U.S. patent application number 09/773904 was filed with the patent office on 2001-09-27 for aromatic vinyl resin material and molded products thereof.
This patent application is currently assigned to IDEMITSU PETROCHEMICAL CO., LTD.. Invention is credited to Sera, Masanori, Takebe, Tomoaki, Teshima, Hideo.
Application Number | 20010025085 09/773904 |
Document ID | / |
Family ID | 17780633 |
Filed Date | 2001-09-27 |
United States Patent
Application |
20010025085 |
Kind Code |
A1 |
Teshima, Hideo ; et
al. |
September 27, 2001 |
Aromatic vinyl resin material and molded products thereof
Abstract
The present invention provides resin materials for producing
molded products endowed with excellent heat resistance, solvent
resistance, toughness, tensile elongation, and transparency.
Specifically, there are provided aromatic vinyl resin materials
which have the following properties: Storage elasticity values
G'(1.0) and G'(0.1) as measured at 300.degree. C., a strain .gamma.
of 20%, and a frequency of 1.0 Hz or 0.1 Hz satisfy the expression,
log[G'(1.0)/G'(0.1)].ltoreq.0.6, the heat of fusion .DELTA.H as
measured over the range 200-295.degree. C. is 8 to 50 (J/g), and
the .sup.1H-NMR peak integrated values for the fraction
corresponding to the temperature range of not lower than 50.degree.
C., as collected from temperature rising election fraction on the
Soxhlet extraction residue by use of cyclohexane or
o-dichlorobenzene, satisfy the relation [1.8-2.1
(ppm)]/[1.0-1.7(ppm))<0.49.
Inventors: |
Teshima, Hideo;
(Ichihara-shi, JP) ; Takebe, Tomoaki;
(Ichihara-shi, JP) ; Sera, Masanori;
(Ichihara-shi, 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
|
Family ID: |
17780633 |
Appl. No.: |
09/773904 |
Filed: |
February 2, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09773904 |
Feb 2, 2001 |
|
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|
09177559 |
Oct 23, 1998 |
|
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6207753 |
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Current U.S.
Class: |
525/315 ;
525/316; 525/324 |
Current CPC
Class: |
C08F 290/044 20130101;
C08F 290/04 20130101 |
Class at
Publication: |
525/315 ;
525/316; 525/324 |
International
Class: |
C08F 255/02; C08F
210/02; C08F 212/06; C08F 212/08; C08F 279/00; C08F 279/02 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 24, 1997 |
JP |
9-292347 |
Claims
What is claimed is:
1. An aromatic vinyl resin material which satisfies the
relationship represented by the following expression: SG
value=log[G'(1.0)/G'(0.1)]<- ;0.6 wherein G'(1.0) is a
storage modulus as measured at a temperature of 300.degree. C., a
strain .gamma. of 20%, and a frequency of 1.0 Hz, and G'(0.1) is a
storage modulus as measured at a temperature of 300.degree. C., a
strain .gamma. of 20%, and a frequency of 0.1Hz.
2. An aromatic vinyl resin material having the following
properties; 1) the heat of fusion .DELTA.H as measured over the
range 200-295.degree. C. with a differential scanning calorimeter
is 8 to 50 (J/g), 2) in .sup.1H-NMR performed on the residue
obtained from Soxhlet extraction using cyclohexane, B/A<0.49
wherein A is an integrated value of a peak appearing at 1.0-1.7
(ppm) and B is an integrated value of a peak appearing at 1.8-2.1
(ppm), and 3) a tensile elongation of not less than 5%.
3. An aromatic vinyl resin material having the following
properties: 1) the heat of fusion .DELTA.H as measured over the
range 200-295.degree. C. with a differential scanning calorimeter
is 8 to 50 (J/g), 2) in .sup.1H-NMR performed on the fraction
eluted at 50.degree. C. or higher through temperature rising
election fraction by use of o-dichlorobenzene (hereinafter referred
to simply as fractionation by o-dichlorobenzene), B/A<0.49
wherein A is an integrated value of a peak appearing at 1.0-1.7
(ppm) and B is an integrated value of a peak appearing at 1.8-2.1
(ppm), and 3) a tensile elongation of not less than 5%.
4. An aromatic vinyl resin material according to claim 1, which is
a graft copolymerization product of an aromatic vinyl monomer (a)
and an ethylene copolymer macromer (b).
5. An aromatic vinyl resin material according to claim 2, which is
a graft copolymerization product of an aromatic vinyl monomer (a)
and an ethylene copolymer macromer (b).
6. An aromatic vinyl resin material according to claim 3, which is
a graft copolymerization product of an aromatic vinyl monomer (a)
and an ethylene copolymer macromer (b).
7. An aromatic vinyl resin material according to claim 4, wherein
the ethylene copolymer macromer (b) is a copolymerization product
of ethylene, a diene monomer, and an optional aromatic vinyl
monomer and optional .alpha.-olefin.
8. An aromatic vinyl resin material as described above in claim 1,
which has a composition composed of (A) an aromatic vinyl polymer,
(B) an ethylene copolymer having a diene-monomer-derived vinyl
group in the molecular chain, and (C) a graft copolymerization
product of an aromatic vinyl monomer (a) and an ethylene copolymer
macromer (b).
9. An aromatic vinyl resin material according to claim 4, in which
a moiety derived from an aromatic vinyl monomer predominantly has a
syndiotactic structure.
10. An aromatic vinyl resin material according to claim 5, in which
a moiety derived from an aromatic vinyl monomer predominantly has a
syndiotactic structure.
11. An aromatic vinyl resin material according to claim 6, in which
a moiety derived from an aromatic vinyl monomer predominantly has a
syndiotactic structure.
12. An aromatic vinyl resin material according to claim 7, in which
a moiety derived from an aromatic vinyl monomer predominantly has a
syndiotactic structure.
13. An aromatic vinyl resin material according to claim 8, in which
a moiety derived from an aromatic vinyl monomer predominantly has a
syndiotactic structure.
14. An aromatic vinyl resin material having a composition composed
of an aromatic vinyl resin material according to claim 1 and a
styrene polymer predominantly having a syndiotactic structure
and/or a rubber-like elastic substance.
15. A molded product obtained through molding of an aromatic vinyl
resin material as described in claims 1.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to an aromatic vinyl resin
material and an aromatic vinyl resin molded product, and more
particularly to an aromatic vinyl resin material that is endowed
with excellent heat resistance, solvent resistance, toughness,
tensile elongation, and transparency, and to an aromatic vinyl
resin molded product thereof.
[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. 62-104818, 63-241009). The
styrene polymer having a syndiotactic structure (hereinafter simply
referred to as "syndiotactic polystyrene" or "SPS") is endowed with
excellent heat resistance and solvent 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. When SPS is used for producing a film that
requires transparency, SPS is cooled rapidly from the molten state
to acquire transparency. However, the thus-obtained film has a
drawback in that it is brittle.
[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, 4-300904).
[0006] However, 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.
[0007] There have been proposed a large number of compositions in
which a rubber-like elastic substance or thermoplastic resin is
added to SPS (Japanese Patent Application Laid-Open (kokai) Nos.
01-146944 and 01-279944). However, due to lack of an effective
compatibility-enhancing agent, dispersion of thermoplastic resin or
the like is insufficient, resulting in deterioration in
transparency.
[0008] There have also been proposed graft copolymers in which a
styrene monomer is graft-copolymerized with a polymer bearing
double bonds in side chains, as well as block copolymers in which a
styrene monomer is block-copolymerized with a macromonomer bearing
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 are
inhomogeneous in copolymer composition and exhibit insufficient
graft ratio, resulting in insufficient improvement in targeted
properties such as toughness, elongation, and impact
resistance.
[0009] In view of the foregoing, an object of the present invention
is to provide an aromatic vinyl resin material for producing a
molded product which is endowed with heat resistance, solvent
resistance, toughness, tensile elongation, and transparency, as
well as to provide a molded product of the resin material.
SUMMARY OF THE INVENTION
[0010] The present inventors carried out extensive studies, and as
a result, found that toughness of a certain resin material is
related to frequency dependency of storage modulus of the material
and that the heat of fusion .DELTA.H over a certain temperature
range and the amount of graft components present in the polymer are
related to good toughness, elongation, and transparency, thus
achieving the present invention.
[0011] Specifically, the present invention provides:
[0012] (1) an aromatic vinyl resin material which satisfies the
relationship represented by the following expression:
SG value=log[G'(1.0)/G'(0)]<0.6
[0013] wherein G'(1.0) is a storage modulus as measured at a
temperature of 300.degree. C., a strain .gamma. of 20%, and a
frequency of 1.0 Hz, and G'(0.1) is a storage modulus as measured
at a temperature of 300.degree. C., a strain .gamma. of 20%, and a
frequency of 0.1 Hz;
[0014] (2) an aromatic vinyl resin material having the following
properties:
[0015] 1) the heat of fusion .DELTA.H as measured over the range
200-295.degree. C. with a differential scanning calorimeter is 8 to
50 (J/g),
[0016] 2) in .sup.1H-NMR performed on the residue obtained from
Soxhlet extraction using cyclohexane,
B/A<0.49
[0017] wherein A is an integrated value of a peak appearing at
1.0-1.7 (ppm) and B is an integrated value of a peak appearing at
1.8-2.1 (ppm), and
[0018] 3) a tensile elongation of not less than 5%;
[0019] (3) an aromatic vinyl resin material having the following
properties:
[0020] 1) the heat of fusion .DELTA.H as measured over the range
200-295.degree. C. with a differential scanning calorimeter is 8 to
50 (J/g),
[0021] 2) in 1H-NMR performed on the fraction eluted at 50.degree.
C. or higher through temperature rising election fraction by use of
o-dichlorobenzene (hereinafter referred to simply as fractionation
by o-dichlorobenzene), B/A<0.49 wherein A is an integrated value
of a peak appearing at 1.0-1.7 (ppm) and B is an integrated value
of a peak appearing at 1.8-2.1 (ppm), and
[0022] 3) a tensile elongation of not less than 5%;
[0023] (4) an aromatic vinyl resin material as described above in
any of (1) to (3), wherein the aromatic vinyl resin material is a
graft copolymerization product of an aromatic vinyl monomer (a) and
an ethylene copolymer macromer (b);
[0024] (5) an aromatic vinyl resin material as described above in
(4), in which the ethylene copolymer macromer (b) is a
copolymerization product of ethylene, a diene monomer, and an
optional aromatic vinyl monomer and optional a-olefin;
[0025] (6) an aromatic vinyl resin material as described above in
any of (1) to (3), which has a composition composed of (A) an
aromatic vinyl polymer, (B) an ethylene copolymer having a
diene-monomer-derived vinyl group in the molecular chain, and (C) a
graft copolymerization product of an aromatic vinyl monomer (a) and
an ethylene copolymer macromer (b);
[0026] (7) an aromatic vinyl resin material as described above in
any of (4) to (6), in which a moiety derived from an aromatic vinyl
monomer predominantly has a syndiotactic structure;
[0027] (8) an aromatic vinyl resin material having a composition
composed of an aromatic vinyl resin material as described above in
any of (1) to (7) and a styrene polymer predominantly having a
syndiotactic structure and/or a rubber-like elastic substance;
and
[0028] (9) a molded product obtained through molding of an aromatic
vinyl resin material as described above in any of (1) to (8)
DESCRIPTION OF THE PREFERRED MODIMENTS
[0029] Embodiments of the present invention will next be
described.
[0030] 1. Aromatic Vinyl Resin Material
[0031] (1) An aromatic vinyl resin material according to the
present invention is such that the storage modulus (G'(1.0)) as
measured at a temperature of 300.degree. C., a strain .gamma. of
20%, and at a frequency of 1.0 Hz and the storage modulus (G'(0.1))
as measured at a temperature of 300.degree. C., a strain .gamma. of
20%, and at a frequency of 0.1 Hz satisfy the relationship
represented by the following expression.
SG value=log[G'(1.0)/G'(0.1)].ltoreq.0.6
[0032] wherein the storage modulus G'(dyne/cm.sup.2) is measured at
a temperature of 300.degree. C., a strain .gamma. of 20%, and a
frequency ranging from 10.sup.-2 Hz to 10.sup.2 Hz through use of
cone plate type rheometer (manufactured by Rheometric Scientific).
G'(1.0) denotes a GI value as measured at a frequency of 1.0 Hz. A
test piece for measurement is manufactured in the following manner.
Briefly, a sample to be measured is pelletized at 300.degree. C.
through use of a small-size kneader. The resultant pellets are
pressed into a sheet (1.0 mm thick) at 300.degree. C., obtaining a
test piece.
[0033] (2) An aromatic vinyl resin material according to the
present invention has the following properties:
[0034] 1) The heat of fusion .DELTA.H as measured over the range
200-295.degree. C. with a differential scanning calorimeter is 8 to
50 (J/g), preferably 10 to 40 (J/g), more preferably 15 to 30
(J/g).
[0035] The heat of fusion .DELTA.H as measured over the range
200-295.degree. C. with a differential scanning calorimeter is
specifically obtained in the following manner. A differential
scanning calorimeter to be used is of model DSC7 manufactured by
Perkin-Elmer Corp. Ten milligrams of a sample are heated to melt in
a nitrogen atmosphere at 300.degree. C. for 5 minutes. The
resulting melt is cooled to 50.degree. C. at a cooling rate of
20.degree. C./min and held at this temperature for 1 minute.
Subsequently, the sample is heated at a rate of 20.degree. C./min,
obtaining a melting endothermic curve. Based on the-obtained curve,
the heat of fusion over the range 200-295.degree. C. is calculated.
When the heat of fusion .DELTA.H is less than 8 (J/g), heat
resistance and solvent resistance may deteriorate. When the heat of
fusion .DELTA.H is in excess of 50 (J/g), toughness may
deteriorate.
[0036] 2) In .sup.1H-NMR performed on the residue obtained in
Soxhlet extraction using cyclohexane: B/A<0.49, preferably
B/A<0.45, more preferably B/A<0.40 (wherein A is an
integrated value of a peak appearing at 1.0-1.7 (ppm) and B is an
integrated value of a peak appearing at 1.8-2.1 (ppm)).
[0037] 3) Tensile elongation is not less than 5%, preferably not
less than 10%, more preferably not less than 20%.
[0038] Tensile elongation is obtained in the following manner. A
sample is press-formed at 300.degree. C. and then cooled through
use of a cold press (die temperature: 30.degree. C.), thereby
obtaining film having a thickness of 100 .mu.m. The film is
annealed at 150.degree. C. for 3 hours and then cooled to room
temperature. A tensile test piece having a dumbbell shape is
blanked out from the film through use of a blanking die having the
S3 size of DIN53504. The test piece is subjected to a tensile test
through use of Autograph AG5000B (manufactured by Shimadzu corp.)
under the following conditions: initial distance between chucks: 20
mm; and pulling rate: 1 mm/min.
[0039] A tensile elongation less than 5% indicates that toughness
of a resin-molded product is relatively low.
[0040] (3) An aromatic vinyl resin material according to the
present invention has the following properties.
[0041] 1) The heat of fusion .DELTA.H as measured over the range
200-295.degree. C. through use of a differential scanning
calorimeter is 8 to 50 (J/g), preferably 10 to 40 (J/g), more
preferably 15 to 30 (J/g).
[0042] 2) In .sup.11-NMR performed on the fraction eluted at
50.degree. C. or higher through fractionation by use of
o-dichlorobenzene, B/A<0.49, preferably B/A<0.45, more
preferably B/A<0.40 (wherein A is an integrated value of a peak
appearing at 1.0-1.7 (ppm) and B is an integrated value of a peak
appearing at 1.8-2.1 (ppm)).
[0043] It will suffice so long as at least either the residue
obtained in Soxhlet extraction using cyclohexane or the fraction
eluted at 50.degree. C. or higher in fractionation using
o-dichlorobenzene satisfies the above requirement for B/A. When B/A
is not less than 0.49, toughness may deteriorate.
[0044] Preferably, in .sup.1H-NMR performed on the fraction eluted
at 110.degree. C. or higher through fractionation using
o-dichlorobenzene, the relation B/A<0.49 is satisfied. More
preferably, in .sup.1H-ER performed on the fraction eluted at
125.degree. C. or higher through fractionation using
o-dichlorobenzene, the relation B/A<0.49 is satisfied.
[0045] The fraction eluted at T.degree. C. or higher in
fractionation using c-dichlorobenzene (ODCB) is obtained in the
following manner. Briefly, 250 milliliters of CDCB is added to 20 g
of sample. The resultant mixture is heated to about 150.degree. C.
and completely dissolved. Subsequently, the resultant solution is
placed in a silica gel column and then cooled to 30.degree. C. at a
cooling rate of 5.degree. C./hour. Next, while letting ODCB flow at
a rate of 10 milliliters/rain, temperature is raised to T.degree.
C. At a constant temperature of T.degree. C., the polymer is eluted
for separation. Then, temperature is raised to 135.degree. C. so as
to completely elute the polymer. The polymer eluted over the
temperature range T-135.degree. C. is precipitated in methanol and
recovered. The thus-collected polymer serves as the fraction eluted
at T.degree. C. or higher in the fractionation.
[0046] .sup.1H-NMR data were obtained through use of the NMR
apparatus, model JNM-EX400, manufactured by JEOL LTD., under the
following conditions: solvent: 1,2,4-trichlorobenzene/benzene
d.sub.6=4/1; temperature of sample: 130.degree. C.; accumulation:
256; pulse angle: 45 degrees; and pulse interval: 9 sec.
[0047] 3) Tensile elongation is not less than 5%, preferably not
less than 10%, more preferably not less than 20%.
[0048] Tensile elongation is obtained in the following manner. A
sample is press-formed at 300.degree. C. and then cooled with a
cold press (die temperature: 30.degree. C.), to thereby obtain film
having a thickness of 100 .mu.m. The film is annealed at
150.degree. C. for 3 hours and then cooled to room temperature. A
tensile test piece having a dumbbell shape is blanked out from the
film through use of a blanking die having the S3 size of DIN53504.
The test piece is subjected to a tensile test through use of
Autograph AG5000B (manufactured by Shiradzu Corp.) under the
following conditions: initial distance between chucks: 20 mm;
pulling rate: 1 mm/min.
[0049] A tensile elongation less than 5% indicates that toughness
of a resin-molded product is relatively low.
[0050] (4) Preferably, an aromatic vinyl resin material according
to the present invention has the following properties:
[0051] 1) Internal haze is not greater than 70%, preferably not
greater than 55%, more preferably not greater than 40%.
[0052] Internal haze is measured in the following manner. A sample
is press-formed at 300.degree. C. and then immediately immersed
into ice water for rapid cooling, to thereby obtain a rapidly
cooled film having a thickness of 25 .mu.m. The film is measured
for internal haze according to JIS K7105. In this case, silicone
oil is applied to one side of each of two glass plates, and the
film is sandwiched between the oil-applied surfaces. A measured
value is corrected on the basis of a blank value as measured
without the film being interposed between the surfaces.
[0053] An internal haze in excess of 70% indicates that
transparency is relatively low.
[0054] 2) The average size of domain component grains obtained by a
light scattering method is 0.01 .mu.m to 3 .mu.m, preferably 0.05
.mu.m to 2 .mu.m, more preferably 0-1 .mu.m to 1 .mu.m.
[0055] The average size of domain component grains is obtained in
the following manner. A sample is press-formed at 300.degree. C.
and then immediately immersed into ice water for rapid cooling,
thereby obtaining a rapidly cooled film having a thickness of 25
.mu.m. A He--Ne laser beam having a wavelength (.lambda.) of 633 nm
is made to impinge onto the film. Scattered light from the film is
measured through use of a photodiode array primary detector to
thereby obtain scattered light intensity distribution I as a
function of scattering angle (.theta.). The natural logarithm of
I(.theta.), lnI(.theta.), is plotted with respect to
(4.pi.n/.lambda.).sup.2sin(.theta./2).sup.2 to thereby obtain an
absolute value Ai of initial inclination. Based on R=(3Ai).sup.1/2,
the domain component's grain size (R) is calculated.
[0056] 2. Specific Embodiments of Aromatic Vinyl Resin Material
[0057] Specific embodiments of the aromatic vinyl resin material
according to the present invention are not particularly limited.
However, the following embodiments (I) to (III) are preferred.
[0058] (I) A graft copolymerization product of an aromatic vinyl
monomer (a) and an ethylene copolymer macromer (b), in which the
ethylene copolymer macromer (b) is a copolymer of ethylene, a diene
monomer, an optional aromatic vinyl monomer, and an optional
a-olefin.
[0059] (II) An aromatic vinyl resin composition composed of (A) an
aromatic vinyl polymer, (B) an ethylene copolymer having a
diene-monomer-derived vinyl group in the molecular chain, and (C) a
graft copolymerization product of an aromatic vinyl monomer (a) and
an ethylene copolymer macromer (i.e., corresponding to the above
copolymer of (I)).
[0060] (III) An aromatic vinyl resin composition composed of an
aromatic vinyl resin material as described above in (I) or (II) and
a styrene polymer predominantly having a syndiotactic structure
and/or a rubber-like elastic material.
[0061] The above-mentioned cases (I) through (III) will next be
described in detail.
[0062] (I) A graft copolymerization product of an aromatic vinyl
monomer (a) and an ethylene copolymer macromer (b):
[0063] (I-l) An example aromatic vinyl monomer (a) is represented
by the following formula (1): 1
[0064] wherein X.sup.1 represents a member which falls within the
following cases 1), 2), or 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; a
represents an integer between 1 and 5 inclusive, wherein when a
.gtoreq.2, X.sup.1 may be identical to or different from one
another. Specifically, mention may be given of styrene;
alkylstyrenes such as p-methylstyrene, m-methylystyrene,
o-methyltyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene,
3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene,
m-ethylstyrene, 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 silyl styrenes.
Mixtures of two or more of these members are also usable. In
addition, vinylnaphthalenes, vinylanthracenes, and their
substituents may also be used.
[0065] (I-2) Ethylene Copolymer Macromer (b)
[0066] The ethylene copolymer macromer (b) is a copolymerization
product obtained by subjecting ethylene, a diene monomer, an
optional aromatic vinyl monomer, and optional .alpha.-olefin to
copolymerization reaction. The macromer (b) is thus an ethylene
copolymer primarily containing a diene-monomer-derived vinyl group
in the molecular chain.
[0067] 1) Ethylene
[0068] No particular limitation is imposed, and a hydrogen may be
substituted by a halogen, etc.
[0069] 2) Diene Monomer
[0070] As used herein, the diene monomer is a monomer having two or
more C.dbd.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, 1,3,5-hexatriene,
1,3,6-heptatriene; 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 (2) and (3), are used. 2
[0071] wherein each of X.sup.2, X.sup.3and X.sup.4 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; each of Y.sup.1 and Y.sup.2 represents CH.sub.2,
an alkylene group, or an alkyledene group; each of b and c
represents an integer between 0 and 20 inclusive.
[0072] Specific examples of the compounds represented by formula
(2) include o-divinylbenzene, m-divinylbenzene, p-divinylbenzene,
(o-, m-, p-)divinyltoluene, (o-, m-, p-)2-propenylstyrene, (o-, m-,
p-)3-butenylstyrene, and (o-, m-, p-) 4-pentenylstyrene.
[0073] Examples of the compounds represented by formula (3) include
the compounds described below. 3
[0074] 3) Aromatic Vinyl Monomer
[0075] Aromatic vinyl monomers which are usable in the present
invention are selected from the compounds described above.
[0076] 4) .alpha.-Olefins
[0077] Monomers which are usable in the present invention are
.alpha.-olefin monomers 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-m-
ethylhexene-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 Copolymer Macromers (b) are Obtained through
Copolymerization of the Above-Listed Monomers.
[0079] <5)-i> With regard to the ethylene copolymer macromers
(b), recurrent units derived from ethylene are preferably contained
in an amount of 99-1 mol %, more preferably 90-20 mol %, still more
preferably 80-30 mol %. Recurrent units derived from diene monomer
are preferably contained in an amount of 10-0.001 mol %, more
preferably 5-0.01 mol %, still more preferably 1-0.05 mol %. In the
case in which aromatic vinyl monomers or .alpha.-olefins are used
as monomers, recurrent units derived from aromatic vinyl monomer
are in amounts of 0-70 mol %, preferably 0-50 mol %, more
preferably 0-30 mol % (exclusive of 0), and recurrent units derived
from .alpha.-olefin are in amounts of 0-70 mol %, preferably 0-50
mol %, more preferably 0-20 mol % (exclusive of 0) In the case in
which the amount of ethylene-derived recurrent units is in excess
of 99 mol %, solubility of the macromers (b) in styrene monomers
becomes low, and subsequently, it becomes difficult to carry out
graft copolymerization. In the case in which the amount of
ethylene-derived recurrent units is less than 1 mol %, macromers
(b) may not function as rubbers. In the case in which the amount of
recurrent units derived from diene is in excess of 10 mol %,
cross-linking may occur along with graft copolymerization. In the
case in which the amount of recurrent units derived from diene is
less than 0.001 mol %, graft copolymerization may not proceed
sufficiently. In the case in which the amount of
aromatic-vinyl-monomer-d- erived recurrent units is in excess of 70
mol %, grass transition temperature may decrease to thereby
deteriorate rubber elasticity. In the case in which the amount of
.alpha.-olefin-derived recurrent units is in excess of 70 mol %,
the macromers (b) tend to form crystals to result in poor
solubility during graft copolymerization.
[0080] <5)-ii> The limiting viscosity [.eta.] of the ethylene
copolymer macromers (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. In the case in which the limiting viscosity is in
excess of 15 dl/g, the viscosity of the macromers (b), when they
are in the form of solution, increases and, as a result, graft
copolymerization may become difficult to carry out. The molecular
weight distribution of the macromers (b) as measured by GPC (gel
permeation chromatography) is 8 or less, preferably 6 ore 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] <5)-iii> Methods for producing ethylene copolymer
macromers (b)
[0082] Methods for producing the ethylene copolymer macromers (b)
are not particularly limited. For example, in order to produce the
macromers (b), it is preferable to carry out copolymerization by
use of 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.
Alternatively and preferably, the macromers (b) may be prepared
through copolymerization by use of a catalyst formed of the
following (a), (b), and (c). (a): a transition metal compound, (b):
an oxygen-containing compound (i) and/or a compound capable of
forming an ionic complex through reaction with transition metal
compound (a) (ii), and (c): an optional alkylation agent.
[0083] <5)-iii-l> Respective Components of the Catalyst
[0084] (a) Transition Metal Compounds:
[0085] various transition metal compounds may be used as the
transition metal compound (a). Usually, it is preferable to use the
compounds shown below.
[0086] (i) Compounds of formula (4): 4
[0087] wherein M.sup.1 represents a metal which belongs to Groups
3-10 of a periodic table or the lanthanoid group; each of E.sup.1
and E.sup.2 represents a ligand selected from among 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,
an octahydrofluorenyl group, a substituted octahydrofluorenyl
group, a heterocyclopentadienyl group, a substituted
heterocyclopentadienyl group, an amido group, a phosphide group, a
hydrocarbon group, and a silicon-containing group, wherein E.sup.1
and E.sup.2 are identical to or different from each other and form
a crosslinked structure together with A.sup.1 and A.sup.2; X5
represents a ligand which may form a .sigma.-bond, wherein when a
plurality of X.sup.5 are present, they may be identical to or
different from one another and may be cross-linked with other
X.sup.5, E.sup.1, E.sup.2, or Y.sup.3; Y.sup.3 represents a Lewis
base, wherein when a plurality of Y.sup.3 are present, they may be
identical to or different from one another and may be cross-linked
with other Y.sup.3, E.sup.1, E.sup.2, or X.sup.5; A.sup.1 and
A.sup.2 represent cross-linking groups formed of hydrocarbon groups
having one or more carbon atoms which may be identical to or
different from one another; d is an integer between 1 and 5
inclusive and represents "(valences of M.sup.1)-2"; and e is an
integer between 0 and 3 inclusive.
[0088] Specific examples of X.sup.5 include a halogen atom, a
C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a C6-C20 aryloxy
group, a C1-C20 amido group, a C1-C20 silicon-containing group, a
C1-C20 phosphide group, a C1-C20 sulfide group, and a C1-C20 acyl
group. Specific examples of Y3 include amines, ethers, phosphines,
and thioethers. Specific examples of A.sup.1 and A.sup.2 include a
group of formula (5) below: 5
[0089] wherein each of T.sup.1 and T.sup.2, which may be identical
to or different from each other, represents a hydrogen atom or a
C1-C20 hydrocarbon group and may be linked to each other to form a
ring; and f is an integer between 1 and 4 inclusive. Specific
examples of the formula (5) group include a methylene group, an
ethylene group, an ethylidene group, a propylidene group, an
isopropylidene group, a cyclohexylidene group, a 1,2-cycrohexylene
group, and a vinylidene group (CH.dbd.CO.dbd.). Of these groups,
the methylene group, ethylene group, and isopropylidene group are
preferred.
[0090] Specific examples of the transition metal compounds of
formula (4) include (1,1'-ethylene)(2,2'-ethylene)-bis
(indenyl)zirconium dichloride,
(1,2'-ethylene)(2,1'-ethylene)-bis(indenyl)zirconium dichloride,
(1,1'-methylene) (2,2'-methylene)-bis(indenyl)zirconium dichloride,
(1,2'-methylene)(2,1-methylene)-bis(indenyl)zirconium dichloride,
(1,1'-isopropylidene)(2,2'-isopropylidene)-bis(indenyl) zirconium
dichloride,
(1,2'-isopropylidene)(2,1'-isopropylidene)-bis(indenyl)zircon- ium
dichloride, (1,1'-ethylene) (2,2'-ethylene)-bis (3-methylindenyl)
zirconium dichloride,
(1,2'-ethylene)(2,1'-ethylene)-bis(3-methylindenyl)- zirconium
dichloride, (1,1'-ethylene)(2,2'-ethylene)-bis(4,5-benzoindenyl)-
zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene)-bis
(4,5-benzoindenyl)zirconium dichloride,
(1,1'-ethylene)(2,2'-ethylene)-bi- s(4-isopropylindenyl) zirconium
dichloride, (1,2'-ethylene)
(2,1'-ethylene)-bis(4-isoprcpylindenyl)zirconium dichloride, (1,140
-ethylene)(2,2'-ethylene)-bis (5,6-dimethylindenyl) zirconium
dichloride, (1,2'-ethylene)(2,1'-ethylene)-bis
(5,6-dimethylindenyl)zirconium dichloride, (1,1'-ethylene)
(2,2'-ethylene)-bis(4,7-diisopropylindenyl)zi- rconium dichloride,
(1,2'-ethylene)(2,1'-ethylene)-bis(4,7-diisopropylinde-
nyl)zirconium dichloride, (1,1'-ethylene)
(2,2'-ethylene)-bis(4-phenylinde- nyl)zirconium dichloride,
(1,2'-ethylene)(2,1'-ethylene)-bis(4-phenylinden- yl)zirconium
dichloride, (1,1'-ethylene)(2,2'-ethylene)-bis(3-methyl-4-iso-
propylindenyl)zirconium dichloride,
(1,2'-ethylene)(2,1'-ethylene)-his(3-m-
ethyl-4-isopropylindenyl)zirconium dichloride,
(1,1'-ethylene)(2,2'-ethyle- ne)-bis(5,6-benzo indenyl)zirconium
dichloride, (1,2'-ethylene)(2,1'-ethyl-
ene)-bis(5,6-benzoindenyl)zirconium dichloride,
(1,1'-ethylene)(2,2'-isopr- opylidene)-bis(indenyl)zirconium
dichloride, (1,2'-ethylene)(2,1'-isopropy- liene)-bis(indenyl)
zirconium dichloride, (1,1,'-isopropylidene)(2,2'-ethy-
lene)-bis(indenyl)zirconium dichloride,
(1,2'-methylene)(2,1'-ethylene)-hi- s(indenyl)zirconium dichloride,
(1,1'-methylenre)(2,2'-ethylene)-bis(inden- yl)zirconium
dichloride, (1,1'-ethylene)(2,2'-methylene)-bis(indenyl)zirco- nium
dichloride, (1,1'-methylene)(2,2'-isopropylidene)
-bis(indenyl)zirconium dichloride,
(1,2'-methylene)(2,1'-isopropylidene)-- bis(indenyl)zirconium
dichloride, (1,1'-isopropylidene)(2,2'-methylene)-bi-
s(indenyl)zirconium dichloride,
(1,1'-methylene)(2,2'-methylene)(3-methylc-
yclopentadienyl)(cyclopentadienyl)zirconium dichloride,
(1,1'-isopropylidene)(2,2'-isopropylidene)(3-methylcyclopentadienyl)(cycl-
opentadienyl)zirconium dichloride,
(1,1'-propylidene)(2,2'-propylidene)(3--
methylcyclopentadienyl)(cyclopentadienyl)zirconium dichloride,
(1,1'-ethylene)(2,2'-methylene)-bis(3-methylcyclopentadienyl)zirconium
dichloride,
(1,1'-methylene)(2,2'-ethylene)-bis(3-methylcyclopentadienyl)
zirconium dichloride,
(1,1'-isopropylidene)(2,2'-ethylene)-bis(3-methylcy-
clopentadienyl)zirconium dichloride,
(1,1'-ethylene)(2,2'-isopropylidene)--
bis(3-methylcyclopentadienyl-1) zirconium dichloride,
(1,1'-methylene)(2,2'-methylene)-bis
(3-methylcyclopentadienyl)zirconium dichloride,
(1,1'-methylene)(2,2'-isopropylidene)-bis(3-methylcyclopentad-
ienyl)zirconium dichloride,
(1,1'-isopropylidene)(2,2'-isopropylidene)-bis-
(3-methylcyclopentadienyl)zirconium dichloride,
(1,1'-ethylene)(2,2'-methy- lene)-bis(3,4-dimethylcyclopentadienyl)
zirconium dichloride,
(1,1'-ethylene)(2,2'-isopropylidene)-bis(3,4-dimethylcyclopentadienyl)zir-
conium dichloride,
(1,1'-methylene)(2,2'-methylene)-bis(3,4-dimethylcyclop-
entadienyl)zirconium dichloride,
(1,1'-methylene)(2,2'-isopropylidene)-bis-
(3,4-dimethylcyclopentadienyl)zirconium dichloride,
(1,1'-isopropylidene)(2,2'-isopropylidene)-bis(3,4-dimethylcyclopentadien-
yl)zirconium dichloride,
(1,2'-ethylene)(2,1'-methylene)-bis(3-methylcyclo- pentadienyl)
zirconium dichloride, (1,2'-ethylene)(2,1'-isopropylidene)-bi-
s(3-methylcyclopentadienyl)zirconium dichloride,
(1,2'-methylene)(2,1'-met- hylene)-bis(3-methylcyclopentadienyl)
zirconium dichloride,
(1,2'-methylene)(2,1'-isopropylidene)-bis(3-methylcyclopentadienyl)zircon-
ium dichloride,
(1,2'-isopropylidene)(2,1'-isopropylidene)-bis(3-methylcyc-
lopentadienyl)zirconium dichloride,
(1,2'-ethylene)(2,1'-methylene)-bis(3,- 4-dimethylcyclopentadienyl)
zirconium dichloride, (1,2'-ethylene)(2,1'-iso-
propylidene)-bis(3,4-dinethylcyclopentadienyl)zirconium dichloride,
(1,2'-methylene)(2,1'-methylene)-bis(3,4-dimethylcyclopentadienyl)
zirconium dichloride,
(1,2'-methylene)(2,1'-isopropylidene)-bis(3,4-dimet-
hylcyclopentadienyl)zirconium dichloride, and
(1,2'-isopropylidene)(2,1'-i-
sopropylidene)-bis(3,4-dimethylcyclopentadienyl) zirconium
dichloride. Compounds corresponding to these compounds in which
zirconium has been replaced by titanium or hafnium may also be
used. However, the transition metal compounds which are useful in
the present invention are not limited only to the above-listed
compounds. Also, analogs of the metal elements belonging to other
groups or lanthanoid group may be used.
[0091] (ii) Compounds represented by the following formula (6) or
(7): 6
[0092] wherein each of E.sup.3, E.sup.4, E.sub.5, and E.sup.6,
which may be identical to or different from each other, represents
a substituted or unsubstituted 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, an octahydrofluorenyl group,
or a substituted octahydrofluorenyl group; each of A.sup.3 and
A.sup.4, which may be identical to or different from each other,
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
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.3 and E.sup.4, 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.3 and A.sup.4 may be linked to each other to
form a ring together with Q; each of R.sup.1, R.sup.2, R.sup.3 and
R.sup.4, which may be identical to or different from each other,
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.2 and
M.sup.3 represents titanium, zirconium, or hafnium.
[0093] Specific examples of E.sup.3, E.sup.4, E.sup.3 and E.sup.6
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, a hexahydroazulenyl group, an
octahydrofluorenyl group, and a 2,7-di-t-butylfluorenyl group.
[0094] Specific examples of A.sup.3 and A.sup.4 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.
[0095] In the case in which A.sup.3 and A.sup.4 are linked to each
other and form a ring structure together with Q, specific examples
of groups which may be formed by A.sup.3, A.sup.4, and Q include a
cyclopentylidene group, a cyclohexylidene group, and a
tetrahydropyran-4-ylidene.
[0096] Preferable examples of R.sup.1, R.sup.2, R.sup.3 and R.sup.4
include a chlorine atom, a methyl group, a phenyl group, and a
trimethylsilylmethyl group.
[0097] 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, diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium
dichloride, isopropylidene(9-fluorenyl)(1-indenyl)zirconium
dichloride, dimethylsilyl-bis-(2-methylindenyl) zirconium
dichloride, dimethylsilyl-bis-(2-methylbenzoindenyl) -zirconium
dichloride, dimethylsilyl-bis-(2-methyl-4-phenylindenyl)zirconium
dichloride, and
dimethylsilyl-bis-(2-methyl-4-naphthylindenyl)zirconium
dichloride.
[0098] (iii) Compounds represented by the following formula (8):
7
[0099] wherein M.sup.4 represents titanium, zirconium, or hafnium;
Cp* represents 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,
an octahydrofluorenyl group or a substituted octahydrofluorenyl
group, each of which is bonded to M.sup.4 via a .eta..sup.5 bonding
mode; X.sup.6 represents a .sigma. ligand; g represents 1 or 2; a
plurality of X.sup.6 may be identical to or different from one
another and may be linked together via an arbitrary group; Y.sup.4
represents O, S, NR, CR.sub.2, or a neutral two-electron donor
selected from OR, SP, NR.sub.2, or PR.sub.z; Z.sub.1 represents
SiR.sub.2, CR.sub.2, SiR.sub.2SiR.sub.2, CR.sub.2CR.sub.2,
CR.dbd.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.4 and Z.sup.1.
[0100] 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)cyclopentad- ienyl group, a tertiary
butylcyclopentadienyl group, a 1,3-di(tertiary butyl)
cyclopentadienyl group, a C1-C20 hydrocarbyl group, or a
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 tetramethylflourenyl 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 -octahydrofluorenyl 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-trimethylhexahydroazulen- yl group.
[0101] X.sup.6 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.
[0102] Specific examples of compounds having the above ligands
include
(t-butylamido)(tetramethylcyclopentadienyl)-1,2-ethanediylzirconium
dichloride, (t-butylamido)
-(tetramethylcyclopentadienyl)-1,2ethanediylti- tanium dichloride,
(methylamido) (tetramethylcyclopentadienyl)-1,2-ethaned-
iylzirconium dichloride, (methylamido)
-(tetramethylcyclopentadienyl)-1,2-- ethanediyltitanium dichloride,
(ethylamido)(tetramethylcyclopentadienyl)1,- 2-methylenetitanium
dichloride, (t-butylamido)dimethyl-(tetramethylcyclope- ntadienyl)
silanetitanium dichioride, (t-butylomido)
(dimethyl(tetramethylcyclopentadienyl)silanezirconium dichloride,
(t-butylamido)dimethyl(tetramethyl-cyclopentadienyl)silanetitanim
dimethyl, (t-butylamido)
dimethyl(tetramethylcyclopentadienyl)silanezirco- nium dimethyl,
(t-butylamido)dimethyl-(tetramethylcyclopentadienyl)-silane-
titanium dibenzyl,
(t-butylamido)dimethyl-(tetramethylcyclopentadienyl)-si-
lanezirconium dibenzyl,
(benzylamido)dimethyl-(tetramethylcyclopentadienyl- )silanetitanium
dichloride, (phenylphosphido)dimethyl-(tetra-methylcyclope-
ntadienyl)-silanezirconium dibenzyl,
(t-butylamido)dimethyl-(tetramethylcy-
clopentadienyl)silanetitanium chloride,
(dimethylaminoethyl)tetramethylcyc- lopentadienyl-titanium(III)
dichloride, 9-(dimethylaminoethyl)octahydro-fl-
uorenyltitanium(III) dichloride, (di-n-butylaminoethyl)
tetramethyl-cyclopentadienyltitanium(III) dichloride,
(dimethylaminomethyl)tetramethyl-cyclopentadienyltitanium(III)
dichloride, and (dimethylaminopropyl)tetramethyl-
cyclopentadienyl-titani- um(III) dichloride.
[0103] (iv) Transition metal compounds having a single X ligand
R.sup.5 represented by the following formula (9):
M.sup.5R.sup.5X.sup.7.sub.h (9)
[0104] wherein M.sup.5 represents a transition metal of Group 4 in
the periodic table or a lanthanide metal; R.sup.5 represents a .pi.
ligand, e.g., a group having a cyclopentadienyl skeleton;
X.sup.7-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.7 may be identical to or different from one
another and may be linked to R.sup.5 via a specific group; and h
represents "(valences of M)-1".
[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
ethylcyclopentadienyl group, a 1,3-di-methylcyclopentadienyl 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. Examples of the indenyl or fluorenyl ligands include 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,
and a substituted octahydrofluorenyl 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-tetrxethylcyclopentadienyltrimethyltitanium,
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,
(1,2,3,4,5,6,7,8-octahydrofluorenyl)titanium trichloride, and
(1,2,3,4,5,6,7,8-octahydrofluorenyl)titanium trimethoxide.
[0106] (v) Compounds represented by formula (10): 8
[0107] wherein M.sup.7 represents a transition metal of Group 4 in
the periodic table; Cp represents a cyclopentadienyl skeleton; Y5
represents O, S, NR, PR, CP, 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.8 and X.sup.9, 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.6 through R.sup.11, 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.
[0108] 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.
[0109] Specific examples of the compounds represented by formula
(10) include
isopropylidene(cyclopentadienyl)(3-t-butyl-5-methyl-2-phenoxy)tit-
anium dichloride, isopropylidene(methylcyclo
pentadienyl)(3-t-butyl-5-meth- yl-2-phenoxy)titanium dichloride,
isopropylidene(dimethylcyclopentadienyl)-
(3-t-butyl-5-methyl-2-phenoxy) titanium dichloride,
isopropylidene(trimethylcyclopentadienyl)(3-t-butyl-5-methyl-2-phenoxy)ti-
tanium dichloride,
isopropylidene(tetramethylcyclopentadienyl)(3-t-butyl-5-
-methyl-2-phenoxy)titanium dichloride,
isopropylidene(n-propylcyclopentadi-
enyl)(3-t-butyl-5-methyl-2-phenoxy) titanium dichloride,
isopropylidene(primary
butylcyclopentadienyl)(3-t-butyl-5-methyl-2-phenox- y)titanium
dichloride, isopropylidene(phenylcyclopentadienyl)(3-t-butyl-5--
methyl-2-phenoxy)titanium dichloride, isopropylidene
(cyclopentadienyl)(3-t-butyl-2-phenoxy)titanium dichloride,
isopropylidene(methylcyclopentadienyl)(3-t-butyl-2-phenoxy)titanium
dichloride,
isopropylidene(dimethylcyclopentadienyl)(3-t-butyl-2-phenoxy)-
titanium dichloride,
isopropylidene(trimethylcyclopentadienyl)(3-t-butyl-2-
-phenoxy)titanium dichloride,
isopropylidene(tetramethylcyclopentadienyl)(-
3-t-butyl-2-phenoxy)titanium dichloride,
isopropylidene(n-propylcyclopenta- dienyl) (3-t-butyl-2-phenoxy)
titanium dichloride, isopropylidene (primary butylcyclopentadienyl)
(3-t-butyl-2-phenoxy)titanium dichloride, isopropylidene
(phenylcyclopentadienyl) (3-t-butyl-2-phenoxy) titanium dichloride,
isopropylidene(cyclopentadienyl)(2-phenoxy) titanium dichloride,
isopropylidene(methylcyclopentadienyl) (2-phenoxy)titanium
dichloride, isopropylidene
(dimethylcyclopentadienyl)(2-phenoxy)titanium dichloride,
isopropylidene(trimethylcyclopentadienyl)(2-phenoxy)titanium
dichloride,
isopropylidene(tetramethylcyclopentadienyl)(2-phenoxy)titaniu- m
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.
[0110] The ethylene copolymers of the present invention are
preferably produced by use of a compound represented by formula (6)
or formula (8), in that they provide excellent copolymerization
ability among the above-described transition metal compounds. More
preferably, a compound represented by formula (8) is used.
[0111] (b) Oxygen-containing compounds (i) and/or compounds capable
of forming an ionic complex through reaction with a transition
metal compound (ii):
[0112] The component (b) which serves as the polymerization
catalyst in the present invention contains the below-described
oxygen-containing compounds (ii) and/or compounds capable of
forming an ionic complex through reaction with a transition metal
compound (ii).
[0113] Oxygen-Containing Compounds (Component (i))
[0114] The oxygen-containing compounds comprise a compound
represented by the below-described formula (11): 9
[0115] and/or a compound represented by the below-described formula
(12): 10
[0116] wherein, each of R.sup.12 through R.sup.18 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. through R.sup.16,
or R.sup.17 and R.sup.18 may be identical to or different from each
other. Each of Y.sup.6 through Y.sup.10 represents a Group 13
element, specifically, B, Al, Ga, In, and Tl, with B and Al being
preferred. Y.sup.6 through Y.sup.8, or Y.sup.9 and Y.sup.10 may be
identical to or different from each other. Each of i through l is a
number between 0 and 50 inclusive, and each of (i+j) and (k+1) is a
number of 1 or more. The preferable range for each of i through l
is 1-20 inclusive, with 1-5 inclusive being particularly
preferred.
[0117] 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 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 5-45%.
[0118] Compounds Capable of Forming an Ionic Complex Through
Reaction with a Transition Metal Compound (Component (II))
[0119] Examples of the compound capable of forming an ionic complex
through reaction with a transition metal compound include
coordination compounds and Lewis acids 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 (13) and (14) may preferably be used:
([L.sup.1-H].sup.n1+).sub.m([M.sup.7X.sup.10X.sup.11 . . .
X.sup.n2].sup.(n2-n3)-).sub.p (13)
([L.sup.2].sup.n4+).sub.q([M.sup.8X.sup.12X.sup.13 . . .
X.sup.n5].sup.(n5-n6)-).sub.r (14)
[0120] wherein L.sup.1 represents a Lewis base; each of M.sup.7 and
M.sup.8 represents a metal selected from Group 5 to Group 15
elements; L.sup.2 represents a M.sup.9, R.sup.19R.sup.20 M.sup.10,
or R.sup.21.sub.3C, wherein M.sup.9 represents a metal of Group 1
or a metal selected from Group 8 to Group 12 elements, M.sup.10
represents 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.10, X.sup.11 through X.sup.n2 and X.sup.12, X.sup.13 through
X.sup.n5 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.7 and n6 represents a valence of M.sub.6, and
each of n3 and n6 is an integer between 1-7 inclusive; n1
represents an ion valence of L.sup.1-H, n4 represents an ion
valence of L.sup.2, and each of n1 and n4 is an integer between 1-7
inclusive; each of n2 and n5 is an integer between 2 and 1
inclusive; each of m and q is an integer of one or more;
p=m.times.nl/(n2-n3); and r=q.times.n4/(n5-n6).
[0121] Examples of M.sup.7 and M.sup.8 include atoms such as B, Al,
Si, P, As, or Sb; examples of M.sup.9 include atoms such as Ag, Cu,
Na, or Li; and examples of M.sup.10 include atoms such as Fe, Co,
or Ni. Examples of X.sup.10 through X.sup.n2 and X.sup.12 through
X.sup.n5 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-tertiary butylphenyl
group, a 2,6-dimethylphenyl 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.
[0122] 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.6CF.sub.3F.sub.4).sub.4.sup.-,
B(C.sub.6H.sub.5).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-diethyl- anilinium, 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).sup.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.6H5).sub.2PH.sub.2.sup.+, (C.sub.6H.sub.5).sub.3PH.sup.+,
(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.2H.sub.5).sub.2P.sup.+.
[0123] Specifically, among the compounds represented by formulas
(13) and (14), the following compounds are preferably used.
Examples of the compound represented by formula (13) 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 tetrakis
(pentafluorophenyl)borate, trityl tetrakis
(pentafluorophenyl)borate, silver hexafluoroarsenate, silver
hexafluoroantimonate, and silver tetrafluoroborate.
[0124] 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, P(C.sub.6F.sub.5).sub.5, and Al(C.sub.6HF.sub.4).sub.3.
In the polymerization catalysts used in the present invention as
the component (B), 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.
[0125] (c) Alkylating Agents:
[0126] There are a variety of alkylating agents, and examples
thereof include alkyl group-containing aluminum compounds
represented by formula (15):
R.sup.22.sub.zAl(OR.sup.23).sub.tX.sup.14.sub.(3-s-t) (15)
[0127] wherein each of R.sup.22 and R.sup.23 represents a C1-C8,
preferably a C1-C4, alkyl group; X.sup.14 represents a hydrogen
atom or a halogen atom; s is defined as 0<s.ltoreq.3, and is
preferably 2 or 3, most preferably 3; t is defined as
0.ltoreq.t<3, and is preferably 0 or 1; alkyl group-containing
magnesium compounds represented by formula (16):
R.sup.24.sub.2Mg (16)
[0128] wherein R.sup.24 represents a C1-C8, preferably a C1-C4,
alkyl group; and alkyl group-containing zinc compounds represented
by formula (17):
R.sup.25.sub.zZn (17)
[0129] wherein R.sup.25 represents a C1-C8, preferably a C1-C4,
alkyl group.
[0130] Among these alkyl group-containing compounds, alkyl
group-containing aluminum compounds, inter alia, trialkylaluminum
compounds and dialkylaluminum compounds, are preferred.
[0131] <5)-iii-2> Methods for Preparing the Catalysts
[0132] Examples of methods for contacting components (a) and (b) of
the catalysts for polymerization with an optional component (c)
include (1) adding the component (c) to a mixture of the component
(a) and the component (b) to thereby provide a catalyst, and
contacting monomers to be polymerized with the catalyst; (2) adding
the component (a) to a mixture of the component (b) and the
component (c) to thereby provide a catalyst, and contacting
monomers to be polymerized with the catalyst; (3) adding the
component (b) to a mixture of the component (a) and the component
(c) to thereby provide a catalyst, and contacting monomers to be
polymerized with the catalyst; (4) individually contacting the
components (a), (b), and (c) with monomer components to be
polymerized; and (5) contacting a mixture of a monomer component to
be polymerized and the component (c) with the catalysts prepared in
the above (1) through (3).
[0133] The above component (a) and component (b) are contacted with
the optional component (c) at the polymerization temperature or in
the temperature range from -20 to 200.degree. C.
[0134] Organic aluminum compounds such as triisobutylaluminum may
be added prior to feeding catalyst components.
[0135] <S)-iii-3> Polymerization Methods
[0136] 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.
[0137] In the obtained ethylene copolymers, the compositional ratio
of structural repeating units derived from monomers may be
appropriately regulated through feed amounts of the monomers.
[0138] (I-3) Graft copolymerization products of aromatic vinyl
monomers (a). and the above-described ethylene copolymer macromers
(b)
[0139] The graft copolymerization products are obtained by
copolymerizing aromatic vinyl monomers (a) and the above-described
ethylene copolymer macromers (b) Preferably, chains derived from
aromatic vinyl monomers in the products have stereospecificity of
highly syndiotactic structure.
[0140] 1) Method for Preparing Graft Copolymerization Products
[0141] No particular limitation is imposed on the method for
preparing the graft copolymerization products. For example, the
graft copolymerization products may be obtained by adding a
powdered ethylene copolymer macromer to a pre-synthesized
syndiotactic aromatic vinyl polymer and heating to initiate
reaction. Preferably, the graft copolymerization products may be
obtained by dissolving the ethylene copolymer macromer in an
aromatic vinyl monomer or a solvent containing the same, then
copolymerizing by use of (a) a transition metal compound, (b) (i)
an oxygen-containing compound and/or (ii) a compound that can form
an ionic complex through reaction with a transition metal compound,
and (c) an optional alkylating agent. In this case, there is
preferably used a method in which the ethylene copolymer macromer
is dissolved in an aromatic vinyl monomer or a solvent containing
the same, 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.
[0142] <1)-i> Components of Catalyst:
[0143] (a) Transition Metal Compounds
[0144] A variety of transition metals may be used as transition
metal compound (a), 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. Moreover, compounds represented by formula (18) or
formula (19) may be used.
M.sup.11R.sup.26.sub.uR.sup.27.sub.vR.sup.28.sub.wR.sup.29.sub.4-(u+v+w)
(18)
M.sup.12R.sup.30.sub.xR.sup.31.sub.yR.sup.22.sub.5-(x+y) (19)
[0145] wherein each of M.sup.11 and M12 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.
[0146] Preferably, each of the metal M.sup.11 and M.sup.12 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 (20):
TiR.sup.33X.sup.15Y.sup.11Z.sup.2 (20)
[0147] 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.15,
Y.sup.11, 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.15, Y.sup.11, 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 (20) compounds.
[0148] 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.
[0149] Also, as titanium compounds, there may be used condensation
titanium compounds represented by the following formula (21):
11
[0150] 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.
[0151] 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
(22):
M.sup.15R.sup.36R .sup.37R.sup.38R.sup.39 (22)
[0152] wherein M.sup.13 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.
[0153] (b) (i) oxygen-containing compounds and/or (ii) compounds
capable of forming an ionic complex through reaction with a
transition metal compound:
[0154] Compounds described in relation to the synthesis of ethylene
copolymer macromers may be used.
[0155] (c) Alkylating agents:
[0156] Those described in relation to the synthesis of ethylene
copolymer macromers may be used.
[0157] <1)-ii> Preparation of Catalysts:
[0158] Examples of methods for contacting components (a) and (b) of
the catalysts for polymerization with optional component (c)
include the following methods (1) through (5). According to method
(1), component (c) is added to a mixture of component (a) and
component (b) 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 (b) in
aromatic vinyl monomer (a) or in a solvent containing aromatic
vinyl monomer (a)). According to method (2), component (a) is added
to a mixture of component (b) and component (c) to thereby provide
a catalyst, and the catalyst is contacted with monomers to be
polymerized. According to method (3), component (b) is added to a
mixture of component (a) and component (c) to thereby provide a
catalyst, and the catalyst is contacted with monomers to be
polymerized. According to method (4), respective components (a),
(b), and (c) are individually contacted with monomer components to
be polymerized. According to method (5), a mixture of a monomer
component to be polymerized and component (c) with a catalyst
prepared by any of the methods (1) through (3).
[0159] The above component (a) and component (b) may be contacted
with the optional component (c) at the polymerization temperature
or in the temperature range of -20 to 200.degree. C.
[0160] The catalysts used in polymerization are thus formed of a
combination of the aforementioned components (a) and (b), or of a
combination of the aforementioned components (a), (b), and (c).
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 (b) is an oxygen-containing compound, the
mole ratio of component (a) to component (b) is preferably from 1:1
to 1:10,000, more preferably from 1:1 to 1:1,000; if the component
(b) is a compound which is capable of forming an ionic complex
through reaction with a transition metal compound, the mole ratio
of component (a) to component (b) is preferably from 0.1:1 to
1:0.1; and if component (c) is used, the mole ratio of component
(a) to component (c) is preferably from 1:0.1 to 1:1,000.
[0161] Prior to feeding catalyst components, organic aluminum
compounds such as triisobutylaluminum may be added so as to
scavenge impurities.
[0162] <I)-iii)> Polymerization Methods:
[0163] 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.
[0164] The proportions of the polymer segment derived from aromatic
vinyl monomer (a) and that derived from ethylene copolymer macromer
(b) in the final graft copolymerization product may be suitably
regulated in accordance with the amounts of aromatic vinyl monomer
(a) and macromer (b) which undergo polymerization.
[0165] (II) An aromatic vinyl resin composition composed of (A) an
aromatic vinyl polymer, (B) an ethylene copolymer having a
diene-monomer-derived vinyl group in the molecular chain, and (C) a
graft copolymerization product of an aromatic vinyl monomer (a) and
an ethylene copolymer macromer (i.e., corresponding to the
aforementioned copolymer (I)):
[0166] (II-1) Constituent Components of the Composition:
[0167] (A) Aromatic Vinyl Polymer:
[0168] The aromatic vinyl polymer is obtained through
polymerization of the above-described aromatic vinyl monomers in
accordance with a known method described, for example, in Japanese
Patent Application Laid-Open (kokai) No. 62-104818. Preferably, the
aromatic-vinyl-monomer-derived recurrent unit of the polymer has a
syndiotactic structure,
[0169] (B) Ethylene copolymer having a diene-monomer-derived vinyl
group in the molecule:
[0170] This copolymer is the same ethylene copolymer macromer as
described in (I) above.
[0171] (C) Graft copolymerization product between aromatic vinyl
monomer (a) and ethylene copolymerization macromer (b):
[0172] This is the same ethylene copolymer macromer as described in
(I) above.
[0173] (D) Other components:
[0174] Other components may also be arbitrarily selected from among
known substances and incorporated as desired. For example, there
may be incorporated thermoplastic resins such as polyolefin resins,
polystyrene resins, polycarbonate, polyester resins, polyamide
resins, polyphenylene ether, and polyphenylene sulfide; and the
following substances such as natural rubber, polybutadiene,
polyisoprene, polyisobutylene, neoprene, polysulfide rubber,
Thiokol rubber, acryl rubber, urethane rubber, silicone rubber,
epichlorohydrin rubber, styrene-butadiene block copolymer (SBR),
hydrogenated styrene-butadiene block copolymer (SEB),
styrene-butadiene-styrene block copolymer (SBS), hydrogenated
styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene
block copolymer (SIR), hydrogenated styrene-isoprene block
copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS),
hydrogenated styrene-isoprene-styrene block copolymer (SEPS),
ethylene propylene rubber (EPR), ethylene-c-olefin copolymer
rubbers such as ethylene-hexene copolymer and ethylene-octene
copolymer, ethylene-styrene copolymer rubber, ethylene-styrene
quasi-random copolymer rubber, ethylene-propyrne-diene rubber
(EPDM), and core-shell particulate elastomers including
butadiene-acrylonitrile-styrene core-shell rubber (ABS),
methylmethacrylate-butadiene-styrene core-shell rubber (MBS),
methylmethacrylate-butylacrylate-styrene core-shell rubber (ES),
octylacrylate-butadiene-styrene core-shell rubber (MABS),
alkylacrylate-butadiene-acrylonitrile-styrene core-shell rubber
(AABS), butadiene-styrene core-shell rubber (SBR), and
siloxane-containing core-shell rubbers led by
methacrylate-butylacrylate siloxane. Also, there may be
incorporated rubber-like elastic substances having elasticity such
as modification products of the above-listed rubbers. Furthermore,
there may be incorporated a variety of other types of ingredients
in such amounts that the effects of the present invention are not
impeded. Examples of such ingredients include inorganic fillers,
antioxidants, nucleating agents, plasticizers, mold-releasing
agents, flame retardants, flame retardant aids, and antistatic
agents.
[0175] Examples of inorganic fillers include fibers such as glass
fiber, carbon fiber and whiskers; and granular or powdery materials
such as talc, carbon black, graphite, titanium dioxide, silica,
mica, calcium carbonate, calcium sulfate, barium carbonate,
magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate,
tin oxide, alumina, kaolin, silicon carbide, metal powder, glass
powder, glass flakes, and glass beads. Of these inorganic fillers,
glass fillers are particularly preferred.
[0176] The inorganic fillers are preferably surface-treated with a
coupling agent (such as a silane coupling agent or titanium
coupling agent) or a similar agent so as to obtain enhanced
adhesion against the resin.
[0177] The inorganic fillers may be used singly or in combination
of two or more.
[0178] (II-2) Preparation of the Composition:
[0179] No particular limitation is imposed on the method for
preparing the above-described aromatic vinyl resin composition. The
order of addition of components, mixing method, and other
conditions may be arbitrarily selected. The composition encompasses
those which are obtained through melt-kneading of a component
mixture. The method of melt-kneading is not particularly limited,
and known methods which are routinely used may be performed.
[0180] (II-3) Proportions of the Respective Components in the
Composition:
[0181] The proportions of the respective components in the
composition are as follows. (A): Aromatic vinyl polymer 0-99% by
weight, preferably 0-50% by weight (exclusive of 0 in both cases).
(B): Ethylene copolymer having a diene-monomer-derived vinyl group
in the molecular chain=0-50% by weight, preferably 0-30% by weight
(exclusive of 0 in both cases). (C): A graft copolymerization
product of aromatic vinyl monomer (a) and ethylene copolymer
macromer (b)=1-100% by weight, preferably 10-100% by weight
(exclusive of 0 in both cases).
[0182] If the aromatic vinyl polymer (A) is contained in an amount
of more than 99% by weight, sufficient toughness may not be
obtained. If the ethylene copolymer having a diene-monomer-derived
vinyl group in the molecular chain (B) is contained in an amount of
more than 50% by weight, elasticity may decrease and moldability
may become poor. If the graft copolymerization product of aromatic
vinyl monomer (a) and ethylene copolymer macromer (b) is less than
1% by weight, sufficient toughness may not be obtained.
[0183] (III) An aromatic vinyl resin composition composed of an
aromatic vinyl resin material as described above in (I) or (II) and
a styrene polymer predominantly having a syndiotactic structure
and/or a rubber-like elastic material:
[0184] (III-1) Constituent Components:
[0185] (a) Styrene Compounds Predominantly Having a Syndiotactic
Structure:
[0186] The term "syndiotactic structure" refers to a structure of a
chemical substance which has a syndiotactic stereochemical
structure, in which the side chains (phenyl groups) alternate
regularly above and below the plane of the backbone (main chain
formed of C.dbd.C bonds). Quantitative determination of tacticity
is carried out through nuclear magnetic resonance using a carbon
isotope (13C--NMR). Tacticity as measured through .sup.13C-NMR is
represented by the proportions of a plurality of consecutive
constituent units; diad when two constituent units are present,
triad when three constituent units are present, and pentad when
five constituent units are present. In the present invention, the
expression "styrene polymer predominantly having a syndiotactic
structure" collectively refers to the following substances which
are generally endowed with a syndiotacticity of 75% or more,
preferably 85% or more, in the case of racemic diad, or of 30% or
more, preferably 50% or more, in the case of racemic pentad:
polystyrene, poly(alkylstyrene), poly(halostyrene),
poly(haloalkylstyrene), polyalkoxystyrene), poly(vinylbenzoic acid
esters), hydrogenated polymers thereof, mixtures thereof, and
copolymers containing any of these members as a predominant
component. Specific examples of poly(alkylstyrene) include
poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene),
poly(tert-butylstyrene), poly(phenylstyrene),
poly(vinylnaphthalene), and poly(vinylstyrene). Specific examples
of poly(halostyrene) include poly(chlorostyrene),
poly(bromostyrene), and poly(fluorostyrene). Specific examples of
poly(haloalkylstyrene) include poly(chloromethylstyrene), and
specific examples of poly(alkoxystyrene) include
poly(methoxystyrene) and poly(ethoxystyrene).
[0187] Of the above-listed styrene polymers, particularly preferred
are polystyrene, poly(p-methylstyrene), poly(m-methylstyrene),
poly(p-tert-butylstyrene), poly(p-chlorostyrene),
poly(m-chlorostyrene), poly(p-fluorostyrene), hydrogenated styrene,
and copolymers containing any of these structural units.
[0188] The above-described styrene polymers predominantly having a
syndiotactic structure may be prepared by known methods. For
example, in an inert hydrocarbon solvent (or without use of a
solvent), styrene monomers (the monomers that correspond to the
styrene polymer of interest) are polymerized by use of a catalyst
obtained through condensation of a titanium compound, water, and
trialkylaluminum (see, for example, Japanese Patent Application
Liad-Open (kokal) No. 62-187708). Also, poly(haloalkylstyrene) and
hydrogenated polymers thereof may be prepared by any method
described, for example, in Japanese Patent Application Liad-Open
(kokai) Nos. 1-46912 and 1-178505.
[0189] These styrene polymers predominantly having a syndiotactic
structure may be used singly or in combination of two or more.
[0190] (b) Rubber-like elastic materials:
[0191] Specific examples of rubber-like elastic materials include
natural rubber, polybutadiene, polyisoprene, polyisobutylene,
neoprene, polysulfide rubber, Thiokol rubber, acryl rubber,
urethane rubber, silicone rubber, epichlorohydrin rubber,
styrene-butadiene block copolymer (SBR), hydrogenated
styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene
block copolymer (SBS), hydrogenated styrene-butadiene-styrene block
copolymer (SEBS), styrene-isoprene block copolymer (SIN),
hydrogenated styrene-isoprene block copolymer (SEP),
styrene-isoprene-styrene block copolymer (SIS), hydrogenated
styrene-isoprene-styrene block copolymer (SEPS), ethylene propylene
rubber (EPR), ethylene-a-olefin copolymer rubbers such as
ethylene-hexene copolymer and ethylene-octene copolymer,
ethylene-styrene copolymer rubber, ethylene-styrene quasi-random
copolymer rubber, ethylene-propyrne-diene rubber (EPDM), and
core-shell particulate elastomers including
butadiene-acrylonitrile-styrene core-shell rubber (ABS),
methylmethacrylate-butadiene-styrene core-shell rubber (MBS),
methylmethacrylate-butylacrylate-styrene core-shell rubber (MAS),
octylacrylate-butadiene-styrene core-shell rubber (MABS),
alkylacrylate-butadiene-acrylonitrile-styrene core-shell rubber
(AABS), butadiene-styrene core-shell rubber (SBR), and
siloxane-containing core-shell rubbers led by
methacrylate-butylacrylate siloxane. Also, there may be used
modification products of these rubbers.
[0192] Of the listed materials, preferred are olefin-type
rubber-like elastic materials, inter alia, those exhibiting rubber
elasticity at room temperature and being endowed with elastic
recovery of 40 or more, preferably 55 or more, particularly
preferably 70 or more. As used herein, the expression "elastic
recovery" refers to the value obtained from the following
procedure. Briefly, the resin which has been melted at a
temperature higher than its melting point is press-formed into film
with a cold press. The film is subjected to blanking through use of
a blanking die having the S3 size of DIN53504, to thereby obtain a
test piece. The test piece is subjected to a tensile test through
use of Autograph AG5000B (manufactured by Shimadzu Corp.).
Specifically, the test piece is pulled to extend by 100% under
conditions in which the initial distance between chucks was 20 mm
and the pulling speed was 1 mm/min. Subsequently, the test piece
was returned towards the original state at the same but opposite
speed, and the strain (%) remaining when the stress reached 0 is
measured as a residual strain. The elastic recovery was calculated
based on the following equation:
Elastic recovery=100-residual strain
[0193] (c) Other components:
[0194] Other components which are arbitrarily selected from among
known ingredients may be incorporated as needed. For specific
examples, reference is made to those listed previously.
[0195] (I1I-2) Proportions of the Constituent Components
[0196] In the composition system constituted by an aromatic vinyl
resin material (I) or (II), and a styrene polymer predominantly
having a syndiotactic structure (a) and/or a rubber-like elastic
material (b), the blend ratio of the "aromatic vinyl resin material
(I) or (II)" to the component(s) "(a) and/or (b)" is arbitrarily
determined. The proportions of (a) and (b) are as follows. (a):
Aromatic vinyl polymer 50-97% by weight, preferably 60-95% by
weight. (b): Rubber-like elastic material 3-50% by weight,
preferably 5-40% by weight, more preferably 10-35% by weight.
[0197] If aromatic vinyl polymers are used in amounts less than 10%
by weight, sufficient heat resistance and solvent resistance cannot
be obtained. On the other hand, amounts in excess of 97% by weight
may result in poor toughness. 3. Molded products formed through
molding of an aromatic vinyl resin material:
[0198] The aromatic vinyl resin materials of the present invention
are molded into a variety of molding products. For example, films,
sheets, stretched films, and injection-molded products may be
formed. The molding method is not limited and any suitable known
method may be used.
EXAMPLES
[0199] The present invention will next be described in more detail
by way of example.
[0200] The evaluation methods are as described above.
[0201] Tm (melting point) was measured by use of DSC-7
(manufactured by Perkin-Elmer Corp.). First, each sample was heated
to 300.degree. C. and allowed to melt for five minutes.
Subsequently, the sample was cooled to 50.degree. C. at 20.degree.
C./min. and held for one minute at the same temperature. The sample
was heated again at 20.degree. C./min and the melting point was
measured.
Example 1
[0202] (1) Synthesis of Ethylene Copolymer Macromer Having a Vinyl
Group Derived from a Diene Monomer in the Molecular Chain.
[0203] In a 2-liter pressure-proof polymerization tank were placed
dehydrated toluene (206 ml), active-alumina-treated purified
styrene (600 ml), active-alumina-treated divinylbenzene (4.5
ml)(manufactured by Nippon Steel Chemical Co., Ltd., high-purity
para isomer T-30, p-divinylbenzene content: 70 wt. %), and
methylaluminoxane (manufactured by Albemarle) such that an aluminum
concentration was 9 mmol. Ethylene was fully dissolved under a
constant gauge pressure of 0.6 MPa, and (t-butylamido) dimethyl
(.eta..sup.5-1,2,3,4-tetrahydro -9-fluorenyl) silanetitanium
dichloride was added thereto such that an aluminum concentration
was 15 .mu.mol. Subsequently, ethylene was subjected to
polymerization at 70.degree. C. for 30 minutes under a constant
ethylene pressure. After removal of ethylene gas, polymerization
was terminated by addition of a small amount of methanol.
[0204] 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 (85
g). The composition was confirmed by .sup.1H-NMR to be
ethylene/styrene/divinylbe- nzene=78.4/21.5/0.1 (mol %).
[0205] (2) Graft Copolymerization
[0206] In a 500-ml separable flask were placed fully-dehydrated
toluene (150 ml) and active-alumina-treated purified styrene (100
ml). The ethylene copolymer macromer (4.0 g) synthesized in
procedure (1) above was substituted with nitrogen and added to the
mixture under stirring. The. macromer was completely dissolved in
the styrene monomer liquid at 50.degree. C.
[0207] Next, the solution of ethylene copolymer macromer in styrene
was heated to 75.degree. C., and truisobutyl 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 20
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.
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: 27.0 g).
[0208] The thus-obtained graft copolymerization product has a total
ethylene copolymer macromer content of 15 wt. %. The product was
dried, melted at 300.degree. C., shaped into a strand, and
pelletized.
[0209] The results are shown in Table 1.
1 TABLE 1 Tensile elongation Tm (.degree. C.) (%) G' (1.0) G' (0.1)
SG value Example 1 270 44 1105 567 0.29 Example 2 271 72 5040 3108
0.21 Example 3 270 48 1044 500 0.32 Comparative 270 2 2.03 1.60
2.10 Example 1 Comparative 270 4 805 104 0.89 Example 2 Comparative
270 5 682 136 0.70 Example 3
Example 2
[0210] The procedure of Example 1 was repeated except that
copolymerization of ethylene copolymer macromer and styrene in the
step "(2) Graft copolymerization" was performed for 5 minutes
instead of 20 minutes. The thus-obtained graft copolymerization
product has a total ethylene copolymer macromer content of 37 wt.
%.
[0211] Also, the polymerized polymer was treated in the same manner
as in Example 1.
[0212] The results are shown in Table 1.
Example 3
[0213] (1) Synthesis of Ethylene Copolymer having a Vinyl Group
Derived from a Diene Monomer in the Molecular Chain
[0214] In a 1-liter pressure-proof polymerization tank were placed
dehydrated toluene (250 ml), active-alumina-treated
p-divinylbenzene (0.6 ml)(manufactured by Nippon Steel Chemical
Co., Ltd., high-purity para isomer T-30), and methylaluminoxane
(manufactured by Albemarle) such that an aluminum concentration was
7.5 mmol. A mixture gas of ethylene and propylene (mol ratio of
8:2)-was fed thereinto under a gauge pressure of 0.6 MPa, and a
steady state was attained. Thereafter,
(t-butylaido)dimethyl(.eta..sup.5-1,2,3,4-tetrahydro-9-fluorenyl)silaneti-
tanium dichloride was added thereto such that titanium
concentration was 7.5 .mu.mol, followed by polymerization at
70.degree. C. for 30 minutes under a constant pressure. After
removal of a gaseous monomer, Polymerization was terminated by
addition of a small amount of methanol.
[0215] The thus-obtained viscous solution was precipitated in
methanol, and a polymer was collected. The polymer was dried at
50.degree. C. under reduced pressure, to thereby obtain an ethylene
copolymer (26 g).
[0216] (2) Graft Copolymerization
[0217] The procedure of Example 1 was repeated. The thus-obtained
graft copolymerization product has a total ethylene copolymer
macromer content of 22 wt. %.
[0218] The product was dried, melted at 300.degree. C., shaped into
a strand, and pelletized.
[0219] The results are shown in Table 1.
Comparative Example 1
[0220] The procedure of Example 1 was performed except that no
ethylene copolymer macromer was added and a styrene monomer was
mixed in advance in toluene at 80.degree. C. in the step "(2) Graft
copolymerization." The same titanium-mixed catalyst as used in
Example 1 (2) was added such that a titanium concentration was 5.0
.mu.mol, followed by polymerization for 20 minutes. Polymerization
was terminated by addition of a small amount of methanol, and the
polymer was washed twice in methanol, each time for 30 minutes.
[0221] After filtration, the polymer was dried at 200.degree. C.
for two hours under reduced pressure, to thereby obtain
syndiotactic polystyrene (SPS)(24.5 g).
[0222] The results are shown in Table 1.
Comparative Example 2
[0223] To SPS used in Comparative Example 1 was added 20 wt. %
ethylene-propylene rubber (EP-0lP manufactured by Japan Synthetic
Rubber Co., Ltd.), and the mixture was shaped into a strand and
pelletized at 300.degree. C.
[0224] The results are shown in Table 1.
Comparative Example 3
[0225] To SPS used in Comparative Example 1 were added 10 wt. %
ethylene-propylene rubber (EP-01P manufactured by Japan Synthetic
Rubber Co., Ltd.) and 10 wt. % SEBS (G1651 manufactured by Shell
Japan Ltd.), and the mixture was shaped into a strand and
pelletized at 300.degree. C.
[0226] The results are shown in Table 1.
Example 4
[0227] (2) Graft Copolymerization
[0228] In a 1-liter separable flask were placed ethylene copolymer
macromer (12.0 g) synthesized in Example 1 (2), fully-dehydrated
toluene (400 ml) and active-alumina-treated purified styrene (100
ml), and-the ethylene-copolymer macromer was completely dissolved.
There was added thereto a mixture of previously-prepared
1,2,3,4,5,6,7,8-octahydrofluoren- yltitanium trimethoxide such that
a titanium concentration was 18 .mu.mol, methylaluminoxane
(manufactured by Albemarle) such that an aluminum concentration was
1.7 mmol, triisobutyl aluminum (380 .mu.mol) (manufactured by TOSOB
AKZO CORPORATION), followed by polymerization at 75.degree. C. for
15 minutes under nitrogen. Polymerization was terminated by
addition of a small amount of methanol. The polymer was washed with
methanol and dried at 60.degree. C. The yield of the polymer was
48.4 g.
[0229] Using the resultant polymer, .sup.1H-NMR analysis was
performed on the residue taken up with boiling cyclohexane. B/A was
confirmed to be 0.26 (wherein A is an integrated value of a peak
appearing at 1.0-1.7 (ppm) and B is an integrated value of a peak
appearing at 1.8-2.1 (ppm)), B/A in the eluted fractions at
50.degree. C. or more through fractionation with o-dichlorobenzene
(ODCB) was confirmed to be 0.27 (wherein A and B are as described
above; the same applies hereinafter), B/A in the eluted fractions
at 110.degree. C. or more through the same was confirmed to be
0.28, and B/A in the eluted fractions at 125.degree. C. or more
through the same was confirmed to be 0.29.
[0230] Further, the obtained polymer was melted at 300.degree. C.
and shaped into a strand, to thereby obtain pellets of the polymer.
The polymer had a heat of fusion .DELTA.H of 21.1 (J/g) over the
range 200-295.degree. C. as measured by use of a differential
scanning calorimeter, a tensile elongation of 96%, an internal haze
of 25.9%, and the mean diameter of the domain components obtained
through light scattering method was 0.6 .mu.m. Also, the SG value
was 0.32.
Example 5
[0231] The procedure of Example 4 was repeated except that the
amount of copolymer macromer synthesized in Example 1 (2) was 4.0
g, that of 1,2,3,4,5,6,7,8-octahydrofluorenyltitanium trimethoxide
was such that titanium concentration was 5 .mu.mol, that of
methylaluminoxane was such that aluminum concentration was 0.6
mmol, and that of triisobutyl aluminum was 125 .mu.mol. The yield
was 21.6 g.
[0232] Using the resultant polymer, .sup.1H-NMR analysis was
performed on the residue taken up with boiling cyclohexane. B/A was
confirmed to be 0.34 (wherein A and B are as described above), and
B/A in the eluted fractions at 125.degree. C. or more through
fractionation with o-dichlorobenzene (ODCB) was confirmed to be
0.35.
[0233] Further, the obtained polymer was melted at 300.degree. C.
and shaped into a strand, to thereby obtain pellets of the polymer.
The polymer had a heat of fusion .DELTA.H of 23.4 (J/g) over the
range 200-295.degree. C. as measured by use of a differential
scanning calorimeter, a tensile elongation of 27%, an internal haze
of 27.8%, and the mean diameter of the domain components obtained
through light scattering method was 0.6 .mu.m. Also, the SG value
was 0.57.
Example 6
[0234] (1) Synthesis of Ethylene Copolymer Having a Vinyl Group
Derived from a Diene Monomer in the Molecular Chain
[0235] In a 2-liter pressure-proof polymerization tank were placed
dehydrated toluene (500 ml), active-alumina-treated purified
styrene (930 ml), active-alumina-treated divinylbenzene (10.5
ml)(manufactured by Nippon Steel Chemical Co., Ltd., high-purity
para isomer T-30, p-divinylbenzene content: 70 wt. %),
methylaluminoxane (manufactured by Albemarle) such that an a]uminum
concentration was 18 mmol, and triisobutyl aluminum (manufactured
by TOSOH AKZO CORPORATION) such that an aluminum concentration was
0.5 mmol. Ethylene was fully melted under a constant pressure of
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
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.
[0236] 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
(115.3 g).
[0237] The composition was confirmed by .sup.1H-NMR to be
ethylene/styrene/divinylbenzene=71.1/28.6/0.4 (mol %).
[0238] (2) Graft Copolymerization
[0239] In a 5-liter polymerization tank were placed ethylene
copolymer macromer (100 g) synthesized in step (1) above,
fully-dehydrated toluene (1500 ml), and active-alumina-treated
purified styrene (1500 ml), and the ethylene copolymer macromer was
completely dissolved. There was added thereto a mixture of
previously-prepared 1,2,3,4,5,6,7,8-octahydrofluoren- yltitanium
trimethoxide such that a titanium concentration was 200 .mu.mol,
methylaluminoxane (manufactured by Albemarle) such that an aluminum
concentration was 22 mmol, and triisobutyl aluminum (5 mmol)
(manufactured by TOSOH AKZO CORPORATION), followed by
polymerization at 75.degree. C. for 90 minutes under nitrogen.
Polymerization was terminated by addition of a small amount of
methanol. The polymer was washed with methanol and dried at
60.degree. C. The yield of the polymer was 570 g.
[0240] Using the resultant polymer, .sup.1H-NMR analysis was
performed on the residue taken up with boiling cyclohexane. B/A was
confirmed to be 0.37, and B/A in the eluted fractions at
125.degree. C. or more through fractionation with o-dichlorobenzene
(ODCB) was confirmed to be 0.38.
[0241] Further, the obtained polymer was melted at 300.degree. C.
and shaped into a strand, to thereby obtain pellets of the polymer.
The polymer had a heat of fusion .DELTA.H of 25.8 (J/g) over the
range 200-295.degree. C. as measured by use of a differential
scanning calorimeter, a tensile elongation of 37%, an internal haze
of 15.7%, and the mean diameter of the domain components obtained
through light scattering method was 0.3 .mu.m. Also, the SG value
was 0.22.
Example 7
[0242] (1) Synthesis of Ethylene Copolymer Having a Vinyl Group
Derived from a Diene Monomer in the Molecular Chain
[0243] In a 1-liter pressure-proof polymerization tank were placed
dehydrated toluene (200 ml), p-(3-butenyl)styrene (40 mmol),
methylaluminoxane (manufactured by Albemarle) such that an aluminum
concentration was 5 mmol, and triisobutyl aluminum (manufactured by
TOSOH AKZO CORPORATION) such that an aluminum concentration was 0.5
mmol. The mixture was regulated such that the flow ratio of
ethylene to propylene was 7:2 and the gauge pressure was 0.9 MPa.
Ethylenebis-. 1,1'-indenylzirconium dichloride was added thereto
such that a zirconium concentration was 2 .mu.mol, followed by
polymerization at 30.degree. C. for 15 minutes.
[0244] After removal of the inert gas, polymerization was
terminated by addition of a small amount of methanol.
[0245] 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 (27.0 g).
[0246] The composition was confirmed by .sup.1H-NM to be
ethylene/propylene/3-butenylstyrene=81.3/18.2/0.5 (mol %).
[0247] (2) Graft Copolymerization
[0248] In a 500-ml separable flask were placed ethylene copolymer
macromer (4.0 g) synthesized in step (1) above, fully-dehydrated
toluene (150 ml), and active-alumina-treated purified styrene (100
ml), and the ethylene copolymer macromer was completely dissolved.
There was added thereto a mixture of previously-prepared
1,2,3,4,5,6,7,8-octahydrofluorenyltitanium trimethoxide such that a
titanium concentration was 7.5 .mu.mol, methylaluminoxane
(manufactured by Albemarle) such that an aluminum concentration was
830 .mu.mol, and triisobutyl aluminum (190 .mu.mol)(manufactured by
TOSOH AKZO CORPORATION), followed by polymerization at 65.degree.
C. for 7 minutes under nitrogen. Polymerization was terminated by
addition of a small amount of methanol. The polymer was washed with
methanol and dried at 60.degree. C. The yield of the polymer was
18.0 g.
[0249] According to the analysis by .sup.1H-NMR performed on the
residue taken up with boiling cyclohexane, B/A was confirmed to be
0.30, and B/A in the eluted fractions at 125.degree. C. or more
through fractionation with o-dichlorobenzene (ODCB) was confirmed
to be 0.31.
[0250] Further, the obtained polymer was melted at 300.degree. C.
and shaped into a strand, to thereby obtain pellets of the polymer.
The polymer had a heat of fusion .DELTA.H of 21.1 (J/g) over the
range 200-295.degree. C. as measured by use of a differential
scanning calorimeter, a tensile elongation of 68%, an internal haze
of 14.3%, and the mean diameter of the domain components obtained
through light scattering method was 0.3 .mu.m.
[0251] (1) Synthesis of Ethylene Copolymer Having no Vinyl Group
Derived from a Diene Monomer in the Molecular Chain
[0252] In a 1-liter pressure-proof polymerization tank were placed
dehydrated toluene (90 ml), active-alumina-treated purified styrene
(210 ml), and methylaluminoxane (manufactured by Albemarle) such
that an aluminum concentration was 4.5 mmol. Ethylene was fully
melted under a constant pressure of 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 7.5 .mu.mol.
Subsequently, ethylene was subjected to polymerization at
70.degree. C. for 30 minutes under a constant ethylene pressure.
After removal of ethylene gas, polymerization was terminated by
addition of a small amount of methanol.
[0253] 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 (29.7 g).
[0254] The composition was confirmed by .sup.1H-NMR to be
ethylene/styrene=79.6/20.4 (mol %).
[0255] (2) Graft Copolymerization
[0256] In a 500-ml separable flask were placed ethylene copolymer
macromer (4.0 g) synthesized in step (1) above, fully-dehydrated
toluene (200 ml), and active-alumina-treated purified styrene (50
ml), and the ethylene copolymer macromer was completely dissolved.
There was added thereto a mixture of previously-prepared
1,2,3,4,5,6,7,8-octahydrofluorenyltitanium trimethoxide such that a
titanium concentration was 7.5 .mu.mol, methylaluminoxane
(manufactured by Albemarle) such that an aluminum concentration was
630 .mu.mol, and triisobutyl aluminum (190 .mu.mol) (manufactured
by TOSOH AKZO CORPORATION), followed by polymerization at
65.degree. C. for 15 minutes under nitrogen. Polymerization was
terminated by addition of a small amount of methanol. The polymer
was washed with methanol and dried at 60.degree. C. The yield of
the polymer was 19.9 g.
[0257] According to the analysis by .sup.1H-NMR performed on the
residue taken up with boiling cyclohexane, B/A was confirmed to be
0.50, and B/A in the eluted fractions at 125.degree. C. or more
through fractionation with o-dichlorobenzene (ODCB) was confirmed
to be 0.50.
[0258] Further, the obtained polymer was melted at 300.degree. C.
and shaped into a strand, to thereby obtain pellets of the polymer.
The polymer had a heat of fusion .DELTA.H of 21.5 (J/g) over the
range 200-295.degree. C. as measured by use of a differential
scanning calorimeter, a tensile elongation of 3.8%, an internal
haze of 87.1%, and the mean diameter of the domain components
obtained through light scattering method was 2.4 .mu.m.
Comparative Example 5
[0259] The procedure of Example 4 was repeated except that
styrene-butadiene block copolymer (4.0 g)(NS312S manufactured by
Nippon Zeon Co., Ltd.) was used in step (2) instead of ethylene
copolymer synthesized in step (1), to thereby obtain a polymer
(20.1 g).
[0260] According to the analysis by .sup.1H-NMR performed on the
residue taken up with boiling cyclohexane, B/A was confirmed to be
0.50, and B/A in the eluted fractions at 125.degree. C. or more
through fractionation with o-dichlorobenzene (ODCB) was confirmed
to be 0.50.
[0261] Further, the obtained polymer was melted at 300.degree. C.
and shaped into a strand, to thereby obtain pellets of the polymer.
The polymer had a heat of fusion .DELTA.H of 21.5 (J/g) over the
range 200-295.degree. C. as measured by use of a differential
scanning calorimeter, a tensile elongation of 4.8%, and an internal
haze of 75.7%. However, the mean diameter of the domain components
obtained through light scattering method could not be measured,
since microphase separation occurred in the polymer itself.
Comparative Example 6
[0262] The procedure of Example 4 was repeated except that
ethylene-propylene copolymer (4.0 g)(EPO1 manufactured by JSR) was
used in step (2) instead of ethylene copolymer synthesized in step
(1), to thereby obtain a polymer (21.1 g).
[0263] According to the analysis by .sup.1H-NMR performed on the
residue taken up with boiling cyclohexane, B/A was confirmed to be
0.50, and B/A in the eluted fractions at 125.degree. C. or more
through fractionation with o-dichlorobenzene (ODCB) was confirmed
to be 0.50.
[0264] Further, the obtained polymer was melted at 300.degree. C.
and shaped into a strand, to thereby obtain pellets of the polymer.
The polymer had a heat of fusion .DELTA.H of 22.5 (J/g) over the
range 200-295.degree. C. as measured by use of a differential
scanning calorimeter, a tensile elongation of 3.8%, an internal
haze of 85.3%, and the mean diameter of the domain components
obtained through light scattering method was 2.8 .mu.m.
Example 8
[0265] Graft copolymer obtained in Example 3, SPS used in
Comparative Example 1, and ethylene-propylene rubber (EP-01P
manufactured by Japan Synthetic Rubber Co., Ltd.) were mixed at the
weight ratio of 50:40:10. The mixture was kneaded at 300.degree. C.
by use of a biaxial extruder (LABO-PIASTMILL manufactured by Toyo
Seiki Co., Ltd.), to thereby obtain pellets of the polymer. The
polymer had a tensile elongation of 25%.
[0266] As described above, the present invention satisfactorily
provides aromatic vinyl resin materials which are endowed with heat
resistance, solvent resistance, toughness, tensile elongation, and
transparency, as well as molded products of the resin
materials.
* * * * *