JP2000159837A - Aromatic vinyl compound/olefin/non-conjugated diene copolymer and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide crosslinked elastomers excellent in mechanical strength, rubber elasticity, high-temperature properties, and transparency as well as a blend with a synthetic rubber and co-vulcanizability. SOLUTION: Aromatic vinyl compound/olefin/non-conjugated diene copolymers comprise 1-70 mol% aromatic vinyl compound, 0.01-20 mol% non-conjugated diene, and 10-98.99 mol% olefin. The copolymers have a head-to-tail chain structure of two or more aromatic vinyl compound units. The olefin is ethylene, and the non-conjugated diene is divinylbenzene or vinylcyclohexene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel aromatic vinyl compound-olefin-non-conjugated diene copolymer and a method for producing the same.

[0002]

2. Description of the Related Art Crosslinked elastomers are widely used in various industrial fields. Among them, EPDM having no double bond in the main chain is excellent in weather resistance, ozone oxidation resistance, and heat aging resistance, and thus has a specific application. Although it is heavily used in the field, there are many points to be improved such as mechanical strength and dynamic fatigue resistance. Also,
Since the polarity is low, the compatibility is low and there is a problem in blending with a synthetic rubber such as SBR and butadiene rubber for improving mechanical properties and co-vulcanization. <Styrene-olefin copolymer-based elastomer and crosslinked product thereof> On the other hand, an aromatic vinyl compound having no stereoregularity and having no styrene chain, ethylene-α-olefin-diene quaternary copolymer for the purpose of improving the above-mentioned problems. Polymers, compositions thereof, and cross-linked products thereof (JP-A-8-225615)
JP-A-8-134140, JP-A-8-134140
No. 43712, JP-A-8-216343) are known. However, these also do not have a head-tail styrene chain structure, so that the above-mentioned compatibility and co-vulcanizability are not sufficient. In addition, the absence of the styrene chain structure of the head-tail and the absence of stereoregularity in any structure contained in the copolymer make the copolymer itself mechanical strength, especially the initial elastic modulus and breaking strength. Is not fully satisfactory. Further, these aromatic vinyl compound-ethylene-α-olefin-diene quaternary copolymers have poor transparency and their uses are limited. <Random stereoregular styrene-ethylene copolymer>
On the other hand, styrene-ethylene copolymers having stereoregularity and a head-tail styrene chain structure have been reported. (Japanese Unexamined Patent Publication (Kokai) No. 9-309925) This copolymer has high mechanical properties (rupture strength, initial elastic modulus) and a styrene chain structure of a head-tail, and microcrystals and partial crystal structures derived from stereoregularity. It features high solvent resistance and high transparency. However, high-temperature properties, that is, mechanical properties at high temperatures are not sufficiently satisfactory.

[0003]

SUMMARY OF THE INVENTION The present invention relates to these conventional elastomers, tertiary regular aromatic vinyl compound-ethylene-α-olefin-diene quaternary copolymers having no styrene chain, or stereoregularity. And improved the drawbacks of styrene-ethylene copolymers having a head-tail styrene chain structure, and combined with blending with synthetic rubber and co-vulcanizability, have excellent mechanical strength, rubber elasticity, high-temperature properties, and transparency. To provide a crosslinked elastomer.

[0004]

That is, 1) The present invention relates to an aromatic vinyl compound of 1 to 70 mol%, a non-conjugated diene 0.1.
An aromatic vinyl compound-olefin-diene copolymer comprising 01 to 20 mol% and 10 to 99.99 mol% of olefin, and a method for producing the same. Further, it is a crosslinked product or a crosslinked molded article. Further, the present invention is the above-mentioned aromatic vinyl compound-olefin-non-conjugated diene copolymer satisfying the following conditions. 1 to 70 mol% of an aromatic vinyl compound, 0.01 to 20 mol% of a non-conjugated diene, and an aromatic vinyl compound-olefin-non-conjugated diene copolymer whose balance is an olefin, 2) 2 or 3 An aromatic vinyl compound-olefin-non-conjugated diene copolymer having a head-tail chain structure of the above aromatic vinyl compound units. 3) An aromatic vinyl compound in which the olefin is ethylene
Olefin-non-conjugated diene copolymer. 4) 4C by 13 C-NMR measurement based on TMS
0.5 to 41 ppm, 43.0 to 43.6 ppm, 4
An aromatic vinyl compound-ethylene-non-conjugated diene copolymer having a chain structure of aromatic vinyl compound units assigned by peaks observed at 2.3 to 43.1 ppm and 43.7 to 44.5 ppm. 5) The stereoregularity of the phenyl group of the alternating structure of the aromatic vinyl compound represented by the following general formula (1) and ethylene contained in the copolymer structure is from 0.75 in isotactic dyad fraction m. An aromatic vinyl compound-ethylene-nonconjugated diene copolymer characterized by being large.

The structure is determined by a nuclear magnetic resonance method (NMR method). The copolymer of the present invention has main peaks at the following positions in 13C-NMR based on TMS. Peaks derived from main chain methylene and main chain methine carbon were around 24 to 25 ppm, around 27 ppm, and 30 ppm.
around ppm, 34-37 ppm, 40-41 ppm
Near and around 42 to 46 ppm, and peaks derived from five carbons of the phenyl group which are not bonded to the polymer main chain were around 126 ppm and 128 ppm,
The peak derived from one carbon atom bonded to the polymer main chain among the phenyl groups is shown at around 146 ppm. Head of aromatic vinyl compound unit contained in aromatic vinyl compound-olefin-non-conjugated diene copolymer of the present invention-
The chain structure linked by the tail is a chain structure of two or more aromatic vinyl compounds that can be represented by the following structure.

[0006]

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Here, n is an arbitrary integer of 2 or more, preferably 3 or more. Ph is an aromatic group such as a phenyl group. Hereinafter, a styrene-ethylene-non-conjugated diene copolymer which is an example of the aromatic vinyl compound-olefin-non-conjugated diene copolymer of the present invention will be described. However, the invention is not limited to styrene-ethylene-non-conjugated diene copolymers. The present invention is based on TMS.
A styrene-ethylene-nonconjugated diene copolymer having a styrene chain structure attributed to a peak observed at 40 to 45 ppm by C-NMR measurement, preferably 42.3 to 43.1 ppm. ,
A styrene-ethylene-non-conjugated diene copolymer having a chain structure of styrene units attributed to peaks observed at 43.7 to 44.5 ppm, more preferably 42.3 to 43. 1 ppm,
43.7-44.5 ppm, 40.5-41.0 pp
m, a styrene-ethylene-nonconjugated diene copolymer having a chain structure of styrene units assigned by peaks observed at 43.0 to 43.6 ppm.

Further, in the copolymer, the stereoregularity of a phenyl group having an alternating structure of styrene and ethylene represented by the following general formula (1) contained in the copolymer structure is determined by isotactic dyad fraction. m is greater than 0.75, preferably greater than 0.85, more preferably greater than 0.95, and the alternating structure index λ given by the following formula (i) is less than 70 and greater than 0.1 And a styrene-ethylene-nonconjugated diene copolymer. λ = A3 / A2 × 100 Formula (i) Here, A3 is three kinds of peaks a and b derived from a styrene-ethylene alternating structure represented by the following general formula (1 ′) and obtained by 13 C-NMR measurement. , C is the sum of the areas. A2 is 13C-NM based on TMS.
It is the total sum of the areas of peaks derived from main chain methylene and main chain methine carbon observed in the range of 0 to 50 ppm by R.

[0009]

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Wherein Ph is an aromatic group such as a phenyl group;
x represents the number of repeating units and represents an integer of 2 or more. )

[0011]

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Wherein Ph is an aromatic group such as a phenyl group;
x represents the number of repeating units and represents an integer of 2 or more. )

The isotactic dyad fraction m of the alternating copolymer structure of ethylene and styrene is calculated from the peak area Ar derived from the r structure of the methylene carbon peak appearing at about 25 ppm and the peak area Am derived from the m structure. , Can be obtained by the following equation (ii). m = Am / (Ar + Am) Formula (ii) The appearance position of the peak may be slightly shifted depending on the measurement conditions and the solvent. For example, using deuterated chloroform as a solvent,
Based on TMS, the peak derived from the r structure is
The peak derived from the m-structure appears around 25.4 to 25.5 ppm, and around 25.2 to 25.3 ppm. Also,
When heavy tetrachloroethane is used as a solvent and the center peak (73.89 ppm) of the triplet of heavy tetrachloroethane is used as a reference, the peak derived from the r structure is 25.3 to 2
Around 5.4 ppm, the peak derived from the m-structure was 25.
Appears around 1-25.2 ppm. Note that the m structure represents a meso diad structure, and the r structure represents a racemic diad structure. In the styrene-ethylene random copolymer of the present invention, the peak attributed to the r structure in the alternating copolymer structure of ethylene and styrene is not substantially observed.

Further, in the styrene-ethylene-nonconjugated diene copolymer of the present invention, the stereoregularity of the phenyl group in the chain structure of styrene units is isotactic. Isotacticity of the stereoregularity of the phenyl group in the chain structure of the styrene unit means that the isotactic dyad fraction ms (or the meso dyad fraction) is 0.5.
It refers to a structure showing a larger, preferably 0.7 or more, more preferably 0.8 or more. The stereoregularity of the chain structure of the styrene unit is determined by the peak position of methylene carbon around 43 to 44 ppm observed by 13C-NMR and the peak position of the main chain proton observed by 1H-NMR. Further, the present copolymer is a styrene-ethylene-non-conjugated diene copolymer having a head-tail styrene chain structure obtained by using a metallocene catalyst capable of producing isotactic polystyrene by homopolymerization of styrene. It can be described as union.

Further, the copolymer has a weight average molecular weight in terms of polystyrene of 10,000 or more, preferably 50,000 or more, particularly preferably 80,000 or more, and a molecular weight distribution (Mw / Mw).
A styrene-ethylene-nonconjugated diene copolymer wherein n) is 6 or less, preferably 4 or less. From the viewpoint of processability, the weight average molecular weight is preferably 1,000,000 or less, particularly preferably 500,000 or less. Here, the weight average molecular weight refers to a molecular weight in terms of polystyrene obtained by using GPC with standard polystyrene. The same applies to the following description.

On the other hand, in the case of a conventionally known pseudo-random copolymer, a head-tail chain structure of styrene cannot be found even at a maximum styrene content of around 50 mol%. Further, even if homopolymerization of styrene is attempted using a catalyst for producing a pseudorandom copolymer, no polymer can be obtained. A very small amount of atactic styrene homopolymer may be obtained depending on the polymerization conditions, etc., which is understood to be formed by cationic polymerization by coexisting methylalumoxane or alkylaluminum mixed therein, or by radical polymerization. Should.

The peak of the methylene carbon of the structure derived from the hetero-bond of styrene in the conventional pseudorandom copolymer having no stereoregularity is 34.0 to 34.5 ppm and 34.5.
It is known to be in two regions of ~ 35.2 ppm. (For example, Polymer Preprints,
Japan, 42 , 2292 (1993)) The styrene-ethylene-nonconjugated diene copolymer of the present invention has a peak attributable to a methylene carbon of a heterogeneous bond structure derived from styrene in a range of 34.5 to 35.2 ppm. It is observed, but is hardly observed at 34.0 to 34.5 ppm. This indicates one of the features of the copolymer of the present invention, and indicates that the phenyl group has a high stereoregularity even in a heterogeneous bond structure derived from styrene as shown in the following formula.

[0018]

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Further, the styrene-ethylene-nonconjugated diene copolymer of the present invention has an alternating structure of ethylene and styrene having high stereoregularity, an ethylene chain of various lengths, a heterogeneous bond of styrene, It has the characteristic of having various structures such as a chain of styrene having a length.
Further, the styrene-ethylene-non-conjugated diene copolymer of the present invention, the ratio of the alternating structure according to the content of styrene in the copolymer, the λ value obtained by the above formula is larger than 0.1 and less than 70, preferably Can be variously changed within a range of more than 0.1 and less than 30.

Since this stereoregular alternating structure is a crystallizable structure, the copolymer of the present invention can be made non-crystalline, by controlling the degree of crystallization by controlling the styrene content or by a suitable method. It is possible to provide various properties such as a polymer having a partially crystalline structure. λ value is 70
Less than 30, especially less than 30, is important for keeping the crystallinity of the copolymer at a low level. Therefore, the present copolymer is characterized in that it exhibits properties as a low crystalline, microcrystalline or non-crystalline polymer.

The copolymer of the present invention has no conventional stereoregularity and no styrene chain (a styrene chain is not observed by ordinary 13C-NMR measurement).
Compared to the ethylene-diene copolymer, the properties such as initial tensile modulus, hardness, breaking strength, solvent resistance, transparency, etc. are improved in each styrene content region and various crystallinities, and a new low Shows physical properties characteristic of crystalline resins, thermoplastic elastomers, and transparent soft resins. The styrene-ethylene-non-conjugated diene copolymer of the present invention, which basically does not contain an elutable plasticizer or a halogen, has a basic feature of high safety. When the alternating index λ value is lower than 30, the copolymer of the present invention has a feature of having various structures in a wide styrene content region because of low alternating property and high randomness. Show. Low styrene content 1
Even in the copolymer of 0 mol% to 50 mol%, the usual 1
The chain structure of styrene is observed by 3C-NMR measurement or by using styrene enriched at carbon-13. The copolymer of the present invention, in which styrene chains are randomly and uniformly present in the copolymer main chain having a low styrene content, is characterized by high initial modulus, high breaking strength and high transparency. The styrene-ethylene-non-conjugated diene copolymer has been described above, but the copolymer of the present invention is not limited to this.

The aromatic vinyl compound used in the present invention includes styrene and various substituted styrenes such as p
-Methylstyrene, m-methylstyrene, o-methylstyrene, ot-butylstyrene, mt-butylstyrene, pt-butylstyrene, p-chlorostyrene,
Examples thereof include o-chlorostyrene, α-methylstyrene, and the like, and compounds having a plurality of vinyl groups in one molecule such as divinylbenzene. Industrially, styrene, p-methylstyrene and p-chlorostyrene are preferably used, and styrene is particularly preferably used.

The olefins used in the present invention include ethylene, α-olefins having 3 to 20 carbon atoms, ie, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and cyclic olefins. I.e., cyclopentene, norbornene,
Preferably, ethylene and propylene are used, particularly preferably ethylene.

Non-conjugated dienes include 1,4-hexadiene, 1,5-hexadiene, ethylidene norbornene, dicyclopentadiene, norbornadiene,
-Vinyl-1 cyclohexene, 3-vinyl-1cyclohexene, 2-vinyl-1cyclohexene, 1-vinyl-
Various cyclovinyl, ortho-, meta-, and para-divinylbenzenes are used, and particularly preferably, various vinylcyclohexenes or divinylbenzenes are used. When various vinylcyclohexenes or divinylbenzenes are used, it is practically preferable because an aromatic vinyl compound-olefin-nonconjugated diene copolymer having a sufficiently high molecular weight can be easily obtained. In these cases, a mixture of non-conjugated dienes may be used. these,
The non-conjugated diene is an aromatic vinyl compound of the present invention-olefin-an aromatic vinyl compound-olefin copolymer structure in the non-conjugated diene copolymer, preferably an aromatic vinyl compound-ethylene copolymer structure. Since it is used to introduce a crosslinking point without impairing the basic physical properties, its copolymerized amount is preferably as small as possible within a range where a practical crosslinking point density can be obtained. Preferably,
0.01 to 20 mol%, more preferably 0.01 to 1
0 mol%, most preferably 0.01 to 3 mol%. Further, if necessary, the following monomer of the fourth component may be copolymerized. Α-olefins other than those selected above having 3 to 20 carbon atoms, ie, propylene, 1-butene,
1-Hexene, 4-methyl-1-pentene, 1-octene and cyclic olefins, ie cyclopentene, norbornene, are suitable.

The copolymer of the present invention is synthesized from an aromatic vinyl compound, an olefin, and a non-conjugated diene monomer using a polymerization catalyst comprising a crosslinked metallocene compound and a cocatalyst. As the bridged metallocene compound to be used, preferably, a metallocene compound represented by the following general formula (2) is used.

[0026]

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In the formula, A and B are an unsubstituted or substituted cyclopentaphenanthryl group (Chem. 8 to 9), an unsubstituted or substituted benzoindenyl group (Chem. 10 to 12), an unsubstituted or substituted cyclopentadienyl. A non-substituted or substituted indenyl group (Chemical Formula 14) or an unsubstituted or substituted fluorenyl group (Chemical Formula 15), and at least one of A and B is an unsubstituted or substituted cycloalkyl group. It is a group selected from a pentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, and an unsubstituted or substituted indenyl group. Preferably, at least one of A and B is a group selected from an unsubstituted or substituted cyclopentaphenanthryl group and an unsubstituted or substituted benzoindenyl group.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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(In the above formulas 8 to 15, R1 to R8
The groups are each hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR ₃ group, a SiR ₃ group or a PR ₂ group (R is Each represents a hydrocarbon group having 1 to 10 carbon atoms), and R1s, R2s, R3s,
4, R5, R6, R7, and R8 may be the same or different. If both A and B are unsubstituted or substituted cyclopentaphenanthryl groups, unsubstituted or substituted benzoindenyl groups, unsubstituted or substituted indenyl groups, they may be the same or different.

Specific examples of the unsubstituted cyclopentaphenanthryl group include a 3-cyclopenta [c] phenanthryl group and a 1-cyclopenta [l] phenanthryl group. As an unsubstituted benzoindenyl group, 4,
5-benzo-1-indenyl, (also known as benzo (e) indenyl), 5,6-benzo-1-indenyl, 6,7-
Benzo-1-indenyl is an example of a substituted benzoindenyl group such as an α-acenaphth-1-indenyl group.

The unsubstituted cyclopentadienyl group is cyclopentadienyl, and the substituted cyclopentadienyl group is 4-aryl-1-cyclopentadienyl,
5-diaryl-1-cyclopentadienyl, 5-alkyl-4-aryl-1-cyclopentadienyl, 4-
Alkyl-5-aryl-1-cyclopentadienyl,
4,5-dialkyl-1-cyclopentadienyl, 5-
Trialkylsilyl-4-alkyl-1-cyclopentadienyl, 4,5-dialkylsilyl-1-cyclopentadienyl and the like can be mentioned.

The unsubstituted indenyl group is 1-indenyl, and the substituted indenyl group is 4-alkyl-1-indenyl, 4-aryl-1-indenyl, 4,5-dialkyl-1-indenyl, 4,6-dialkyl -1-
Indenyl, 5,6-dialkyl-1-indenyl,
4,5-diaryl-1-indenyl, 5-aryl-
1-indenyl, 4-aryl-5-alkyl-1-indenyl, 2,6-dialkyl-4-aryl-1-indenyl, 5,6-diaryl-1-indenyl, 4,
5,6-triaryl-1-indenyl and the like. Examples of the unsubstituted fluorenyl group include a 9-fluorenyl group, and examples of the substituted fluorenyl group include a 7-methyl-9-fluorenyl group and a benzo-9-fluorenyl group. In the above general formula (2), Y is a carbon or silicon which has a bond to A and B and has another substituent, and is hydrogen or a methylene group having a hydrocarbon group having 1 to 15 carbon atoms. . The substituents may be different or the same. Y may have a cyclic structure such as a cyclohexylidene group and a cyclopentylidene group. Preferably,
Y has a bond with A and B, and is hydrogen or a group having 1 to 15 carbon atoms.
Is a substituted methylene group substituted with a hydrocarbon group. Examples of the hydrocarbon substituent include an alkyl group, an aryl group, a cycloalkyl group, and a cycloaryl group. The substituents may be different or the same. Particularly preferably, Y _{is, -CH 2 -, - CMe 2} -, - CEt 2 -, -
CPh _2- , cyclohexylidene, cyclopentylidene and the like. Here, Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group. X is hydrogen, halogen,
An alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, and 1 carbon atom
A silyl group having from 4 to 4 hydrocarbon substituents, having from 1 to 1 carbon atoms
It is an alkoxy group having 0 or a dialkylamide group having an alkyl substituent having 1 to 6 carbon atoms. Halogen is chlorine, bromine, etc., alkyl group is methyl group, ethyl group, etc., aryl group is phenyl group, etc., alkylaryl group is benzyl group, silyl group is trimethylsilyl group, etc., and alkoxy group is Examples of the group include a methoxy group, an ethoxy group and an isopropoxy group, and examples of the dialkylamide group include a dimethylamide group. M is zirconium, hafnium, or titanium. Particularly preferred is zirconium. As for the complex in which a racemic body or a meso body exists, a racemic body is preferably used, but a racemic body, a mixture of meso bodies, or a meso body may be used. As for the complex in which a pseudo-racemic body or a pseudo-meso form is present, a pseudo-racemic form is preferably used, but a pseudo-racemic form, a mixture of the pseudo-meso form, or a pseudo-meso form may be used.

Examples of such a transition metal catalyst component include the following compounds. For example, dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium bisdimethylamide, di-n-propylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium Dichloride, dii
-Propylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, cyclohexylidenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, cyclopentylidenebis (3-
Cyclopenta [c] phenanthryl) zirconium dichloride, diphenylmethylenebis (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (4,5-benzo-1-indenyl) (3
-Cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (5,6-benzo-1-indenyl) (3-cyclopenta [c] phenanthryl)
Zirconium dichloride, dimethylmethylene (6,7-
Benzo-1-indenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (1-indenyl) (3-cyclopenta [ c] phenanthryl) zirconium dichloride, dimethylmethylene (1-fluorenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (4-phenyl-1-indenyl) (3-
Cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (4-naphthyl-1-indenyl) (3-cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylene (3-cyclopenta [c] phenanthryl) (4,5-naphtho- 1-indenyl) zirconium dichloride, dimethylmethylene (3-cyclopenta [c] phenanthryl) (α-acenaphth-1-indenyl) zirconium dichloride, dimethylmethylenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylenebis (1 -Cyclopenta [l] phenanthryl) zirconium bisdimethylamide, di-n-propylmethylenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride, - propyl methylene bis (1-cyclopenta [l] phenanthryl) zirconium dichloride, cyclohexylidene bis (1-cyclopenta [l]
Phenanthryl) zirconium dichloride, cyclopentylidenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride, diphenylmethylenebis (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (4,5-benzo-1)
-Indenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (5,
6-benzo-1-indenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (6,7-benzo-1-indenyl) (1
-Cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (cyclopentadienyl)
(1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (1-indenyl)
(1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (1-fluorenyl)
(1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (4-phenyl-1-
Indenyl) (1-cyclopenta [l] phenanthryl) zirconium dichloride, dimethylmethylene (4-
Naphthyl-1-indenyl) (1-cyclopenta [l]
Phenanthryl) zirconium dichloride, dimethylmethylene (1-cyclopenta [l] phenanthryl)
(4,5-naphth-1-indenyl) zirconium dichloride, dimethylmethylene (1-cyclopenta [l] phenanthryl) (α-acenaphth-1-indenyl) zirconium dichloride, dimethylmethylene (1-cyclopenta [l] phenanthryl) (3 -Cyclopenta [c] phenanthryl) zirconium dichloride, dimethylmethylenebis (4,5-benzo-1-indenyl)
Zirconium dichloride {also known as dimethylmethylenebis (benzo [e] indenyl) zirconium dichloride}, di-n-propylmethylenebis (4,5-benzo-
1-indenyl) zirconium dichloride, dii-propylmethylenebis (4,5-benzo-1-indenyl)
Zirconium dichloride, cyclohexylidenebis (4,5-benzo-1-indenyl) zirconium dichloride, cyclopentylidenebis (4,5-benzo-1
-Indenyl) zirconium dichloride, diphenylmethylenebis (4,5benzo-1-indenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (1-indenyl) )
(4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (1-fluorenyl) (4
5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (4-phenyl-1-indenyl) (4,5-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (4-naphthyl-1-indenyl) (4 5-benzo-1-indenyl) zirconium dichloride, dimethylmethylenebis (5,6-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (5,6-benzo-1-indenyl) (1
-Indenyl) zirconium dichloride, dimethylmethylenebis (6,7-benzo-1-indenyl) zirconium dichloride, dimethylmethylene (6,7-benzo-
1-indenyl) (1-indenyl) zirconium dichloride, dimethylmethylenebis (4,5-naphth-1-
(Indenyl) zirconium dichloride, dimethylmethylenebis (α-acenaphth-1-indenyl) zirconium dichloride, dimethylmethylenebis (4,5-benzo-1-indenyl) zirconiumbis (dimethylamide), dimethylmethylene (1-indenyl) (4 , 5-
Benzo-1-indenyl) zirconium bis (dimethylamide) and the like. Although the zirconium complex has been exemplified above, the same compounds as described above are preferably used for the titanium and hafnium complexes. Further, a mixture of a racemic body and a meso body may be used. Preferably, racemic or pseudo-racemic is used. In these cases, a D-form or an L-form may be used. As the co-catalyst used in the present invention, a co-catalyst conventionally used in combination with a transition metal catalyst component can be used. As such a co-catalyst, an aluminoxane (or alumoxane) or a boron compound is used. It is preferably used. Further, the present invention provides a method for producing an aromatic vinyl compound-olefin-nonconjugated diene copolymer in which the cocatalyst used in this case is an aluminoxane (or alumoxane) represented by the following general formulas (5) and (6). Is the way.

[0041]

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In the formula, R represents an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or hydrogen, and m represents 2 to 10 carbon atoms.
It is an integer of 0. Each R may be the same or different.

[0043]

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In the formula, R ′ is an alkyl group having 1 to 5 carbon atoms,
An aryl group having 6 to 10 carbon atoms or hydrogen, and n is 2 to 1
It is an integer of 00. Each R 'may be the same or different. As the aluminoxane, methylalumoxane, ethylalumoxane and triisobutylalumoxane are preferably used, and methylalumoxane is particularly preferably used. If necessary, a mixture of these different alumoxanes may be used. These alumoxanes may be used in combination with alkylaluminums, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, and alkylaluminums containing halogen, for example, dimethylaluminum chloride. The addition of the alkyl aluminum is effective for removing a polymerization inhibitor such as a polymerization inhibitor in styrene, styrene, water in a solvent, and other substances that inhibit polymerization, and rendering the polymerization reaction harmless. However, by pre-distilling styrene, solvent, etc., bubbling with a dry inert gas, or reducing these amounts to a level that does not affect the polymerization by a known method such as passing through a molecular sieve,
Alternatively, slightly increase the amount of alumoxane used,
Alternatively, if it is added, it is not always necessary to add the alkyl aluminum during the polymerization. In the present invention, a boron compound can be used as a promoter together with the above transition metal catalyst component.

The boron compound used as a promoter is
Triphenylcarbenium tetrakis (pentafluorophenyl) borate {trityltetrakis (pentafluorophenyl) borate}, lithium tetra (pentafluorophenyl) borate, tri (pentafluorophenyl) borane, trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate , Tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (n-butyl) ammoniumtetra (p-
Tolyl) phenyl borate, tri (n-butyl) ammonium tetra (p-ethylphenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, trimethylammonium tetra (p
-Tolyl) borate, trimethylammonium tetrakis-3,5-dimethylphenylborate, triethylammonium tetrakis-3,5-dimethylphenylborate, tributylammonium tetrakis-3,5-dimethylphenylborate, tributylammonium tetrakis-2,4-dimethyl Phenyl borate, anilinium tetrakis pentafluorophenyl borate, N,
N′-dimethylanilinium tetraphenyl borate,
N, N'-dimethylanilinium tetrakis (p-tolyl) borate, N, N'-dimethylanilinium tetrakis (m-tolyl) borate, N, N'-dimethylanilinium tetrakis (2,4-dimethylphenyl) borate N, N'-dimethylanilinium tetrakis (3,5-dimethylphenyl) borate, N, N'-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N'-diethylanilinium tetrakis (pentafluorophenyl) Borate, N, N'-
2,4,5-pentamethylanilinium tetraphenyl borate, N, N'-2,4,5-pentaethylanilinium tetraphenyl borate, di- (isopropyl)
Ammonium tetrakis pentafluorophenyl borate, di-cyclohexylammonium tetraphenyl borate, triphenylphosphonium tetraphenyl borate, tri (methylphenyl) phosphonium tetraphenyl borate, tri (dimethylphenyl) phosphonium tetraphenyl borate, triphenylcarbenium tetrakis (p- Tolyl) borate, triphenylcarbenium tetrakis (m-tolyl) borate, triphenylcarbenium tetrakis (2,4-dimethylphenyl) borate, triphenylcarbenium tetrakis (3,5-dimethylphenyl) borate, tropylium tetrakispenta Fluorophenyl borate, tropylium tetrakis (p-tolyl) borate, tropylium tetrakis (m-tri ) Borate, tropylium tetrakis (2,4-dimethylphenyl) borate, tropylium tetrakis (3,5-dimethylphenyl) borate. These boron compounds and the above-mentioned organoaluminum compounds may be used simultaneously. In particular, when a boron compound is used as a co-catalyst, the addition of an alkyl aluminum compound such as triisobutyl aluminum is effective for removing impurities such as water contained in the polymerization system that adversely affect the polymerization.

In producing the copolymer of the present invention, ethylene, the aromatic vinyl compound exemplified above, and dienes are brought into contact with a transition metal catalyst component which is a metal complex and a cocatalyst. As the method, any known method can be used. As a method of the above copolymerization, a method of polymerizing in a liquid monomer without using a solvent, or pentane, hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, xylene,
There is a method in which a saturated aliphatic or aromatic hydrocarbon such as chloro-substituted benzene, chloro-substituted toluene, methylene chloride, chloroform or the like or a halogenated hydrocarbon is used alone or in a mixed solvent. If necessary, a method such as batch polymerization, continuous polymerization, batch polymerization, slurry polymerization, preliminary polymerization, or gas phase polymerization can be used. Conventionally, when styrene is used as a monomer component, gas-phase polymerization cannot be adopted because of its low vapor pressure. However, when a catalyst composed of the transition metal catalyst component for polymerization of the present invention and a cocatalyst is used, the copolymerization ability of styrene is extremely high, so that copolymerization is possible even at a low styrene monomer concentration. That is, copolymerization of olefin, styrene and non-conjugated diene is possible even under a low styrene partial pressure under gas phase polymerization conditions. In this case, the transition metal catalyst component for polymerization and the cocatalyst may be used by being supported on a suitable known carrier.

The copolymerization temperature is suitably from -78 ° C to 200 ° C. A polymerization temperature lower than -78 ° C is industrially disadvantageous, and a temperature higher than 200 ° C is not suitable because decomposition of the metal complex occurs. More preferably, industrially, it is 0 ° C to 1 ° C.
It is 60 ° C, particularly preferably 30 ° C to 160 ° C. The pressure during the copolymerization is suitably from 0.1 to 100 atm.
It is preferably 1 to 30 atm, particularly preferably 1 to 30 atm.
-10 atm. When an organoaluminum compound is used as a cocatalyst, it is used in an aluminum atom / complex metal atom ratio of 0.1 to 100,000, preferably 10 to 10,000 with respect to the metal of the complex. If it is less than 0.1, the metal complex cannot be activated effectively, and if it exceeds 100,000, it is economically disadvantageous. When a boron compound is used as a co-catalyst, the boron compound is used in a ratio of boron atom / complex metal atom ratio of 0.01 to 100, preferably 0.1 to 100.
1 to 10, particularly preferably 1. If it is less than 0.01, the metal complex cannot be activated effectively, and if it exceeds 100, it is economically disadvantageous. The metal complex and the cocatalyst may be mixed and prepared outside the polymerization tank, or may be mixed in the tank during polymerization.

The aromatic vinyl compound-olefin-nonconjugated diene copolymer of the present invention can be made into a crosslinked product by any known crosslinking method. Among them, dynamic vulcanization is preferably used. The dynamic vulcanization referred to in the present invention is a technique for simultaneously causing dispersion and crosslinking by strongly kneading various compounds in a molten state under a temperature condition at which a crosslinking agent reacts,
A. Y. Coran et al. (Rub. Chem. An
d Technol. vol. 53.141- (198
0)). The kneading machine at the time of dynamic vulcanization is usually carried out using a closed kneader such as a Banbury mixer or a pressure kneader, a single-screw or twin-screw extruder. The kneading temperature is usually 130 to 300 ° C, preferably 150 to 200 ° C.
° C. The kneading time is usually 1 to 30 minutes. As a cross-linking agent for dynamic vulcanization, an organic peroxide or a phenol resin cross-linking agent is usually preferably used. Specific examples of the organic peroxide include dicumyl peroxide, 2,5.
-Dimethyl-2,5-di (tert-butylperoxy) -hexane, 2,5-dimethyl-2,5-di (te
rt-butylperoxy) -hexyne-3, di-ter
t-butyl peroxide and the like. As a crosslinking aid, a maleimide compound or a polyfunctional vinyl monomer such as divinylbenzene or trimethylolpropane trimethacrylate can be used.

The polymer obtained by crosslinking the aromatic vinyl compound-olefin-non-conjugated diene copolymer of the present invention has high transparency and improves mechanical properties at high temperatures, such as breaking strength, tensile modulus and compression set. Elastomer. Further, the aromatic vinyl compound-olefin-non-conjugated diene copolymer of the present invention is blended with another resin such as a crystalline olefin resin, and is subjected to so-called dynamic vulcanization in the presence of an organic peroxide or a phenol resin crosslinking agent. (Dynamic heat treatment). Examples of the crystalline olefin resin used herein include a homopolymer of an α-olefin having 2 to 20 carbon atoms or a copolymer thereof. As specific examples of these crystalline olefin resins,
Ethylene homopolymer by low pressure method, high pressure method, etc .; copolymer of ethylene with at least 30 mol% of other α-olefin, at least one vinyl monomer such as vinyl acetate and ethyl acrylate; propylene homopolymer ,
Random copolymer of propylene with 10 mol% or less of other α-olefin, block copolymer of propylene with 30 mol% or less of other α-olefin, 1-butene homopolymer, 1-butene and 10 Mol% or less of other α
-Random copolymer with olefin, 4-methylpentene-1 homopolymer, 4-methylpentene-1 and 20
A random copolymer with another α-olefin of mol% or less can be mentioned. Among the above crystalline olefin resins,
Ethylene homopolymer, propylene homopolymer or propylene-α-olefin copolymer having a propylene content of 50 mol% or more is particularly preferred. The above-mentioned crystalline olefin resins can be used alone or in combination. In the present invention, the amount of the crosslinking agent used is usually an aromatic vinyl compound-olefin-non-conjugated diene copolymer 10
It is used in a ratio of 0.04 to 15 parts by weight with respect to 0 parts by weight.

Further, the composition of the aromatic vinyl compound-olefin-non-conjugated diene copolymer or the aromatic vinyl compound-olefin-non-conjugated diene copolymer and the crystalline olefin resin of the present invention improves the physical properties. For purposes, blends with other polymers are also possible. For example, polystyrene, poly (styrene-acrylonitrile), PMM
Blends with A, ABS, SBS, SIS, SEBS, SEPS and the like. Further, the aromatic vinyl compound of the present invention having a different aromatic vinyl compound content-olefin-
Blends of non-conjugated diene copolymers are also available. These may be reacted with the main component in addition to the dynamic vulcanization reaction or may be used as a mere blend material after the reaction is completed.

The resin composition of the present invention may contain a softener, a heat stabilizer, an antistatic agent, a weather stabilizer, an antioxidant, a filler, if necessary, as long as the object of the present invention is not impaired. And additives such as a coloring agent and a lubricant.
As the filler, specifically, calcium carbonate, talc,
Clay, calcium silicate, magnesium carbonate, magnesium hydroxide and the like. Examples of softeners that can be added as necessary to adjust the hardness and fluidity of the product include mineral oils such as paraffinic, naphthenic, aroma-based process oils and liquid paraffins. Various materials such as a softener, castor oil, linseed oil and the like are used. These softeners may be added at the time of kneading, or may be contained in advance in the production of the aromatic vinyl compound-olefin-nonconjugated diene copolymer (so-called oil-extended rubber). The amount of the softening agent to be added is generally preferably from 0 to 150 parts by weight based on 100 parts by weight of the aromatic vinyl compound-olefin-nonconjugated diene copolymer.

[0052]

The present invention will be described below with reference to examples.
The present invention is not limited to the following examples. In the following description, Cp is a cyclopentadienyl group, In
d is a 1-indenyl group, BInd is 4,5-benzo-1
-Indenyl group, Flu represents a 9-fluorenyl group, Me represents a methyl group, Et represents an ethyl group, tBu represents a tertiary-butyl group, and Ph represents a phenyl group.

The copolymers obtained in each of the examples and comparative examples were analyzed by the following means. The 13C-NMR spectrum was measured using a heavy chloroform solvent or a heavy 1,1,2,2-tetrachloroethane solvent using α-500 manufactured by JEOL Ltd. with reference to TMS. Here, the measurement based on TMS is as follows.
First, the shift value of the center peak of the triplet 13C-NMR peak of heavy 1,1,2,2-tetrachloroethane was determined based on TMS. Next, the copolymer was placed in a heavy 1,1,2,2
-Dissolved in tetrachloroethane and 13C-NMR was measured, and each peak shift value was calculated based on the triplet center peak of heavy 1,1,2,2-tetrachloroethane.
The shift value of the triplet center peak of heavy 1,1,2,2-tetrachloroethane was 73.89 ppm. The 13C-NMR spectrum measurement for quantifying the peak area is NO
The pulse width was 45 ° by a proton gate decoupling method in which E was erased, and the repetition time was 5 seconds as a standard. Incidentally, the measurement was carried out under the same conditions except that the repetition time was changed to 1.5 seconds, and the quantitative value of the peak area of the copolymer coincided with the case of the repetition time of 5 seconds within the measurement error range. Determination of the styrene content in the copolymer was performed by 1H-NMR, and the equipment was α- manufactured by JEOL Ltd.
500 and AC-250 manufactured by BRUCKER were used.
Using a heavy chloroform solvent or heavy 1,1,2,2-tetrachloroethane, based on TMS, a peak derived from a phenyl group proton (6.5 to 7.5 ppm) and a proton peak derived from an alkyl group (0.8 to 7.5 ppm). 3 ppm). The non-conjugated diene content in the copolymer was similarly determined by 1H-NMR, and was determined from the intensity of the area of the side chain vinyl group. For the molecular weight in the examples, a weight average molecular weight in terms of standard polystyrene was determined using GPC (gel permeation chromatography). THF at room temperature
The copolymer soluble in water is THF
It measured using LC-8020. The copolymer insoluble in THF at room temperature was converted to 135 using 1,2,4-trichlorobenzene as a solvent using a 150 CV apparatus manufactured by Waters.
Measured in ° C. DSC measurement was carried out by Seiko Electronics DSC
Using 200, the glass transition point (Tg) was measured at a heating rate of 10 ° C./min under a stream of N ₂ .

Example 1 <Synthesis of copolymer> rac-dimethylmethylenebis (4,5-benzo-1-indenyl) was used as a transition metal compound.
Using zirconium dichloride under the conditions shown in Table 1,
It carried out as follows. Polymerization was carried out using an autoclave having a capacity of 10 L, a stirrer and a jacket for heating and cooling. 4000 ml of dehydrated toluene, 800 m of styrene
and heated and stirred at an internal temperature of 50 ° C. About 10 nitrogen
The system was purged by bubbling 0 L, and 10 ml of 1,4-hexadiene was added. Further, 8.4 mmol of triisobutylaluminum and 8.4 mmol of methylalumoxane (PMAO, manufactured by Tosoh Akzo Co., Ltd.) were added based on Al. Immediately, ethylene was introduced and the pressure was 1.1 MPa (1
After stabilization at 0 Kg / cm ² G), 8.4 μm of the transition metal compound was added from the catalyst tank installed on the autoclave.
mol, triisobutylaluminum 0.84 mmol
About 50 ml of a toluene solution in which was dissolved was added to the autoclave. Polymerization was carried out for 1 hour while maintaining the internal temperature at 50 ° C. and the pressure at 1.1 MPa. After the completion of the polymerization, the resulting polymerization solution was poured little by little into excess methanol which was vigorously stirred to precipitate the produced polymer. It was dried under reduced pressure at 70 ° C. until no change in weight was observed.
g of polymer were obtained.

Examples 2 and 3 Polymerization was carried out in the same manner as in Example 1 under the conditions shown in Table 1. Table 1 shows the polymerization conditions and results of each example.

[0056]

[Table 1]

Table 2 shows the composition of the obtained polymer, the molecular weight determined by GPC, and the glass transition point determined by DSC.

[0058]

[Table 2]

FIG. 1 shows a GPC chart of the copolymer obtained in Example 3 as a typical example of the styrene-ethylene-nonconjugated diene copolymer of the present invention. In the GPC measurement of the polymer obtained in each example, as shown in FIG. 1, the GPC curves obtained with different detectors (RI and UV) were as follows.
The agreement within the error range of the experiment indicates that the copolymer has a very uniform composition distribution. The single glass transition point obtained by DSC in Table 2 also indicates a uniform composition of the copolymer.

The styrene-ethylene-non-conjugated diene copolymer of the present invention is a copolymer mainly containing a typical structure represented by the following general formula at an arbitrary ratio. 13
The methine and methylene carbon regions of the C-NMR spectrum show peaks that can be assigned to the following. a to o are symbols indicating carbons shown in the following chemical structural formulas of Chemical Formulas 18 to 27. Based on the center peak (73.89 ppm) of the triplet of heavy tetrachloroethane, the following peaks are shown. (1) Alternating structure of styrene and ethylene

[0061]

Embedded image

(In the formula, Ph represents a phenyl group, x represents the number of repeating units, and represents an integer of 2 or more.)

That is, a structure consisting of a methine carbon connected to a Ph group and three methylene carbons sandwiched between the methine carbons, which can be represented by the following formula, is shown.

[0064]

Embedded image

General formula (hydrogen atom is omitted for simplicity) (2) Chain structure of ethylene

[0066]

Embedded image

(3) Structure consisting of an ethylene chain and one unit of styrene

[0068]

Embedded image

(4) Structure composed of styrene unit inversion (tail-to-tail structure)

[0070]

Embedded image

(5) an ethylene unit or a structure comprising an ethylene chain and two head-tail chains of a styrene unit;

[0072]

Embedded image

Or a structure in which a styrene unit and a styrene-ethylene alternate structural unit are randomly bonded.

[0074]

Embedded image

Alternating structure unit

[0076]

Embedded image

[0077]

Embedded image

(6) Structure comprising a head-tail chain of three or more styrene units

[0079]

Embedded image

25.1 to 25.2 ppm (c) 36.4 to 36.5 ppm (b) 44.8 to 45.4 ppm (a) 29.4 to 29.9 ppm (g) 36.5 to 36.8 ppm (E) 27.2 to 27.6 ppm (f) 45.4 to 46.1 ppm (d, h) 34.5 to 34.9 ppm (i) 42.3 to 43.1 ppm (j) 43.7 to 44 5.5 ppm (k) 35.6-36.1 ppm (l) 24.0-24.9 ppm (m) 40.5-41.0 ppm (n) 43.0-43.6 ppm (o) A slight shift, a microstructure of a peak, or a peak shoulder may occur due to the influence of measurement conditions, a solvent, or the like, or a long-range effect from an adjacent structure.

The assignment of these peaks was made by Macromo
recules, 13 , 849 (1980), Stu
f. Surf. Sci. Catal. , 517,199
0, J.P. Appl. Polymer Sci. , 53 ,
1453 (1994); Polymer Phys
s. Ed. , 13 , 901 (1975), Macrom.
olecules, 10 , 773 (1977), European Patent 416815, Japanese Patent Application Laid-Open No. 4-130114, 13C-NMR Inadequate method,
DEPT method and 13C-NMR database STN
(Specinfo) peak shift prediction.

The structural index λ of the copolymer obtained in each Example
And the isotactic dyad fraction m value of the styrene unit-ethylene unit alternating structure were determined according to the above formulas (i) and (ii), respectively. It is shown in Table 3.

[0083]

[Table 3]

[0084]

According to the present invention, a conventional crosslinked elastomer can be used.
The styrene-ethylene copolymer having a stereoregularity and a head-tail styrene chain structure is improved, and the mechanical strength, A crosslinked elastomer having excellent rubber elasticity, high-temperature properties, and transparency is provided and can be efficiently manufactured.

[Brief description of the drawings]

FIG. 1 is a GPC chart of the copolymer obtained in Example 3.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 212/36 C08F 212/36 F term (Reference) 4J028 AA01A AB00A AB01A AC01A AC10A AC28A BA00A BA01B BA02B BB00A BB00B BB01B BC12B BC25B EB01 EB02 EB16 EB17 EB18 EB21 EC04 GA14 4J100 AA02P AA03P AA04P AA16P AA17P AA19P AB02Q AB03Q AB04Q AB07Q AB16R AR04P AR11P AR16R AS11R AS15R BB01Q CA05 CA11 DA01 DA04 FA10

Claims (12)

[Claims] 1 to 70 mol% of an aromatic vinyl compound, 0.01 to 20 mol% of a non-conjugated diene and olefin 10
-Aromatic vinyl compound-olefin-non-conjugated diene copolymer, characterized in that the amount is from 9 to 99.99 mol%. 2. The aromatic vinyl compound-olefin-non-conjugated diene copolymer according to claim 1, which has a head-tail chain structure of two or more aromatic vinyl compound units. . 3. The aromatic vinyl compound-olefin-non-conjugated diene copolymer according to claim 2, wherein the olefin is ethylene. 4. The method according to claim 2, wherein the non-conjugated diene is divinylbenzene or vinylcyclohexene.
The aromatic vinyl compound-olefin-non-conjugated diene copolymer described in the above. 5. A 42.3 to 43.1 ppm, 43.7 to 44.3 ppm by 13 C-NMR measurement based on TMS.
The aromatic vinyl compound-ethylene-non-conjugated diene copolymer according to claim 3, wherein the copolymer has an aromatic vinyl compound unit chain structure attributed to a peak observed at 5 ppm. 6. 40.5 to 41 ppm, 43.0 to 43.6 p by 13 C-NMR measurement based on TMS.
pm, 42.3-43.1 ppm, 43.7-44.5
The aromatic vinyl compound-ethylene-non-conjugated diene copolymer according to claim 3, which has a chain structure of an aromatic vinyl compound unit assigned by a peak observed in ppm. 7. The stereoregularity of a phenyl group in an alternating structure of an aromatic vinyl compound represented by the following general formula (1) and ethylene contained in the copolymer structure is 0 in isotactic dyad fraction m. The aromatic vinyl compound-ethylene-non-conjugated diene copolymer according to claim 3, wherein the copolymer is larger than 0.75. Embedded image (Wherein Ph represents an aromatic group, x represents the number of repeating units, and 2
Represents the above integer. ) 8. The method according to claim 1, wherein the aromatic vinyl compound, the olefin and the non-conjugated diene are polymerized using a polymerization catalyst comprising a transition metal compound represented by the following general formula (2) and a co-catalyst. A method for producing an aromatic vinyl compound-olefin-nonconjugated diene copolymer according to any one of claims 1 to 7. Embedded image In the formula, A and B represent an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group,
A group selected from an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group or an unsubstituted or substituted fluorenyl group, wherein at least one of A and B is an unsubstituted or substituted cyclopentaphenanthryl group , An unsubstituted or substituted benzoindenyl group or an unsubstituted or substituted indenyl group. Y is a methylene, silylene or ethylene group which has a bond with A and B, and additionally has hydrogen or a hydrocarbon group having 1 to 15 carbon atoms. The substituents may be different or the same. Y may have a cyclic structure. X is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms, An alkoxy group having 1 to 10 carbon atoms or a dialkylamide group having an alkyl substituent having 1 to 6 carbon atoms. M is zirconium, hafnium, or titanium. 9. A composition comprising 30 to 99% by weight of the aromatic vinyl compound-olefin-nonconjugated diene copolymer according to any one of claims 1 to 7. 10. A molded article obtained by molding the composition according to claim 9. 11. A molded product obtained by crosslinking the aromatic vinyl compound-olefin-non-conjugated diene copolymer according to any one of claims 1 to 7. 12. A molded article obtained by crosslinking the composition according to claim 9.