one another; each of Y.sup.7 and Y.sup.8 represents
CH.sub.2, an alkylene group, or an alkyledene group; each of g and
h represents an integer between 0 and 20 inclusive.
[0075] Specific examples of the compounds represented by formula
(5) include o-divinylbenzene, m-divinylbenzene, p-divinylbenezene,
(o-, m-, p-)divinyltoluene, (o-, m-, p-)2-propenylstyrene, (o-, m-,
p-)3-butenylstyrene, and (o-, m-, p-)4-pentenylstyrene. Examples of
the compounds represented by formula (6) include the compounds
described below. 17
[0076] (4) .alpha.-Olefins (D)
[0077] .alpha.-Olefins (D) which are usable in the present
invention are those other than ethylene. Specific examples include
.alpha.-olefins such as propylene, butene-1, pentene-1, hexene-1,
heptene-1, octene-1, nonene-1, decene-1, 4-phenylbutene-1,
6-phenylhexene-1, 3-methylbutene-1, 4-methylpentene-1,
3-methylpentene-1, 3-methylhexene-1, 4-methylhexene-1,
5-methylhexene-1, 3,3-dimethylpentene-1, 3,4-dimethylpentene-1,
4,4-dimethylpentene-1, and vinylcyclohexane; halogen-substituted
.alpha.-olefins such as hexafluoropropene, tetrafluoroethylene,
2-fluoropropene, fluoroethylene, 1,1-difluoroethylene,
3-fluoropropene, trifluoroethylene, and 3,4-dichlorobutene-1; and
cycloolefins such as cyclopentene, cyclohexene, norbornene,
5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,
5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene,
5,5,6-trimethylnorbornene, 5-phenylnorbornene; and
5-benzylnorbornene. One, two or more of the above-listed compounds
may be used in the present invention.
[0078] (5) The ethylene copolymers (b) are obtained through
copolymerization of the above-listed monomers.
[0079] In the ethylene copolymers, recurrent units derived from
aromatic vinyl monomer (A) are contained in an amount of 1-98 mol
%, preferably 3-50 mol %, more preferably 5-35 mol %; recurrent
units derived from ethylene (B) are contained in an amount of 1-98
mol %, more preferably 50-97 mol %, and more preferably 65-95 mol
%; and recurrent units derived from diene monomer (C) are contained
in an amount of 0.001-10 mol %, preferably 0.01-5 mol %, more
preferably 0.05-3 mol %. In the case in which .alpha.-olefins (D)
are optionally used as monomers, recurrent units derived from
.alpha.-olefin (D) are in amounts of 0-90 mol % (exclusive of 0),
preferably 0-50 mol % (exclusive of 0), more preferably 0-30 mol %
(exclusive of 0). If the amount of the recurrent units attributed
to aromatic vinyl monomer (A) is in excess of 98 mol %, brittleness
of the copolymer itself of the present invention increases, whereas
the corresponding amount is less than 1 mol %, compatibility with
aromatic vinyl resins may deteriorate, leading to poor grafting
ability upon use as a macromonomer. If the amount of the recurrent
units attributed to ethylene (B) is less than 1 mol %, brittleness
of the copolymer itself increases, whereas the corresponding amount
is in excess of 98 mol %, crystallinity is excessively high, and
solubility upon graft copolymerization may decrease. If the amount
of the recurrent units attributed to diene monomer (C) is less than
0.001 mol %, grafting ability upon use as a macromonomer is
insufficient, whereas the corresponding amount is in excess of 10
mol %, crosslinking reaction may occur. In addition, if the amount
of the recurrent units attributed to .alpha.-olefin (D) is in
excess of 90 mol %, crystallinity is excessively high, and
solubility upon graft copolymerization may decrease.
[0080] The limiting viscosity [.eta.] of the ethylene copolymers
(b) is 0.01-15 dl/g, preferably 0.1-12 dl/g, more preferably 0.5-10
dl/g, as measured in decalin at 135.degree. C. In the case in which
the limiting viscosity is less than 0.01 dl/g, poor compatibility
results when graft copolymerization is carried out, whereas in the
case in which the limiting viscosity is in excess of 15 dl/g,
solubility upon graft polymerization may become poor. The molecular
weight distribution of the ethylene copolymers as measured by GPC
(gel permeation chromatography) is 8 or less, preferably 6 or less,
more preferably 4 or less. If the molecular weight distribution is
in excess of 8, graft copolymerization may not be carried out
efficiently, and in addition, physicochemical properties of the
resultant graft copolymers may become lowered.
[0081] 2. Methods for producing ethylene copolymers
[0082] Methods for producing the ethylene copolymers of the present
invention are not particularly limited. For example, in order to
produce the ethylene copolymers (b), it is preferable to use a
catalyst system formed of a combination of vanadium halide or
titanium halide such as vanadium tetrachloride, vanadium
oxytrichloride or titanium tetrachloride, or vanadium compounds
such as tri(acetylacetonate)vanadium- ,
tri(2-methyl-1,3-butanedionato)vanadium, or
tri(1,3-butanedionato)vanadi- um; and organic aluminum compounds
such as trialkylaluminum or dialkylaluminum monohalide.
[0083] Alternatively and preferably, the ethylene copolymers may be
prepared through copolymerization by use of a catalyst formed of
the following (E), (F), and (G). (E): a transition metal compound,
(F): an oxygen-containing compound (i) and/or a compound capable of
forming an ionic complex through reaction with transition metal
compound (E) (ii), and (G): an optional alkylation agent.
[0084] (1) Respective components of the catalyst
[0085] (a) Transition metal compounds (E):
[0086] Various transition metal compounds may be used as the
transition metal compound (E) . Usually, it is preferable to use
the compounds shown below.
[0087] (i) Compounds of formula (3): 18
[0088] wherein M.sup.1 represents titanium, zirconium, or hafnium;
Cp represents a cyclopentadienyl group or a substituted
cyclopentadienyl group which is bonded to M.sup.1 via a .eta..sup.5
bonding mode, an indenyl group, a substituted indenyl group, a
fluorenyl group, a substituted fluorenyl group, a hexahydroazulenyl
group, a substituted hexahydroazulenyl group, a tetrahydroindenyl
group, a substituted tetrahydroindenyl group, a tetrahydrofluorenyl
group, a substituted tetrahydrofluorenyl group, an
octahydrofluorenyl group, or a substituted octahydrofluorenyl
group; X.sup.1 represents a .sigma. ligand; e represents 1 or 2; a
plurality of X.sup.1 may be identical to or different from one
another and may be linked together via an arbitrary group; Y.sup.6
represents O, S, NR, PR, CR.sub.2, or a neutral two-electron donor
selected from OR, SR, NR.sub.2, or PR.sub.2; Z.sup.1 represents
SiR.sub.2, CR.sub.2, SiR.sub.2SiR.sub.2, CR.sub.2CR.sub.2, CR=CR,
CRSiR.sub.2, GeR.sub.2, BR, or BR.sub.2; R represents hydrogen, an
alkyl group, an aryl group, a silyl group, a haloalkyl group, a
haloaryl group, or a combination of at least two of the above
groups selected so as to have 20 or fewer non-hydrogen atoms; and
two or more of the above R may further form a condensed ring system
with Z.sup.1 or with Y.sup.6 and Z.sup.1.
[0089] In the present description, examples of the substituted
cyclopentadienyl group include cyclopentadienyl groups substituted
with one or more C1-C6 alkyl groups such as a
methylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group,
a 1,2,4-trimethylcyclopentadienyl group, a
1,2,3,4-tetramethylcyclopentadienyl group, a
trimethylsilylcyclopentadienyl group, a 1,3-di
(trimethylsilyl)cyclopenta- dienyl group, a tertiary
butylcyclopentadienyl group, a 1,3-di(tertiary
butyl)cyclopentadienyl group, a C1-C20 hydrocarbyl group, or a
C1-C20 halohydrocarbyl group. Examples of the substituted indenyl
group include a methylindenyl group, a dimethylindenyl group, a
tetramethylindenyl group, and a hexamethylindenyl group. Examples
of the substituted tetrahydroindenyl group include a
4,5,6,7-tetrahydroindenyl group, a
1-methyl-4,5,6,7-tetrahydroindenyl group, a
2-methyl-4,5,6,7-tetrahydroin- denyl group, a
1,2-dimethyl-4,5,6,7-tetrahydroindenyl group, a
1,3-dimethyl-4,5,6,7-tetrahydroindenyl group, a
1,2,3-trimethyl-4,5,6,7-t- etrahydroindenyl group, a
1,2,3,4,5,6,7-heptamethyl-4,5,6,7-tetrahydroinde- nyl group, a
1,2,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyl group, a
1,3,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyl group, and a
4,5,6,7-tetrahydro-1,2,3-trimethylindenyl group. Examples of the
substituted fluorenyl group include a methylfluorenyl group, a
dimethylfluorenyl group, a tetramethylfluorenyl group, and an
octamethylfluorenyl group. Examples of the substituted
tetrahydrofluorenyl group include a 1,2,3,4-tetrahydrofluorenyl
group and a 9-methyl-1,2,3,4-tetrahydrofluorenyl group, and
examples of the substituted octahydrofluorenyl group include a
9-methyl-octahydrofluoreny- l group. Examples of the substituted
hexahydroazulenyl group include a 1-methylhexahydroazulenyl group,
a 2-methylhexahydroazulenyl group, a 1,2-dimethylhexahydroazulenyl
group, a 1,3-dimethylhexahydroazulenyl group, and a
1,2,3-trimethylhexahydroazulenyl group.
[0090] X.sup.1 represents a .sigma. ligand, and examples include
hydrido, halogen, alkyl, silyl, aryl, arylsilyl, amido, aryloxy,
alkoxy, silyloxy, phosphido, sulfido, acyl, cyanido, azido,
acetylacetonato, and a combination thereof.
[0091] Specific examples of compounds having the above ligands
include (t-butylamido)
(tetramethylcyclopentadienyl)-1,2-ethanediylzirconium dichloride,
(t-butylamido)-(tetramethylcyclopentadienyl)-1,2-ethanediylti-
tanium dichloride,
(methylamido)(tetramethylcyclopentadienyl)-1,2-ethanedi-
ylzirconium dichloride,
(methylamido)-(tetramethylcyclopentadienyl)-1,2-et-
hanediyltitanium dichloride,
(ethylamido)(tetramethylcyclopentadienyl)-met- hylenetitanium
dichloride, (t-butylamido)dimethyl-(tetramethylcyclopentadi-
enyl)silanetitanium dichloride,
(t-butylamido)dimethyl(tetramethylcyclopen-
tadienyl)-silanezirconium dichloride,
(t-butylamido)dimethyl-(tetramethyl--
cyclopentadienyl)-silanetitanium dimethyl,
(t-butylamido)dimethyl-(tetrame- thyl-cyclopentadienyl)silanezircon
ium dimethyl, (t-butylamido)dimethyl-(t-
etramethylcyclopentadienyl)-silanetitanium dibenzyl,
(t-butylamido)dimethyl-(tetramethylcyclopentadienyl)-silanezirconium
dibenzyl,
(benzylamido)dimethyl-(tetramethylcyclopentadienyl)silanetitani- um
dichloride,
(phenylphosphido)dimethyl-(tetramethylcyclopentadienyl)-sil-
anezirconium dibenzyl,
(t-butylamido)dimethyl-(tetramethylcyclopentadienyl-
)silanetitanium chloride,
(dimethylaminoethyl)tetramethylcyclopentadienyl-- titanium(III)
dichloride, 9-(dimethylaminoethyl)octahydro-fluorenyltitaniu-
m(III) dichloride,
(di-n-butylaminoethyl)tetramethyl-cyclopentadienyltitan- ium(III)
dichloride, (dimethylaminomethyl)tetramethyl-cyclopentadienyltita-
nium(III) dichloride, and
(dimethylaminopropyl)tetramethylcyclopentadienyl- -titanium(III)
dichloride.
[0092] (ii) Compounds represented by the following formula (7):
19
[0093] wherein M.sup.2 represents a transition metal of Group 4 in
the periodic table; Cp represents a cyclopentadienyl skeleton;
Y.sup.9 represents O, S, NR, PR, CR.sub.2, or a neutral
two-electron donor selected from OR, SR, NR.sub.2, and PR.sub.2; B
represents an atom of Group 14 in the periodic table; R represents
hydrogen, an alkyl group, an aryl group, a silyl group, a haloalkyl
group, a haloaryl group, or a combination of at least two of the
above groups selected so as to have 20 or fewer non-hydrogen atoms;
each of X.sup.6 and X.sup.7, which may be identical to or different
from each other, represents a hydrogen atom, a halogen atom, a
C1-C20 hydrocarbyl group, a C1-C20 halohydrocarbyl group, a C1-C20
alkoxy group, a C6-C20 aryloxy group, or a C2-C20 di-substituted
amino group; and each of R.sup.8 through R.sup.13, which may be
identical to or different from one another and may be arbitrarily
linked to form a ring, represents a hydrogen atom, a halogen atom,
a C1-C20 hydrocarbyl group, a C1-C20 halohydrocarbyl group, a
C1-C20 alkoxy group, a C6-C20 aryloxy group, a C2-C20
di-substituted amino group, or a C1-C20 silyl group.
[0094] The groups having a cyclopentadienyl skeleton in the above
Cp represent a group such as a cyclopentadienyl group, a
substituted cyclopentadienyl group, an indenyl group, a substituted
indenyl group, a fluorenyl group, a substituted fluorenyl group, a
hexahydroazulenyl group, a substituted hexahydroazulenyl group, a
tetrahydroindenyl group, a substituted tetrahydroindenyl group, a
tetrahydrofluorenyl group, a substituted tetrahydrofluorenyl group,
a octahydrofluorenyl group, or a substituted octahydrofluorenyl
group. Examples of B include a carbon atom, a silicon atom, and a
germanium atom, with a carbon atom and a silicon atom being
preferred.
[0095] Specific examples of the compounds represented by formula
(7) include
isopropylidene(cyclopentadienyl)(3-t-butyl-5-methyl-2-phenoxy)tit-
anium dichloride,
isopropylidene(methylcyclopentadienyl)(3-t-butyl-5-methy-
l-2-phenoxy)titanium dichloride,
isopropylidene(dimethylcyclopentadienyl)(-
3-t-butyl-5-methyl-2-phenoxy)titanium dichloride,
isopropylidene(trimethyl-
cyclopentadienyl)(3-t-butyl-5-methyl-2-phenoxy)titanium dichloride,
isopropylidene(tetramethylcyclopentadienyl)(3-t-butyl-5-methyl-2-phenoxy)-
titanium dichloride, isopropylidene(n-propylcyclopentadienyl)
(3-t-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene
(primary
butylcyclopentadienyl)(3-t-butyl-5-methyl-2-phenoxy)titanium
dichloride,
isopropylidene(phenylcyclopentadienyl)(3-t-butyl-5-methyl-2-p-
henoxy)titanium dichloride,
isopropylidene(cyclopentadienyl)(3-t-butyl-2-p- henoxy)titanium
dichloride, isopropylidene(methylcyclopentadienyl)(3-t-but-
yl-2-phenoxy)titanium dichloride,
isopropylidene(dimethylcyclopentadienyl)-
(3-t-butyl-2-phenoxy)titanium dichloride,
isopropylidene(trimethylcyclopen-
tadienyl)(3-t-butyl-2-phenoxy)titanium dichloride,
isopropylidene(tetramet-
hylcyclopentadienyl)(3-t-butyl-2-phenoxy)titanium dichloride,
isopropylidene(n-propylcyclopentadienyl)
(3-t-butyl-2-phenoxy)titanium dichloride, isopropylidene(primary
butylcyclopentadienyl)(3-t-butyl-2-phe- noxy)titanium dichloride,
isopropylidene(phenylcyclopentadienyl)(3-t-butyl-
-2-phenoxy)titanium dichloride,
isopropylidene(cyclopentadienyl)(2-phenoxy- )titanium dichloride,
isopropylidene(methylcyclopentadienyl)(2-phenoxy)tit- anium
dichloride,
isopropylidene(dimethylcyclopentadienyl)(2-phenoxy)titan- ium
dichloride,
isopropylidene(trimethylcyclopentadienyl)(2-phenoxy)titani- um
dichloride,
isopropylidene(tetramethylcyclopentadienyl)(2-phenoxy)titan- ium
dichloride, isopropylidene(n-propylcyclopentadienyl)
(2-phenoxy)titanium dichloride, isopropylidene(primary
butylcyclopentadienyl)(2-phenoxy)titanium dichloride, and
isopropylidene(phenylcyclopentadienyl)(2-phenoxy)titanium
dichloride. Examples also include the above compounds in which
titanium is substituted with zirconium or hafnium and in which
isopropylidene is substituted with dimethylsilylene,
diphenylsilylene, or methylene. Examples further include the above
compounds in which dichloride is substituted with dibromide,
diiodide, dimethyl, dibenzyl, dimethoxide, or diethoxide.
[0096] (iii) Compounds represented by the following formula (8) or
(9): 20
[0097] wherein each of E.sup.1 through E.sup.4 represents a
substituted or unsubstituted cyclopentadienyl group, an indenyl
group, or a fluorenyl group, a substituted fluorenyl group; each of
A.sup.1 and A.sup.2 represents a hydrogen atom, a C1-C10 alkyl
group, a C6-C20 aryl group, a C6-C20 alkylaryl group, a C6-C20
arylalkyl group, a C6-C20 haloaryl group, or a C1-C20 hydrocarbon
group containing a hetero atom which is selected from among oxygen,
nitrogen, sulfur, and silicon; Q, which connects E.sup.1 and
E.sup.2, represents a C2-C10 hydrocarbon group, a C1-C10
hydrocarbon group containing silicon, germanium, or tin, a carbon
atom, a silicon atom, a germanium atom, or a tin atom; A.sup.1 and
A.sup.2 may be linked to each other to form a ring together with Q;
each of R.sup.14 through R.sup.17 represents a halogen atom, a
hydrogen atom, a C1-C10 alkyl group, a silicon-containing alkyl
group, a C6-C20 aryl group, a C6-C20 alkylaryl group, or a C6-C20
arylalkyl group; each of M.sup.3 and M.sup.4 represents titanium,
zirconium, or hafnium.
[0098] Specific examples of E.sup.1 through E.sup.4 mentioned above
include a cyclopentadienyl group, a methylcyclopentadienyl group, a
dimethylcyclopentadienyl group, a tetramethyl-cyclopentadienyl
group, an indenyl group, a 3-methylindenyl group, a
tetrahydroindenyl group, a fluorenyl group, a methylfluorenyl
group, and a 2,7-di-t-butylfluorenyl group.
[0099] Specific examples of A.sup.1 and A.sup.2 include a hydrogen
atom, a methyl group, an ethyl group, a propyl group, a phenyl
group, a toluyl group, a fluorophenyl group, a methoxyphenyl group,
and a benzyl group.
[0100] In the case in which A.sup.1 and A.sup.2 are linked to each
other and form a ring structure together with Q, specific examples
of groups which may be formed by A.sup.1, A.sup.2, and Q include a
cyclopentylidene group, a cyclohexylidene group, and a
tetrahydropyran-4-ylidene group.
[0101] Preferable examples of R.sup.14 through R.sup.17 include a
chlorine atom, a methyl group, a phenyl group, and a
trimethylsilylmethyl group.
[0102] Specific examples of the above-mentioned transition metal
compounds include ethylenebis(1-indenyl)zirconium dichloride,
ethylenebis(tetrahydro-1-indenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)-(fluorenyl)zirconium dichloride,
methylphenylmethylene-(cyclopentadienyl) (fluorenyl)zirconium
dichloride, and
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride.
[0103] (iv) Transition metal compounds having a single .pi. ligand
R.sup.16 represented by the following formula (10):
M.sup.5R.sup.18X.sup.8.sub.i (10)
[0104] wherein M.sup.5 represents a transition metal of Group 4 in
the periodic table or a lanthanide metal; R.sup.18 represents a
.pi. ligand, e.g., a group having a cyclopentadienyl skeleton;
X.sup.8 represents a hydrogen atom, a halogen atom, a C1-C20
hydrocarbyl group, a C1-C20 alkoxy group, a C1-C20 thioalkoxy
group, a C6-C20 aryl group, a C6-C20 aryloxy group, a C6-C20
thioaryloxy group, an amino group, or an alkylsilyl group; a
plurality of X.sup.8 may be identical to or different from one
another and may be linked to R.sup.18 via a specific group; and i
represents the valence of M.sup.5.
[0105] Examples of the compounds represented by formula (9) include
mono(cyclopentadienyl)transition metal compounds,
mono(indenyl)transition metal compounds, and
mono(fluorenyl)transition metal compounds. Examples of the
substituted cyclopentadienyl group include cyclopentadienyl groups
substituted with one or more C1-C6 alkyl groups such as a
methylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group,
a 1,2,4-trimethylcyclopentadienyl group, a
1,2,3,4-tetramethylcyclopentadie- nyl group, a
trimethylsilylcyclopentadienyl group, a 1,3-di (trimethylsilyl)
cyclopentadienyl group, a tertiary butylcyclopentadienyl group, a
1,3-di(tertiary butyl)cyclopentadienyl group, and a
pentamethylcyclopentadienyl group. Titanium is preferably used as a
transition metal. Examples of the titanium compounds include
cyclopentadienyltrimethyltitanium,
cyclopentadienyltriethyltitanium,
cyclopentadienyltripropyltitanium,
cyclopentadienyltributyltitanium,
methylcyclopentadienyltrimethyltitanium,
1,2-dimethylcyclopentadienyltrim- ethyltitanium
1,2,4-trimethylcyclopentadienyltrimethyltitanium,
1,2,3,4-tetramethylcyclopentadienyltrimethyltitanium,
pentamethylcyclopentadienyltrimethyltitanium,
pentamethylcyclopentadienyl- triethyltitanium,
pentamethylcyclopentadienyltripropyltitanium,
pentamethylcyclopentadienyltributyltitanium,
cyclopentadienylmethyltitani- um dichloride,
cyclopentadienylethyltitanium dichloride,
pentamethylcyclopentadienylmethyltitanium dichloride,
pentamethylcyclopentadienylethyltitanium dichloride,
cyclopentadienyldimethyltitanium monochloride,
cyclopentadienyldiethyltit- anium monochloride,
cyclopentadienyltitanium trimethoxide, cyclopentadienyltitanium
triethoxide, cyclopentadienyltitanium tripropoxide,
cyclopentadienyltitanium triphenoxide,
pentamethylcyclopentadienyltitanium trimethoxide,
pentamethylcyclopentadi- enyltitanium triethoxide,
pentamethylcyclopentadienyltitanium tripropoxide,
pentamethylcyclopentadienyltitanium triphenoxide,
cyclopentadienyltitanium trichloride,
pentamethylcyclopentadienyltitanium trichloride,
cyclopentadienylmethoxytitanium dichloride,
cyclopentadienyldimethoxytitanium chloride,
pentamethylcyclopentadienylme- thoxytitanium dichloride,
cyclopentadienyltribenzyltitanium,
pentamethylcyclopentadienylmethyldiethoxytitanium, indenyltitanium
trichloride, indenyltitanium trimethoxide, indenyltitanium
triethoxide, indenyltrimethyltitanium, indenyltribenzyltitanium,
pentamethylcyclopentadienyltitanium trithiomethoxide,
pentamethylcyclopentadienyltitanium trithiophenoxide.
[0106] (b) Oxygen-containing compounds (i) and/or compounds capable
of forming an ionic complex through reaction with a transition
metal compound (ii) (F):
[0107] The component (F) which serves as the polymerization
catalyst in the present invention contains the below-described
oxygen-containing compounds (i) and/or compounds capable of forming
an ionic complex through reaction with a transition metal compound
(ii).
[0108] (i) Oxygen-containing compounds
[0109] The oxygen-containing compounds comprise a compound
represented by the below-described formula (1): 21
[0110] and/or a compound represented by the below-described formula
(2): 22
[0111] wherein, each of R.sup.1 through R.sup.7, which may be
identical to or different from one another, represents a C1-C8
alkyl group, specifically, a methyl group, an ethyl group, an
n-propyl group, an isopropyl group, a butyl group, a pentyl group,
a hexyl group, a heptyl group, or an octyl group. R.sup.1 to
R.sup.5 may be identical to or different from one another. Each of
R.sup.6 and R.sup.7, which may be identical to or different from
each other. Each of Y.sup.1 through Y.sup.5 represents a Group 13
element, specifically, B, Al, Ga, In, and Tl, with B and Al being
preferred. Y.sup.1 through Y.sup.5 may be identical to or different
from one another, wherein Y.sup.1 and Y.sup.5 may be identical to
or different from each other. Each of a through d is a number
between 0 and 50 inclusive, and each of (a+b) and (c+d) is a number
of 1 or more. The preferable range for each of a through d is 1-20
inclusive, with 1-5 inclusive being particularly preferred.
[0112] Preferable examples of the oxygen-containing compounds used
as the above-mentioned catalyst component, particularly examples of
alkylaluminoxanes, include compounds having a proportion of the
high-magnetic field component in a methyl proton signal region of
50% or less based on an aluminum-methyl (Al--CH.sub.3) bond
measured through a .sup.1H--NMR spectrum. Briefly, when the above
oxygen-containing compound is subjected to measurement of its
.sup.1H--NMR spectrum in a solvent toluene at room temperature, a
methyl proton signal based on Al--CH.sub.3 is observed in the range
between 1.0 and -0.5 ppm with tetramethylsilane (TMS) as a
standard. Since the proton signal of TMS (0 ppm) exists in the
region for observing a methyl proton based on Al--CH.sub.3, a
methyl proton signal is measured with a methyl proton signal
ranging from toluene of 2.35 ppm to the TMS standard as a standard.
The signal is formed of a high-magnetic field component (i.e., from
0.1 to -0.5 ppm) and the other component (i.e., from 1.0 to -0.1
ppm). The compounds which may preferably be used have a
high-magnetic field component of 50% or less, preferably 45-5%.
[0113] (ii) Compounds capable of forming an ionic complex through
reaction with a transition metal compound
[0114] Examples of the compound capable of forming an ionic complex
through reaction with a transition metal compound include Lewis
acids and coordination compounds comprising a cation and an anion
containing a metal to which a plurality of groups are bonded. There
exist a variety of coordination compounds which comprise a cation
and an anion containing a metal to which a plurality of groups are
bonded, and compounds represented by the below-described formulas
(11) and (13) may preferably be used:
([L.sup.1-H].sup.j+).sub.k([M.sup.6X.sup.9X.sup.10. . .
X.sup.n1].sup.(n1-n3)-).sub.m (11)
([L.sup.2].sup.p+).sub.q([M.sup.7X.sup.11X.sup.12. . .
X.sup.n2].sup.(n2-n4)-).sub.r (12)
[0115] wherein L.sup.1represents a Lewis base, each of M.sup.6 and
M.sup.7 represents a metal selected from Group 5 to Group 15
elements; L.sup.2 represents the below-mentioned M.sup.8,
R.sup.19R.sup.20M.sup.9, or R.sup.21.sub.5C, wherein M.sup.8
represents a metal of Group 1 or a metal selected from Group 8 to
Group 12 elements; M.sup.9represents a metal selected from Group 8
to Group 10 elements; each of R.sup.19 and R.sup.20 represents a
cyclopentadienyl group, a substituted cyclopentadienyl group, an
indenyl group, or a fluorenyl group; R.sup.21 represents an alkyl
group; each of X.sup.9, X.sup.10 through X.sup.n1 and X.sup.11,
X.sup.12 through X.sup.n2 represents a hydrogen atom, a
dialkylamino group, an alkoxy group, an aryloxy group, a C1-C20
alkyl group, a C6-C20 aryl group, an alkylaryl group, an arylalkyl
group, a substituted alkyl group, an organic metalloid group, or a
halogen atom; n3 represents a valence of M.sup.6 and n4 represents
a valence of M.sup.7, and is an integer between 1-7 inclusive; each
of n1 and n2 is an integer between 2 and 8 inclusive; j represents
an ion valence of L.sup.1-H and p represents an ion valence of
L.sup.2, and each of j and p is an integer between 1-7 inclusive;
each of k and q is an integer of one or more; m=kxj/(n1-n3); and
r=qxp/(n2-n4).
[0116] Examples of M.sup.6 and M.sup.7 include atoms such as B, Al,
Si, P, As, or Sb; examples of M.sup.8 include atoms such as Ag, Cu,
Na, or Li; and examples of M.sup.9 include atoms such as Fe, Co, or
Ni. Examples of X.sup.9, X.sup.10 through X.sup.n1 and X.sup.11,
X.sup.12 through X,.sup.n2 include dialkylamino groups such as a
dimethylamino group or a diethylamino group; alkoxy groups such as
a methoxy group, an ethoxy group, or an n-butoxy group; aryloxy
groups such as a phenoxy group, a 2,6-dimethylphenoxy group, or a
naphthyloxy group; C1-C20 alkyl groups such as a methyl group, an
ethyl group, an n-propyl group, an isopropyl group, an n-butyl
group, an n-octyl group, or a 2-ethylhexyl group; C6-C20 aryl
groups, alkylaryl groups, or arylalkyl groups such as a phenyl
group, a p-tolyl group, a benzyl group, a pentafluorophenyl group,
a 3,5-di(trifluoromethyl)phenyl group, a 4-tert-butylphenyl group,
a 2,6dimethylphenyl group, a 3,5-dimethylphenyl group, a
2,4-dimethylphenyl group, or a 1,2-dimethylphenyl group; halogens
such as F, Cl, Br, or I; organic metalloid groups such as a
pentamethylantimonyl; a trimethylsilyl, a trimethylgermyl group, a
diphenylarsenyl, a dicyclohexylantimonyl, or a diphenylboron group.
Examples of the (substituted) cyclopentadienyl group represented by
R.sup.19 and R.sup.20, respectively, include a
methylcyclopentadienyl group, a butylcyclopentadienyl group, and a
pentamethylcyclopentadienyl group.
[0117] Specific examples of the anion containing a metal to which a
plurality of groups are bonded include
B(C.sub.6F.sub.5).sub.4.sup.-, B(C.sub.6HF.sub.4).sub.4.sup.-,
B(C.sub.6H.sub.2F.sub.3).sub.4.sup.-,
B(C.sub.6H.sub.3F.sub.2).sub.4.sup.-,
B(C.sub.6H.sub.4F).sub.4.sup.-, B(C.sub.6H.sub.5).sub.4.sup.-,
B(C.sub.6CF.sub.3F.sub.4).sub.4.sup.-,
B(C.sub.6C.sub.2H.sub.5F.sub.4).sub.4.sup.-, PF.sub.6.sup.-,
P(C.sub.6F.sub.5).sub.6.sup.-, and Al(C.sub.6HF.sub.4).sub.4.sup.-.
Examples of the metal-containing cation include Cp.sub.2Fe.sup.+,
(MeCp).sub.2Fe.sup.+, (t-BuCp).sub.2Fe.sup.+,
(Me.sub.2Cp).sub.2Fe.sup.+, (Me.sub.3Cp).sub.2Fe.sup.+,
(Me.sub.4Cp).sub.2Fe.sup.+, (Me.sub.5Cp).sub.2Fe.sup.+, Ag.sup.+,
Na.sup.+, and Li.sup.+and examples of the other cations include
nitrogen-containing compounds such as pyridinium,
2,4-dinitro-N,N-diethylanilinium, diphenylammonium,
p-nitroanilinium, 2,5-dichloroanilinium,
p-nitro-N,N-dimethylanilinium, quinolinium, N,N-dimethylanilinium,
or N,N-diethylanilinium; carbenium compounds such as
triphenylcarbenium, tri(4-methylphenyl)carbenium, or
tri(4-methoxyphenyl)carbenium; alkylphosphonium ions such as
CH.sub.3PH.sub.3.sup.+, C.sub.2H.sub.5PH.sub.3.sup.+,
C.sub.3H.sub.7PH.sub.3.sup.+, (CH.sub.3).sub.2PH.sub.2.sup.+,
(C.sub.2H.sub.5).sub.2PH.sub.2.sup.+,
(C.sub.3H.sub.7).sub.2PH.sub.2.sup.- +, (CH.sub.3).sub.3PH.sup.+,
(C.sub.2H.sub.5).sub.3PH.sup.+,(C.sub.3H.sub.- 7).sub.3PH.sup.+,
(CF.sub.3).sub.3PH.sup.+, (CH.sub.3).sub.4P.sup.+,
(C.sub.2H.sub.5).sub.4P.sup.+, or (C.sub.3H.sub.7).sub.4P.sup.+;
and arylphosphonium ions such as C.sub.6H.sub.5PH.sub.3.sup.+,
(C.sub.6H.sub.5).sub.2PH.sub.2.sup.+,
(C.sub.6H.sub.5).sub.3PH.sup.30 , (C.sub.6H.sub.5).sub.4P.sup.+,
(C.sub.2H.sub.5).sub.2(C.sub.6H.sub.5) PH.sup.+, (CH.sub.3)
(C.sub.6H.sub.5)PH.sub.2.sup.+,
(CH.sub.3).sub.2(C.sub.6H.sub.5)PH.sup.+, or
(C.sub.2H.sub.5).sub.2(C.sub- .6H.sub.5).sub.2P.sup.+.
[0118] Specifically, among the compounds represented by formulas
(11) and (12), the following compounds are preferably used.
Examples of the compound represented by formula (11) include
triethylammonium tetraphenylborate, tri(n-butyl)ammonium
tetraphenylborate, trimethylammnonium tetraphenylborate,
triethylammonium tetrakis(pentafluorophenyl)borate,
tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,
triethylammonium hexafluoroarsenate, pyridinium
tetrakis(pentafluorophenyl)borate, pyrrolinium
tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate, and methyldiphenylammonium
tetrakis(pentafluorophenyl)borate. Examples of the compound
represented by formula (14) include ferrocenium tetraphenylborate,
dimethylferrocenium tetrakis(pentafluorophenyl)borate, ferrocenium
tetrakis(pentafluorophenyl)borate, decamethylferrocenium
tetrakis(pentafluorophenyl)borate, acetylferrocenium
tetrakis(pentafluorophenyl)borate, formylferrocenium
tetrakis(pentafluorophenyl)borate, cyanoferrocenium tetrakis
(pentafluorophenyl)borate, silver tetraphenylborate, silver
tetrakis(pentafluorophenyl)borate, trityl tetraphenylborate, trityl
tetrakis(pentafluorophenyl)borate, silver hexafluoroarsenate,
silver hexafluoroantimonate, and silver tetrafluoroborate.
[0119] Examples of the Lewis acids which may be used include
B(C.sub.6F.sub.5).sub.3, B(C.sub.6HF.sub.4).sub.3,
B(C.sub.6H.sub.2F.sub.3).sub.3, B(C.sub.6H.sub.3F.sub.2).sub.3,
B(C.sub.6H.sub.4F).sub.3, B(C.sub.6CF.sub.3F.sub.4).sub.3,
PF.sub.5, and Al(C.sub.6HF.sub.4).sub.3. In the polymerization
catalysts used in the present invention as the component (F),
oxygen-containing compounds may exclusively be used singly or in
combination of two or more species serving as the component (i) or
compounds being able to form an ionic complex through reaction with
a transition metal compound may exclusively be used singly or in
combination of two or more species serving as the component (ii).
Alternatively, the component (i) and the component (ii) may
appropriately used in combination.
[0120] (c) Alkylating agents (G):
[0121] There are a variety of alkylating agents, and examples
thereof include alkyl group-containing aluminum compounds
represented by formula (13):
R.sup.22.sub.SAl (OR.sup.23) .sub.tX.sup.13.sub.3-S-t (13)
[0122] wherein each of R.sup.22 and R.sup.23 represents a C1-C8,
preferably a C1-C4, alkyl group; X.sup.13 represents a hydrogen
atom or a halogen atom; s is defined as 0<s<3, and is
preferably 2 or 3, most preferably 3; t is defined as 0<t<3,
and is preferably 0 or 1; alkyl group-containing magnesium
compounds represented by formula (14):
R.sup.24.sub.2Mg (14)
[0123] wherein R.sup.24 represents a C1-C8, preferably a C1-C4,
alkyl group; and alkyl group-containing zinc compounds represented
by formula (15):
R.sup.25.sub.2Zn (15)
[0124] wherein R.sup.25 represents a C1-C8, preferably a C1-C4,
alkyl group.
[0125] Among these alkyl group-containing compounds, alkyl
group-containing aluminum compounds, inter alia, trialkylaluminum
compounds and dialkylaluminum compounds, are preferred.
[0126] (2) Methods for preparing the catalysts
[0127] Examples of methods for contacting components (E) and (F) of
the catalysts for polymerization with an optional component (G)
include (1) adding the component (G) to a mixture of the component
(E) and the component (F) to thereby provide a catalyst, and
contacting monomers to be polymerized with the catalyst; (2) adding
the component (E) to a mixture of the component (F) and the
component (G) to thereby provide a catalyst, and contacting
monomers to be polymerized with the catalyst; (3) adding the
component (F) to a mixture of the component (E) and the component
(G) to thereby provide a catalyst, and contacting monomers to be
polymerized with the catalyst; (4) individually contacting the
components (E), (F), and (G) with monomer components to be
polymerized; and (5) contacting a mixture of a monomer component to
be polymerized and the component (G) with the catalysts prepared in
the above (1) through (3).
[0128] The above component (E) and component (F) are contacted with
the optional component (G) at the polymerization temperature or in
the temperature range from -20 to 200.degree. C.
[0129] Organic aluminum compounds such as triisobutylaluminum may
be added prior to feeding catalyst components so as to scavenge
impurities.
[0130] (3) Polymerization methods
[0131] Bulk polymerization may be employed as the polymerization
method, and polymerization may be conducted in aliphatic
hydrocarbon solvents such as pentane, hexane, or heptane; alicyclic
hydrocarbon solvents such as cyclohexane; and aromatic hydrocarbon
solvents such as benzene, toluene, xylene, or ethylbenzene. No
particular limitation is imposed on the polymerization temperature,
and it is typically 0-200.degree. C., preferably 20-100.degree.
C.
[0132] In the obtained aromatic vinyl graft copolymers, the
compositional ratio of polymer segment derived from aromatic vinyl
monomer (H) and that derived from ethylene copolymer macromer (I)
can be regulated through feed amounts of the monomers (I).
[0133] 3. Aromatic vinyl graft copolymers
[0134] The aromatic vinyl graft copolymers of the present invention
are graft copolymerization products between an aromatic vinyl
monomer (H) and the above-described ethylene copolymer (hereinafter
may be referred to as ethylene copolymer macromer) (I). The
ethylene copolymer macromer (I) is obtained through
copolymerization of aromatic vinyl monomer (A), ethylene (B), and
diene monomer (C), wherein the amount of the recurrent units
attributed to aromatic vinyl monomer (A) is 1-98 mol %, the amount
of the recurrent units attributed to ethylene (B) is 1-98 mol %,
and the amount of the recurrent units attributed to diene monomer
(C) is 0.001-10 mol %. The molecular chain of the aromatic vinyl
graft copolymer is an ethylene copolymer having a vinyl group
attributed to a diene monomer. The chains derived from aromatic
vinyl monomers in the polymer products have stereospecificity of
highly syndiotactic structure.
[0135] (1) Aromatic vinyl monomers (H)
[0136] Specific description of the aromatic vinyl monomers (H) is
omitted, since the aromatic vinyl monomers (H) which are usable in
the present invention are identical to those which are used as
copolymerization components in the preparation of the
aforementioned ethylene copolymers.
[0137] (2) Ethylene copolymer macromers (I)
[0138] The ethylene copolymer macromers (I) of the present
invention are obtained through copolymerization of aromatic vinyl
monomer (A), ethylene (B), diene monomer (C), and an optional
.alpha.-olefin (D), and are identical to those listed for the
aforementioned ethylene copolymers. Therefore, detailed description
thereof is omitted.
[0139] The aromatic vinyl graft copolymers of the present invention
are obtained through copolymerization of the aforementioned
aromatic vinyl monomer (A) and the aforementioned ethylene
copolymer macromer (I). The aromatic vinyl graft copolymers are
preferably constituted by 97-50 wt %, more preferably 95-50 wt %,
most preferably 90-60 wt %, of the polymer segment attributed to
aromatic vinyl monomer (H), and 3-50 wt %, more preferably 5-50 wt
%, most preferably 10-40 wt %, of a polymer segment attributed to
the ethylene copolymer (I). The polymer segment attributed to
ethylene copolymer (I) encompasses components both grafted and not
grafted. In the case in which the polymer segment attributed to
ethylene copolymer (I) is present in an amount of less than 3 wt %,
satisfactory effect for improving toughness may not be obtained,
whereas the corresponding amount is in excess of 50 wt %, the melt
viscosity of the graft copolymer will increase, and thus molding
may become difficult or the elastic modulus may decrease, to
thereby cause deformation during mold release following molding.
The graft ratio ("weight of grafted components among the segments
of ethylene copolymer (I)"/"weight of polymer segments attributed
to ethylene copolymer (I) containing both grafted components and
non-grafted components") is prferably 10 wt % or more, more
preferably 20 wt % or more. If the ratio is less than 10 wt %,
sufficient effect for improving toughness of the graft copolymer
may not be obtained.
[0140] The limiting viscosity [.eta.] of the aromatic vinyl graft
copolymer of the present invention is 0.05-10 dl/g, preferably
0.1-8 dl/g, more preferably 1-5 dl/g, as measured in decalin at
135.degree. C. If the limiting viscosity is less than 0.05 dl/g,
satisfactory compatibility-enhancing effect may not be exhibited,
and thus toughness may not be satisfactorily improved. On the other
hand, if the limiting viscosity is in excess of 10 dl/g, the
viscosity when the copolymer is melted extremely increases, to
thereby hamper polymerization of the aromatic vinyl monomer to
result in a reduced graft efficiency.
[0141] In the aromatic vinyl graft copolymers of the present
invention, the chain attributed to an aromatic vinyl monomer has a
stereospecificity of highly syndiotactic structure; i.e., in the
case of racemic diad, a syndiotacticity of 75% or more, preferably
not less than 85%, and in the case of racemic pentad, a
syndiotacticity of 30% or more, preferably not less than 50%. When
a mixture of two or more monomers is used as a styrene monomer, the
segment derived from the styrene monomer may be a random or block
copolymerization product of the monomers.
[0142] 4. Method for preparing aromatic vinyl graft copolymers
[0143] No particular limitation is imposed on the method for
preparing the aromatic vinyl graft copolymers. For example, they
may be obtained by adding a powdery ethylene copolymer macromer (I)
to a syndiotactic aromatic vinyl polymer powder which has already
been synthesized and heating to initiate reaction. Preferably, the
ethylene copolymer macromer (I) may be obtained by dissolving in an
aromatic vinyl monomer (H) or in a solvent containing the monomer
(H), then copolymerizing by use of: (E) a transition metal
compound, (H) (i) an oxygen-containing compound and/or (ii) a
compound that can form an ionic complex through reaction with a
transition metal compound (E), and (G) an optional alkylating
agent. In this case, there is preferably used a method in which the
ethylene copolymer macromer (I) is dissolved in an aromatic vinyl
monomer (H) or a solvent containing the same (H), in view of
conducting homogeneous reaction. No particular limitation is
imposed on the solvent, and hydrocarbon solvents such as toluene,
benzene, or ethylbenzene are preferably used. Next will be
described catalysts preferably used for copolymerization.
[0144] (1) Components of catalyst:
[0145] (a) Transition metal compounds (J)
[0146] A variety of transition metals may be used as (a) transition
metal compound (J), and there may be used the aforementioned
transition metal compounds serving as the component of the
polymerization catalyst for the above-described ethylene copolymer
macromer (I). Moreover, compounds represented by formula (16) or
formula (17) may be used.
M.sup.10R.sup.26.sub.uR.sup.27.sub.vR.sup.28.sub.wR.sup.29.sub.4-(u+v+w)
(16)
M.sup.11R.sup.30.sub.xR.sup.31.sub.yR.sup.32.sub.3-(x+y) (17)
[0147] wherein each of M.sup.10 and M.sup.11 represents a metal
that belongs to Groups 3-6 or the lanthanum group; each of R.sup.26
through R.sup.32 represents an alkyl group, an alkoxy group, an
aryl group, an alkylaryl group, an arylalkyl group, an aryloxy
group, an acyloxy group, a cyclopentadienyl group, an alkylthio
group, an arylthio group, a substituted cyclopentadienyl group, an
indenyl group, a substituted indenyl group, fluorenyl group, an
amino group, an amide group, an acyloxy group, a phosphide group, a
halogen atom, or a chelating agent; each of u, v, and w is an
integer between 0 and 4 inclusive; each of x and y is an integer of
0 and 3 inclusive; and two of R.sup.26 through R.sup.29 or two of
R.sup.30 through R.sup.32 may be cross-linked by use of CH.sub.2 or
Si(CH.sub.3).sub.2 to form a complex.
[0148] Preferably, each of the metal M.sup.10 and M.sup.11 that
belongs to Groups 3-6 or the lanthanum group is a metal that
belongs to group 4, inter alia, titanium, zirconium, and hafnium.
Preferable titanium compounds are represented by the following
formula (18):
T i R.sup.33X.sup.14Y.sup.10Z.sup.2 (18)
[0149] wherein R.sup.33 represents a cyclopentadienyl group, a
substituted cyclopentadienyl group, an indenyl group, a substituted
indenyl group, or a fluorenyl group, and each of X.sup.14,
Y.sup.10, and Z.sup.2 represents a hydrogen atom, a C1-C20 alkyl
group, a C1-C20 alkoxy group, a C6-C20 aryl group, alkylaryl group,
arylalkyl group, C6-C20 aryloxy group, C1-C20 acyloxy group, C1-C50
amino group, amide group, phosphide group, alkyl thio group,
arylthio group, or a halogen atom. Compounds in which one of
X.sup.14, Y.sup.10 and Z.sup.2, and R.sup.33 are cross-linked with
CH.sub.2, SiR.sub.2, etc. also fall within the definition of the
formula (18) compounds.
[0150] Of these titanium compounds, those having no halogen atom
are preferred. Particularly, titanium compounds having a single
.pi.-electron system ligand as described above are preferred.
[0151] Also, as titanium compounds, there may be used condensation
titanium compounds represented by the following formula (19):
23
[0152] wherein each of R.sup.34 and R.sup.35 represents a halogen
atom, C1-C20 alkoxy group, or an acyloxy group; and z is a number
between 2 and 20 inclusive. These titanium compounds may be
transformed into complexes by use of esters or ether before
use.
[0153] Examples of other transition metal compounds which serve as
component (a) include those having two
conjugate-.pi.-electron-containing ligands, and specifically,
mention may be given of at least one compound selected from among
the transition metal compounds represented by the following formula
(20):
M.sup.12R.sup.36R.sup.37R.sup.38R.sup.39 (20)
[0154] wherein M.sup.12 represents titanium, zirconium, or hafnium;
each of R.sup.36 and R.sup.37 represents a cyclopentadienyl group,
a substituted cyclopentadienyl group, an indenyl group, or a
fluorenyl group; and each of R.sup.38 and R.sup.39 represents a
hydrogen atom, a halogen atom, a C1-C20 hydrocarbon group, a C1-C20
alkoxy group, an amino group, or a C1-C20 thioalkoxy group, wherein
R.sup.36 and R.sup.37 may be cross-linked by the mediation of a
C1-C5 hydrocarbon group, a C1-C20 alkylsilyl group having 1-5
silicon atoms, or a C1-C20 germanium-containing hydrocarbon group
having 1-5 germanium atoms.
[0155] (b) (i) oxygen-containing compounds and/or (ii) compounds
capable of forming an ionic complex through reaction with a
transition metal compound (F):
[0156] Compounds described in relation to the synthesis of ethylene
copolymer macromers may be used.
[0157] (c) Alkylating agents (G):
[0158] Those described in relation to the synthesis of ethylene
copolymer macromers may be used.
[0159] (2) Preparation of catalysts:
[0160] Examples of methods for contacting components (J) and (F) of
the catalysts for polymerization with optional component (G)
include the following methods (1) through (5). According to method
(1), component (G) is added to a mixture of component (J) and
component (F) to thereby provide a catalyst. The catalyst is
contacted with monomers to be polymerized (i.e., in the present
invention, a solution obtained by dissolving macromer (I) in
aromatic vinyl monomer (H) or in a solvent containing aromatic
vinyl monomer (H)). According to method (2), component (E) is added
to a mixture of component (F) and component (G) to thereby provide
a catalyst, and the catalyst is contacted with monomers to be
polymerized. According to method (3), component (F) is added to a
mixture of component (J) and component (G) to thereby provide a
catalyst, and the catalyst is contacted with monomers to be
polymerized. According to method (4), respective components (J),
(F), and (G) are individually contacted with monomer components to
be polymerized. According to method (5), a mixture of a monomer
component to be polymerized and component (G) with a catalyst
prepared by any of the methods (1) through (3).
[0161] The above component (J) and component (Fb) may be contacted
with the optional component (G) at the polymerization temperature
or in the temperature range of -20 to 200.degree. C.
[0162] The catalysts used in polymerization are thus formed of a
combination of the aforementioned components (J) and (F), or of a
combination of the aforementioned components (J), (F), and (G).
Other catalyst components may also be incorporated in the catalyst
system. The proportions of respective catalysts may vary in
accordance with conditions and thus are not univocally determined.
Usually, if the component (F) is an oxygen-containing compound, the
mole ratio of component (J) to component (F) is preferably from 1:1
to 1:10,000, more preferably from 1:1 to 1:1,000; if the component
(F) is a compound which is capable of forming an ionic complex
through reaction with a transition metal compound, the mole ratio
of component (J) to component (F) is preferably from 0.1:1 to
1:0.1; and if component (G) is used, the mole ratio of component
(J) to component (G) is preferably from 1:0.1 to 1:1,000.
[0163] Prior to feeding catalyst components, organic aluminum
compounds such as triisobutylaluminum may be added so as to
scavenge impurities.
[0164] (3) Polymerization methods:
[0165] Bulk polymerization may be employed as the polymerization
method, and polymerization may be conducted in aliphatic
hydrocarbon solvents such as pentane, hexane, or heptane; alicyclic
hydrocarbon solvents such as cyclohexane; and aromatic hydrocarbon
solvents such as benzene, toluene, xylene, or ethylbenzene. No
particular limitation is imposed on the polymerization temperature,
and it is typically 0-200.degree. C., preferably 20-100.degree.
C.
[0166] The proportions of the polymer segment derived from aromatic
vinyl monomer (H) and that derived from ethylene copolymer macromer
(I) in the final aromatic vinyl graft copolymer may be suitably
regulated in accordance with the amounts of aromatic vinyl monomer
(H) and macromer (I) which undergo polymerization.
EXAMPLES
[0167] The present invention will next be described in more detail
by way of example.
Example 1
[0168] In a 2-liter pressure-proof polymerization tank were placed
dehydrated toluene (260 ml), active-alumina-treated purified
styrene (600 ml), active-alumina-treated p-divinylbenzene (4.5
ml)(manufactured by Nippon Steel Chemical Co., Ltd., high-purity
para isomer T-30), and methylaluminoxane (manufactured by Albermer)
such that an aluminum concentration was 9 mmol. Ethylene was fully
melted under a constant pressure of 0.6 MPa, and
(t-butylamido)dimethyl (.eta.-1,2,3, 4-tetrahydro-9-fluorenyl)
silanetitanium dichloride was added thereto such that an titanium
concentration was 15 .mu.mol. Subsequently, ethylene was subjected
to polymerization at 70.degree. C. for 30 minutes under a constant
ethylene pressure.
[0169] After removal of ethylene gas, polymerization was terminated
by addition of a small amount of methanol.
[0170] The obtained viscous solution was precipitated in methanol,
and a polymer was recovered. The polymer was dried at 50.degree. C.
under reduced pressure, to thereby obtain an ethylene copolymer
(83.8 g).
[0171] The composition was confirmed by .sup.1H--NMR to be
ethylene/styrene/divinylbenzene=78.4/21.5/0.1 (mol %). The amount
of divinylbenzene was calculated from the NMR peak corresponding to
the vinyl groups. Styrenic vinyl groups were confirmed to exist in
the molecular chain.
[0172] No cross-linked product in a gel form was produced. The
obtained ethylene copolymer had a [.eta.] of 1.3 and a molecular
weight distribution (Mw/Mn) of 1.87 as measured by GPC.
Example 2
[0173] The procedure of Example 1 was repeated except that the
amount of dehydrated toluene was 500 ml, the amount of
active-alumina-treated purified styrene was 930 ml, the amount of
active-alumina-treated p-divinylbenzene (manufactured by Nippon
Steel Chemical Co., Ltd., high-purity para isomer T-30) was 10.5
ml, the amount of methylaluminoxane (manufactured by Albermer) was
such that an aluminum concentration was 18 mmol,
triisobutylaluminoxane (manufactured by Tosoh-Akzo Co., Ltd.) was
further added thereto such that an aluminum concentration was 0.5
mmol, the amount of (t-butylamido) dimethyl
(.eta..sup.5-1,2,3,4-tetrahydro-9-fluorenyl)silanetitanium
dichloride was such that an titanium concentration was 30 .mu. mol,
and polymerization temperature was 90.degree. C.
[0174] An ethylene copolymer was obtained in an amount of 115.3
g.
[0175] The composition was confirmed by .sup.1H--NMR to be
ethylene/styrene/divinylbenzene=71.1/28.6/0.4 (mol %). The amount
of divinylbenzene was calculated from the NMR peak corresponding to
the vinyl groups. Styrenic vinyl groups were confirmed to exist in
the molecular chain.
[0176] No cross-linked product in a gel form was obtained. The
obtained ethylene copolymer had a [.eta.] of 1.4 and a molecular
weight distribution (Mw/Mn) of 1.89 as measured by GPC.
Example 3
[0177] The procedure of Example 1 was repeated except that the
capacity of the pressure-proof container was 1 liter; no toluene
was used; active-alumina-treated purified styrene (200 ml),
active-alumina-treated p-divinylbenzene (1.5 ml)(manufactured by
Nippon Steel Chemical Co., Ltd., high-purity para isomer T-30), and
methylaluminoxane (manufactured by Albermer) (in the concentration
as reduced to the aluminum concentration of 5.0 mmol) were added; a
mixture gas of ethylene and propylene (8:2 by mol ratio) was then
continuously added thereto until ethylene and propylene were fully
dissolved and the pressure in the container reached a steady state
at 0.6 MPa; and (t-butylamido) dimethyl
(.eta..sup.5-1,2,3,4-tetrahydro-9-fluorenyl)silanetitanium
dichloride was added thereto such that a titanium concentration was
5 .mu.mol, to thereby obtain an ethylene-propylene copolymer (15.2
g).
[0178] The composition was confirmed by .sup.1H--NMR to be
ethylene/propylene/styrene/divinylbenzene=68.5/12.2/19.1/0.3 (mol
%). The amount of divinylbenzene was calculated from the NMR peak
corresponding to the vinyl groups. Styrenic vinyl groups were
confirmed to exist in the molecular chain.
[0179] No cross-linked product in a gel form was produced. The
obtained ethylene copolymer had a [.eta.] of 1.2 and a molecular
weight distribution (Mw/Mn) of 1.51 as measured by GPC.
Example 4
[0180] (1) Synthesis of ethylene copolymer macromer
[0181] In a 2-liter pressure-proof polymerization tank were placed
dehydrated toluene (500 ml), active-alumina-treated purified
styrene (1000 ml), active-alumina-treated divinylbenzene (5.0
ml)(manufactured by Nippon Steel Chemical Co., Ltd., high-purity
para and meta isomer T-30, divinylbenzene content: 70 wt.%), and
methylaluminoxane (manufactured by Albermer) such that an aluminum
concentration was 18 mmol. Ethylene was fully melted under a
constant pressure of 0.8 MPa, and
(t-butylamido)dimethyl(tetramethyl-.eta..sup.5cyclopentadienyl)silanetita-
nium dichloride was added thereto such that a titanium
concentration was 30 .mu.mol. Subsequently, ethylene was subjected
to polymerization at 70.degree. C. for 90 minutes under a constant
ethylene pressure. After removal of ethylene gas, polymerization
was terminated by addition of a small amount of methanol.
[0182] The resultant viscous solution was precipitated in methanol,
and a polymer was recovered. The polymer was dried at 50.degree. C.
under reduced pressure, to thereby obtain an ethylene copolymer
(115 g).
[0183] The composition was confirmed by .sup.1H--NMR to be
ethylene/styrene/divinylbenzene=71.3/28.5/0.2 (mol %). The limiting
viscosity [.eta.] was 1.4.
[0184] (2) Synthesis of aromatic vinyl graft copolymer
[0185] In a 500-ml separable flask were placed fully-dehydrated
toluene (150 ml) and active-alumina-treated purified styrene (100
ml). After purge with nitrogen, the ethylene copolymer macromer
(6.0 g) synthesized in procedure (1) above was added to the mixture
under stirring. The macromer was completely dissolved in the
styrene monomer liquid at 50.degree. C.
[0186] Next, the solution of ethylene copolymer macromer in styrene
was heated to 75.degree. C., and triisobutyl aluminum (1.0 mmol)
was added thereto. Subsequently, a titanium-mixed catalyst prepared
in advance was added thereto such that a titanium concentration was
5.0 .mu.mol, and the mixture was subjected to polymerization for 10
minutes under stirring. The mixture ratio of the titanium-mixed
catalyst was methylaluminoxane:triisobutyl
aluminum:titanium=75:25:1 (mol ratio), and the titanium was in the
form of 1,2,3,4,5,6,7,8-octahydrofluorenyltitaniu- m
trimethoxide.
[0187] Polymerization was terminated by addition of a small amount
of methanol. The polymer was washed with methanol and dried at
50.degree. C. under reduced pressure for 12 hours, to thereby
obtain a polymer (yield: 17.1 g).
[0188] The thus-obtained aromatic vinyl graft copolymer had a total
ethylene copolymer macromer content of 35 wt. %. The ethylene
copolymer macromer had a limiting viscosity [.eta.] of 1.4 dl/g.
The graft ratio was 37.1 wt.%, and the tensile elongation was
95%.
Example 5
[0189] The procedure of Example 4 was repeated except that, in step
(2), the amount of toluene was 400 ml, the amount of ethylene
copolymer macromer was 12.0 g, the amount of titanium-mixed
catalyst was such that a titanium concentration was 15.0 .mu.mol,
to thereby obtain a polymer (yield: 44.4 g).
[0190] The thus-obtained aromatic vinyl graft copolymer had a total
ethylene copolymer macromer content of 27 wt. %. The ethylene
copolymer macromer had a limiting viscosity [.eta.] of 1.4 dl/g.
The graft ratio was 62.8 wt. %, and the tensile elongation was
94%.
Example 6
[0191] (1) Synthesis of ethylene copolymer macromer
[0192] In a 2-liter pressure-proof polymerization tank were placed
dehydrated toluene (500 ml), active-alumina-treated purified
styrene (1000 ml), active-alumina-treated divinylbenzene (5.0
ml)(manufactured by Nippon Steel Chemical Co., Ltd., high-purity
para and meta isomer T-30, divinylbenzene content: 70 wt. %), and
methylaluminoxane (manufactured by Albermer) such that an aluminum
concentration was 25 mmol. Subsequently, a mixture gas of ethylene
and propylene (8:2 by mol ratio) was continuously added thereto
until ethylene and propylene were fully dissolved and the pressure
in the container reached a steady state at 0.6 Mpa, and
(t-butylamido)dimethyl(tetramethyl-.eta..sup.5-cyclopentadienyl)-
silanetitanium dichloride was then added thereto such that a
titanium concentration was 30 .mu.mol, followed by polymerization
at 70.degree. C. for 90 minutes under a constant ethylene pressure.
After removal of ethylene gas, polymerization was terminated by
addition of a small amount of methanol.
[0193] The thus-obtained viscous solution was precipitated in
methanol, and a polymer was recovered. The polymer was dried at
50.degree. C. under reduced pressure, to thereby obtain an ethylene
copolymer (108 g).
[0194] The composition was confirmed by .sup.1H--NMR to be
ethylene/propylene/styrene/divinylbenzene=57.8/13.8/28.2/0.2 (mol
%). The limiting viscosity [.eta.] was 1.2.
[0195] (2) Synthesis of aromatic vinyl graft copolymer
[0196] The procedure of Example 5 was repeated except that ethylene
copolymer macromer obtained in step (1) above was used in an amount
of 12 g. The yield of the polymer was 35.8 g.
[0197] The thus-obtained aromatic vinyl graft copolymer had a total
ethylene copolymer macromer content of 34 wt. %. The ethylene
copolymer macromer had a limiting viscosity [.eta.] of 1.2 dl/g.
The graft ratio was 61.5 wt. %, and the tensile elongation was
88%.
Comparative Example 1
[0198] (1) Synthesis of ethylene copolymer macromer having no vinyl
groups
[0199] The procedure of Example 4 was repeated except that
p-divinylbenzene was not used in step (1), to thereby synthesize an
ethylene copolymer macromer having no vinyl groups.
[0200] The amount of the obtained ethylene copolymer was 125 g, and
the composition was confirmed to be
ethylene/styrene/divinylbenzene=73.6/26.4- /0 (mol %). The limiting
viscosity [.eta.] was 1.5.
[0201] (2) Synthesis of aromatic vinyl graft copolymer
[0202] The procedure of Example 4 was repeated except that ethylene
copolymer macromer obtained in the step (1) above was used instead.
The yield of the polymer was 15.9 g.
[0203] The thus-obtained product had a total ethylene copolymer
macromer content of 25 wt. %. The ethylene copolymer macromer had a
limiting viscosity [.eta.] of 1.5 dl/g. The graft ratio was 0 wt.
%, and the tensile elongation was 6%.
Comparative Example 2
[0204] Polystyrene having a homo-type syndiotactic structure
(Mw=200,000) and SEBS (G1651; manufactured by Shell Chemical Co.,
Ltd.) were mixed at a weight ratio of 80:20, and the mixture was
pelletized at 300.degree. C. by use of a biaxial extruder (30 mm.O
slashed.; manufactured by Ikegai Steelwork Co., Ltd.)
[0205] The thus-obtained product had an SEBS content of 20 wt. %.
The graft ratio was 0 wt. %, and the tensile elongation was
13%.
[0206] The respective evaluation items for the above aromatic vinyl
graft copolymer were measured as follows:
[0207] (1) Ethylene copolymer macromer content (wt. %)
[0208] This is represented by % by weight of ethylene copolymer
macromer contained in the aromatic vinyl graft copolymer, and
obtained through the following equation: amount of incorporated
ethylene copolymer macromer/amount of final polymer.
[0209] (2) Graft ratio (wt. %)
[0210] This is represented by the following expression: "weight of
grafted components among the segments of ethylene copolymer
(I)"/"weight of copolymer segments attributed to ethylene copolymer
(I) containing both grafted components and non-grafted components."
Specifically, "weight of grafted components among the segments of
ethylene copolymer (I)" represents the value of the total weight of
ethylene copolymer macromer minus the weight of non-grafted
ethylene copolymer macromer, and "weight of copolymer segments
attributed to ethylene copolymer (I) containing both grafted
components and non-grafted components" represents the total weight
of the ethylene copolymer macromer obtained in step (1) above. The
amount of non-grafted components is the weight of ethylene
copolymer which is recovered from a methylene chloride phase
obtained by subjecting a fine dry powder of the graft copolymer to
a 6hr Soxhlet extraction in methylene chloride.
[0211] (3) Tensile elongation (%)
[0212] A pellet of aromatic vinyl graft copolymer was heated to
300.degree. C. and shaped into a press sheet having a thickness of
100 .mu.m, followed by annealing at 200.degree. C. for 30 minutes
so as to fully crystallize. Subsequently, dumbbell-shaped test
pieces were punched out and subjected to a tensile elongation
test.
[0213] The tensile elongation test was performed by use of a
SHIMADZU AUTOGRAPH AG5000B. The dumbbell type was DIN-53504. The
tensile rate was 1.0 mm/sec, and the initial length was 20 mm.
[0214] As described above, the ethylene copolymers obtained by the
present invention are endowed with excellent heat resistance,
chemical resistance, etc., as well as with remarkable toughness,
elongation, and compatibility. Therefore, they are very useful in
the following applications among others: macromonomers for
obtaining syndiotactic polystyrene graft copolymers which are
advantageously used as a raw material for complex materials or
heat-resistant elastomers; and compatibility-enhancing agents for a
composition containing a syndiotactic polystyrene and a rubber
component or a composition containing typical polystyrene and a
rubber component.
* * * * *