JP3121109B2 - Olefin copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel olefin copolymer. More specifically, the present invention provides
Syndiotactic polystyrene chain that has excellent heat resistance, chemical resistance and electrical properties, has good toughness, tensile strength, tensile elongation, tensile elasticity and compatibilizing ability, and is useful as a material for composite materials and heat-resistant elastomers. The present invention relates to an olefin-based copolymer having as a graft component.

[0002]

2. Description of the Related Art In general, styrene-based polymers include those having an atactic structure having a stereoregularity by radical polymerization of a styrene-based monomer and those having an isotactic structure obtained using a Ziegler-based catalyst. But
The research group of the present inventors previously succeeded in developing a styrenic polymer having a high syndiotacticity, and further synthesized a syndiotactic styrenic polymer obtained by copolymerizing this styrenic monomer and other components. Polymers have been developed (Japanese Patent Laid-Open Nos. 62-104818 and 63-24109).
No.). These syndiotactic styrene-based polymers or copolymers are excellent in heat resistance, chemical resistance and electrical properties, and are expected to be applied to various fields. However, the styrene-based polymer, particularly syndiotactic polystyrene, has insufficient toughness and elongation, and has poor compatibility with other resins, so that its use is inevitably limited. As a means for remedying such a defect, a method of grafting an α-olefin to syndiotactic polystyrene (Japanese Patent Application No. 3-89073) has been proposed, but in this method, the method comprises an α-olefin chain. Since the soft segment does not have a structure sandwiched between the hard segments consisting of styrene chains,
In some cases, it cannot be sufficiently developed into an elastomer. On the other hand, a method using a divinylbenzene residue in a polymer main chain as a graft initiation reaction point has been attempted (JP-A-1-118510, JP-A-1-123811).
Publication), using this olefin-based graft precursor,
An example in which syndiotactic polystyrene is graft-copolymerized has not been known so far.

[0003]

SUMMARY OF THE INVENTION Under such circumstances, the present invention is intended to maintain the excellent heat resistance, chemical resistance, and electrical properties inherent in syndiotactic polystyrene, as well as toughness and tensile strength. Olefin copolymer with syndiotactic polystyrene chain as a graft component, which has improved tensile strength, tensile elongation, tensile elasticity and compatibility with olefin resins and diene resins, and is useful as a material for composite materials and heat-resistant elastomers The purpose of this is to provide.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to develop an olefin copolymer having a syndiotactic polystyrene chain as a graft component having the above-mentioned preferable properties. As a result, the stereoregularity of the styrene chain obtained by graft copolymerizing a styrene-based monomer at a specific ratio to an ethylene / α-olefin copolymer having a polymerizable carbon-carbon double bond in the side chain is high. It has been found that an olefin copolymer having a syndiotactic structure and having a reduced viscosity or a melt index and a tensile strength characteristic in a specific range can achieve the object. The present invention has been completed based on such findings. That is, the present invention provides an ethylene / α-olefin copolymer having a polymerizable carbon-carbon double bond in a side chain,
It is obtained by graft copolymerization of a styrene monomer, and has a high syndiotactic structure in which the stereoregularity of the chain composed of styrene monomer units is high, and its content is 0.
Reduced viscosity at a concentration of 0.05 g / deciliter in 1,2,4-trichlorobenzene at a temperature of 135 ° C. of 0.05 to 25 deciliter / g, or 300 The melt index measured under a load of 2.16 kg at 0.001 ° C. is 0.001 to 500 g / 10 min, the tensile strength is 200 to 500 kg / cm ² , the tensile elongation is 100 to 600%, and the tensile modulus is 1,000. ~ 2
An object of the present invention is to provide an olefin-based copolymer characterized by having a weight of 000 kg / cm ² .

[0005] The ethylene / α-olefin copolymer having a polymerizable carbon-carbon double bond in the side chain in the present invention is not particularly limited, and various copolymers can be mentioned. Preferred copolymers are ethylene,
It is a copolymer comprising an α-olefin having 3 to 20 carbon atoms and a diene monomer. Here, specific examples of the α-olefin include propylene; butene-1; hexene-1; octene-1; decene-1; heptene-1;
Pentene-1; nonene-1; 4-phenylbutene-1;
6-phenylhexene-1; 3-methylbutene-1; 4
-Methylpentene-1; 3-methylpentene-1; 3-
Methylhexene-1; 4-methylhexene-1; 5-methylhexene-1; 3,3-dimethylpentene-1;
3,4-dimethylpentene-1; 4,4-dimethylpentene-1; vinylcyclohexane; vinylcyclohexene and the like. Further, a halogen-substituted α-olefin can also be used, and examples of the halogen-substituted α-olefin include hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; fluoroethylene; 1,1-difluoroethylene; Propene; trifluoroethylene; 3,4-dichlorobutene-1 and the like. Then, the α-olefin may contain a cyclic olefin as necessary. Examples of the cyclic olefin include norbornene;
Methyl norbornene; 5-ethylnorbornene; 5,6
-Dimethylnorbornene; 1-methylnorbornene; 5
-Ethyl norbornene and the like. These α-
The olefins may be used alone or in combination of two or more. Where ethylene · α
-As the olefin copolymer, the ethylene component is 40 to
98 mol%, preferably 50 to 97 mol%, and the α-olefin component is in the range of 60 to 2 mol%, preferably 50 to 3 mol%.

On the other hand, diene monomers are used to introduce a double bond into a side chain. For example, 1,
3-butadiene; chloroprene; isoprene; 1,3-
Hexadiene; having 4 to 4 carbon atoms such as 1,3-heptadiene
20, conjugated diene compounds, cyclic olefins such as vinyl norbornene, and a general formula

[0007]

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Wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ³ is a hydrogen atom, a halogen atom or 1 to 8 carbon atoms. And m represents 0 or an integer of 1 to 4, and when m is 2 or more, a plurality of R ² may be the same or different. And the like. Among these, the vinylstyrene-based compound represented by the above general formula (I) or (II) is particularly preferred.
Here, R ¹ in the general formula (I) represents a hydrocarbon group having 1 to 20 carbon atoms, and R ² in the general formulas (I) and (II)
Represents a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ³ represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and m represents 0 or an integer of 1 to 4. The above general formula (I)
Specific examples of the vinylstyrene compound represented by are, for example, p- (2-propenyl) styrene, m- (2-propenyl) styrene, p- (3-butenyl) styrene,
m- (3-butenyl) styrene, o- (3-butenyl)
Styrene, p- (4-pentenyl) styrene, m- (4
-Pentenyl) styrene, o- (4-pentenyl) styrene, p- (7-octenyl) styrene, p- (2-methyl-3-butenyl) styrene, p- (1-methyl-3)
-Butenyl) styrene, p- (3-methyl-3-butenyl) styrene, p- (2-ethyl-3-butenyl) styrene, p- (2-ethyl-4-pentenyl) styrene,
m- (2-methyl-3-butenyl) styrene, o- (2
-Methyl-3-butenyl) styrene, 4-vinyl-4 '
-(3-butenyl) biphenyl, 4-vinyl-4'-
(4-pentenyl) biphenyl, 4-vinyl-3'-
(3-butenyl) biphenyl, 4-vinyl-2 '-(4
-Pentenyl) biphenyl, 4-vinyl-4- (2-methyl-3-butenyl) biphenyl, m- (3-butenyl) -α-methylstyrene, o- (3-butenyl) -α
-Methylstyrene, p-3-butenyl) -α-methylstyrene and the like.

As the vinylstyrene compound represented by the general formula (II), there may be mentioned the compounds exemplified in the above general formula (I) in which the α-olefin residue is substituted by a vinyl group. . Specific examples include divinylbenzene, divinyltoluene, and isopropenylstyrene. In the present invention, the diene monomers may be used alone or in combination of two or more. In the ethylene / α-olefin copolymer having a polymerizable carbon-carbon double bond in the side chain used in the present invention, the graft point is not styrene-based in order to control the graft efficiency and the graft chain length in a wide range. Advantageously, it is a saturated double bond. In order to produce such an ethylene / α-olefin copolymer, a catalyst mainly composed of a transition metal compound and an organometallic compound (particularly, trialkylaluminum), or a supported transition metal compound and an organometallic compound And ethylene, the α-olefin and the diene monomer, particularly those represented by the general formulas (I) and (II)
May be copolymerized with one selected from the vinylstyrene compounds represented by Thereby, a styrenic double bond can be introduced into the side chain.

When a graft starting point is formed using the vinylstyrene compound represented by the general formula (II),
A crosslinked product is easily formed, a sufficient reaction rate cannot be obtained, and an unreacted monomer remains, so that it is likely to be restricted in production.
On the other hand, when the graft starting point is generated using the vinylstyrene-based compound represented by the general formula (I), cross-linking hardly occurs and the reaction rate is high. Although it is possible to produce a grafted product using an α-olefinic double bond residue as a graft starting point, it is difficult to control the graft chain length and grafting efficiency in a wide range. The thus obtained ethylene / α-olefin copolymer having a polymerizable carbon-carbon double bond in the side chain may have any of an atactic structure, an isotactic structure, and a syndiotactic structure. . The copolymerization mode may be a random type or a block type. Further, the unsaturated group content is desirably in the range of 1 × 10 ⁻⁵ to 15 mol%, preferably 1 × 10 ⁻⁴ to 10 mol%.
As for the molecular weight, the reduced viscosity at a concentration of 0.05 g / deciliter measured in 1,2,4-trichlorobenzene at a temperature of 135 ° C. is preferably in the range of 0.01 to 30 deciliter / g. In addition, as long as an ethylene / α-olefin-based copolymer can be produced, an ethylene / α-olefin-based copolymer containing a component partially insoluble in a solvent can be used. As the ethylene / α-olefin copolymer obtained as described above,
Particularly preferred are ethylene / propylene copolymer and ethylene / butene-1 copolymer. Further, an ethylene / diene copolymer having a graft starting point or an ethylene / α-olefin / diene copolymer having a graft starting point is also preferable.

The olefin copolymer of the present invention is obtained by graft copolymerizing a styrene monomer to the ethylene / α-olefin copolymer. Here, the styrene monomer is represented by the general formula (III)

[0012]

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Wherein R ⁴ is a substituent containing at least one of a hydrogen atom, a halogen atom or a carbon atom, a tin atom and a silicon atom; n is an integer of 1 to 5; , Each R ⁴ may be the same or different. ] It is a compound represented by these. As such a compound, specifically, for example, styrene; p-methylstyrene; o-
2,4-dimethylstyrene; 3,4-dimethylstyrene; 3,5-dimethylstyrene; alkylstyrene such as p-tert-butylstyrene, p-chloro Styrene; m-chlorostyrene; o-chlorostyrene; p-bromostyrene; m-bromostyrene; o-bromostyrene; p-fluorostyrene; m-fluorostyrene; o-fluorostyrene; Halogenated styrene, such as 4-vinylbiphenyl; 3-vinylbiphenyl; vinylbiphenyls such as 2-vinylbiphenyl, 1- (4-vinylphenyl) -naphthalene; 2- (4-vinylphenyl) -naphthalene; 1- (3-vinylphenyl) -naphthalene; 2
-(3-vinylphenyl) -naphthalene; 1- (2-vinylphenyl) -naphthalene; vinylphenylnaphthalenes such as 2- (2-vinylphenyl) naphthalene;
-(4-vinylphenyl) -anthracene; 2- (4-
9- (4-vinylphenyl) -anthracene; 1- (3-vinylphenyl)
-Anthracene; 2- (3-vinylphenyl) -anthracene; 9- (3-vinylphenyl) -anthracene;
1- (2-vinylphenyl) -anthracene; 2- (2
-Vinylphenyl) -anthracene; vinylphenylanthracenes such as 9- (2-vinylphenyl) -anthracene; 1- (4-vinylphenyl) -phenanthrene; 2- (4-vinylphenyl) -phenanthrene;
-(4-vinylphenyl) -phenanthrene; 4- (4
-Vinylphenyl) -phenanthrene; 9- (4-vinylphenyl) -phenanthrene; 1- (3-vinylphenyl) -phenanthrene; 2- (3-vinylphenyl)
-(3-vinylphenyl) -phenanthrene; 4- (3-vinylphenyl) -phenanthrene; 9- (3-vinylphenyl) -phenanthrene;
1- (2-vinylphenyl) -phenanthrene; 2-
(2-vinylphenyl) -phenanthrene; 3- (2-
2- (2-vinylphenyl) -phenanthrene; vinylphenylphenanthrenes such as 9- (2-vinylphenyl) -phenanthrene; 1- (4-vinylphenyl) -pyrene; 2-
(4-vinylphenyl) -pyrene; 1- (3-vinylphenyl) -pyrene; 2- (3-vinylphenyl) -pyrene; 1- (2-vinylphenyl) -pyrene; 2- (2-
Vinylphenylpyrenes such as vinylphenyl) -pyrene; 4-vinyl-p-terphenyl; 4-vinyl-m-
Terphenyl; 4-vinyl-o-terphenyl; 3-vinyl-p-terphenyl; 3-vinyl-m-terphenyl; 3-vinyl-o-terphenyl; 2-vinyl-p-
Vinyl terphenyls such as terphenyl; 2-vinyl-m-terphenyl; 2-vinyl-o-terphenyl;
Vinylphenylterphenyls such as 4- (4-vinylphenyl) -p-terphenyl, 4-vinyl-4'-methylbiphenyl;4-vinyl-3'-methylbiphenyl;4-vinyl-2'-methylbiphenyl2-methyl-4-vinylbiphenyl; vinylalkylbiphenyls such as 3-methyl-4-vinylbiphenyl, 4-vinyl-4′-fluorobiphenyl; 4-vinyl-3′-fluorobiphenyl; 4-vinyl-2 '-Fluorobiphenyl;4-vinyl-2-fluorobiphenyl;4-vinyl-3-fluorobiphenyl;4-vinyl-4'-chlorobiphenyl;4-vinyl-3'-chlorobiphenyl;
-Vinyl-2'-chlorobiphenyl; 4-vinyl-2-
4-vinyl-3-chlorobiphenyl; 4-vinyl-4'-bromobiphenyl;4-vinyl-3'-bromobiphenyl;4-vinyl-2'-bromobiphenyl; 4-vinyl-2-bromobiphenyl 4-
Halogenated vinyl biphenyls such as vinyl-3-bromobiphenyl; trialkylsilylvinyl biphenyls such as 4-vinyl-4'-trimethylsilylbiphenyl;4-vinyl-4'-trimethylstannylbiphenyl; 4-vinyl-4 ' Trialkylstannylvinylbiphenyls such as tributylstannylbiphenyl,
Trialkylsilylmethylvinylbiphenyls such as 4-vinyl-4′-trimethylsilylmethylbiphenyl,
4-vinyl-4'-trimethylstannylmethylbiphenyl; trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4'-tributylstannylmethylbiphenyl, p-chloroethylstyrene; m-chloroethylstyrene; o- Halogen-substituted alkylstyrenes such as chloroethylstyrene, p-trimethylsilylstyrene; m-trimethylsilylstyrene; o-trimethylsilylstyrene; p-triethylsilylstyrene;
O-triethylsilylstyrene; alkylsilylstyrenes such as p-dimethyltert-butylsilylstyrene; p-dimethylphenylsilylstyrene; p-methyldiphenylsilylstyrene; phenyl groups such as p-triphenylsilylstyrene Halogen-containing silylstyrenes such as p- (p-dimethylchlorosilylstyrene; p-methyldichlorosilylstyrene; p-trichlorosilylstyrene; p-dimethylbromosilylstyrene; p-dimethyliodosilylstyrene; -Trimethylsilyl)
Silyl group-containing silyl styrenes such as dimethylsilyl styrene are exemplified. These styrene monomers may be used alone or in combination of two or more.

There are various methods for producing the olefin-based copolymer of the present invention.
A compound mainly composed of a transition metal compound and (b) an aluminoxane or a compound capable of forming an ionic complex by reacting with (B) (a) a transition metal compound and (c) a transition metal compound. Is used. There are various types of the transition metal compound of the component (a), and preferably, the general formula (IV) M ¹ R ⁵ ... R ^k (IV) wherein M ¹ is Ti , Zr, Cr, V, Nb, Ta or Hf, wherein R ^{5 to} R ^k are a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, An aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group,
Acyloxy group having 1 to 20 carbon atoms, allyl group, substituted allyl group, acetylacetonate group, substituted acetylacetonate group, substituent containing silicon atom, or carbonyl, oxygen molecule, nitrogen molecule, Lewis base, chain unsaturated Ligands such as hydrocarbon or cyclic unsaturated hydrocarbon, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group,
It represents a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. K represents the valence of the metal, and usually represents an integer of 2 to 5].

The substituted cyclopentadienyl group includes, for example, methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group;
1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group; 1,2,4-trimethylcyclopentadienyl group; pentamethylcyclopentadiene An enyl group; and a trimethylsilylcyclopentadienyl group. Further, the ligands of R ^{5 to} R ^k may form a crosslinked body by a covalent bond between the ligands. Specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom,
Examples of the iodine atom and the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an octyl group and a 2-ethylhexyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a phenoxy group. Examples of the aryl group having 6 to 20 carbon atoms, and examples of the alkylaryl group and the arylalkyl group include a phenyl group, a tolyl group, a xylyl group, and a benzyl group. Examples of the acyloxy group having 1 to 20 carbon atoms, such as a group, include a heptadecylcarbonyloxy group, a substituent containing a silicon atom, such as a trimethylsilyl group and a (trimethylsilyl) methyl group; and Lewis bases, such as dimethyl ether, diethyl ether, Ethers such as tetrahydrofuran,
Thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as benzonitrile, trimethylamine; triethylamine; tributylamine; N, N-dimethylaniline; pyridine;
As chain unsaturated hydrocarbons such as 2,2′-bipyridine; amines such as phenanthroline, and phosphines such as triethylphosphine and triphenylphosphine,
Examples of cyclic unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene, and derivatives thereof include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, and cyclooctatetra. And ene and derivatives thereof. Examples of the crosslink by a covalent bond include a methylene bridge, a dimethylmethylene bridge,
Ethylene crosslinking, dimethylsilylene crosslinking, dimethylstannylene crosslinking and the like can be mentioned.

Specific examples of the titanium compound include tetramethoxytitanium, tetraethoxytitanium, tetra-n
-Butoxytitanium, tetraisopropoxytitanium, titanium tetrachloride, titanium trichloride, titanium dichloride, titanium hydride, cyclopentadienyltrimethyltitanium, cyclopentadienyltriethyltitanium, cyclopentadienyltripropyltitanium, cyclopentadi Enyltributyltitanium, methylcyclopentadienyltrimethyltitanium, 1,2-dimethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltripropyltitanium Titanium, pentamethylcyclopentadienyl tributyl titanium, cyclopentadienyl methyl titanium dichloride, cyclopentadienyl ethyl titanium dichloride, pentamethyl cyclopen Dienyl methyl titanium dichloride, pentamethyl click cyclopentadienyl ethyl titanium dichloride, cyclopentadienyl dimethyl titanium monochloride, cyclopentadienyl diethyl titanium monochloride, cyclopentadienyltitanium trimethoxide,
Cyclopentadienyl titanium triethoxide, cyclopentadienyl titanium tripropoxide, cyclopentadienyl titanium triphenoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium triethoxide, pentamethyl Cyclopentadienyl titanium tripropoxide, pentamethylcyclopentadienyl titanium tributoxide, pentamethylcyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadi Enylmethoxytitanium dichloride, cyclopentadienyldimethoxytitanium chloride, pentamethylcyclopentadienylmethoxytitanium dichloride, cyclopentadienyl Revenge Le titanium, pentamethylcyclopentadienyl methyl diethoxy titanium, indenyl titanium trichloride, indenyl titanium trimethoxide, indenyl titanium triethoxide, indenyl trimethyl titanium, etc. indenyl tribenzylamine titanium and the like.

Among the transition metal compounds represented by the general formula (IV), specific examples of the zirconium compound in which M ¹ is zirconium include dicyclopentadienyl zirconium dichloride, tetrabutoxy zirconium, zirconium tetrachloride, Phenyl zirconium, cyclopentadienyl zirconium trimethoxide, pentamethylcyclopentadienyl zirconium trimethoxide, cyclopentadienyl tribenzyl zirconium,
Pentamethylcyclopentadienyl tribenzyl zirconium, bisindenyl zirconium dichloride, zirconium dibenzyl dichloride, zirconium tetrabenzyl, tributoxy zirconium chloride, triisopropoxy zirconium chloride, (pentamethyl cyclopentadienyl) trimethyl zirconium, (pentamethyl (Cyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) trichlorozirconium, (Cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethylzil , (Methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium, (dimethylcyclo (Pentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, bis (cyclopentadienyl) dimethylzirconium, bis ( Cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzyl Zirconium,
Bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) ) Dimethyl zirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium , Bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (pentamethylcyclo (Natadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium, ethylenebis (indenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium Dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropyl (cyclopentadienyl) (9- Fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethyldi Koniumu,
Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethyl zirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclobutyl (9-fluorenyl) (cyclo Pentadienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3
5-trimethylcyclopentadienyl) dimethyl zirconium and the like.

Specific examples of the vanadium compound include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride,
Examples thereof include vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium, dicyclopentadienyl vanadium, dicyclopentadienyl vanadium dichloride, cyclopentadienyl vanadium dichloride, and dicyclopentadienyl methyl vanadium. Specific examples of the niobium compound include niobium pentachloride, tetrachloromethyl niobium, dichlorotrimethyl niobium, dicyclopentadienyl niobium dichloride, dicyclopentadienyl niobium trihydride, pentabutoxy niobium and the like. Specific examples of the tantalum compound include tantalum pentachloride, dichlorotrimethyl tantalum, dicyclopentadienyl tantalum trihydride, and pentabutoxy niobium. Specific examples of the chromium compound include chromium trichloride, tetrabutoxychrome, and tetramethyl. Chromium, dicyclopentadienyl chromium, dibenzene chromium and the like can be mentioned.

Further, as other transition metal compounds,
What carried the transition metal compound on a carrier such as a magnesium compound or a silicon compound can be used,
A compound obtained by modifying the above transition compound with an electron donating compound can also be used. Particularly preferred among these transition metal compounds are titanium compounds and zirconium compounds. As the catalyst (A) in the present invention, (b) aluminoxane is used together with the transition metal compound (a). This aluminoxane is obtained by contacting an organoaluminum compound with a condensing agent, and has the general formula (V)

[0020]

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Wherein R ⁶ represents an alkyl group having 1 to 20 carbon atoms, preferably a methyl group, and p represents a number of 0 to 50, preferably 5 to 30. Aluminoxane represented by the general formula (VI)

[0022]

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Wherein R ⁶ is the same as above, and q is 2
-50, preferably 5-30. And the like. Examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum. Of these, trimethylaluminum is preferred. Examples of the condensing agent include water as a typical one, and any other condensing agent capable of condensing trialkylaluminum, for example, copper sulfate pentahydrate, water adsorbed on inorganic or organic substances, and the like. One.

In general, the contact product of an organoaluminum compound such as a trialkylaluminum and water is mixed with an unreacted trialkylaluminum and various condensation products together with the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane. Are molecules in which these are intricately associated, and these are various products depending on the contact conditions between the trialkylaluminum and water as a condensing agent. The method of contacting the alkyl aluminum compound with water at this time is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization, and water is added later, and furthermore, a metal salt or the like is contained. There is a method of reacting water of crystallization, water adsorbed on inorganic or organic substances with an organoaluminum compound. The water may contain up to about 20% of amines such as ammonia and ethylamine, sulfur compounds such as hydrogen sulfide, and phosphorus compounds such as phosphite. Although this reaction proceeds even without solvent, it is preferable to carry out the reaction in a solvent. Preferred solvents include hexane, heptane and
Examples thereof include aliphatic hydrocarbons such as decane and aromatic hydrocarbons such as benzene, toluene and xylene.

When the aluminoxane (for example, alkylaluminoxane) is used after the above-mentioned contact reaction, when a hydrated compound or the like is used, the solid residue is filtered off, and the filtrate is subjected to a temperature of 30 to 200 ° C. under normal pressure or reduced pressure. , Preferably 4
20 minutes to 8 hours at a temperature of 0 to 150 ° C., preferably 3 minutes
What heat-treated while evaporating a solvent in the range of 0 minute to 5 hours is preferable. In this heat treatment, the temperature may be appropriately determined depending on various conditions, but is usually in the above range. Generally, at a temperature lower than 30 ° C., no effect is exhibited,
On the other hand, when the temperature exceeds 200 ° C., thermal decomposition of the alkylaluminoxane itself occurs, and neither is preferable. The reaction product is obtained as a colorless solid or solution depending on the conditions of the heat treatment. The product thus obtained can be dissolved or diluted with a hydrocarbon solvent, if necessary, and used as a catalyst solution.

A preferred example of an aluminoxane, particularly an alkylaluminoxane, which is a contact product of an organoaluminum compound used as a catalyst component and a condensing agent, is an aluminum-methyl group (Al- The high magnetic field component in the methyl proton signal region based on the CH ₃ ) bond is 50% or less. In other words, at room temperature of the above contact product, when observing the proton nuclear magnetic resonance ⁽¹ H-NMR) spectra in toluene solvent, methyl proton signal based on the "Al-CH _3" is tetramethylsilane (TMS) standard In the range of 1.0 to -0.5 ppm. TMS
Is located in the methyl proton observation region based on “Al—CH ₃ ”.
—CH ₃ ”, the TMS
Methyl proton signal of toluene 2.35
ppm and the high magnetic field component (i.e., -0.1 to -0.0.
5 ppm) and other magnetic field components (ie, 1.0 to -0.1 pp)
m), the component having the high magnetic field component of 50% or less, preferably 45 to 5% of the whole can be suitably used as the catalyst component.

In the present invention, the catalyst (B) includes
(A) A transition metal compound together with (c) a transition metal compound
Compounds that can form an ionic complex by reacting with
You. There is no particular limitation on this compound, for example,
Formulas (VII) and (VIII) ([L¹-R⁷]^{U +})_V (M^TwoZ¹Z^Two... Z^e]^(ef)-)_W ... (VII) or ([L^Two]^{U +})_V (M^ThreeZ¹Z^Two... Z^e]^(ef)-)_W ... (VIII) (However, L^TwoIs M^Four, R⁸R⁹M^Five, R^Ten _ThreeC or R¹¹
M^FiveWhere L¹Is a Lewis base, M^TwoAnd M^ThreeIs the circumference
VB, VIB, VIIB, VIII, IB, II of the Periodic Table
An element selected from group B, IIIA, IVA and V, M^Four
And M^FiveAre the IIIB, IV, V, and VI groups of the periodic table, respectively.
Group B, VIIB, VIII, I, IB, IIA, IIB
And an element selected from group VIIA, Z¹~ Z^eIs water
Element atom, dialkylamino group, alkoxy group, carbon number 1
Alkoxy group having 20 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms
Si group, C1-20 alkyl group, C6-20
Aryl group, alkylaryl group, arylalkyl
Group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, carbon number
1 to 20 acyloxy groups, organic metalloid groups or halo
Gen atom, Z¹~ Z^eTwo or more
They may combine to form a ring. R⁷Is hydrogen atom, carbon
An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms
Group, alkylaryl group or arylalkyl group
Then R⁸And R⁹Is a cyclopentadienyl group,
Substituted cyclopentadienyl, indenyl or fluoro
Renyl group, R^TenIs an alkyl group having 1 to 20 carbon atoms, aryl
Represents an alkyl group, an alkylaryl group or an arylalkyl group.
You. R¹¹Is tetraphenylporphyrin, phthalocyanine
And macrocyclic ligands such as f is M^Two, M^ThreeValence of
Is an integer of 1 to 7, e is an integer of 2 to 8, and u is [L¹−
R⁷], [L ^TwoAn integer of 1 to 7 and v is 1
The above integer, w = (v × u) / (ef). 〕so
It is a compound represented.

[0028] Here, specific examples of the Lewis base represented by L ^1, ammonia, methylamine, aniline, dimethylamine, diethylamine, N- methylaniline, diphenylamine, trimethylamine, triethylamine, tri -n- butylamine, N , N-dimethylaniline, methyldiphenylamine, pyridine;
Amines such as 2′-bipyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phenanthroline, triethylphosphine,
Phosphines such as triphenylphosphine and diphenylphosphine; ethers such as dimethyl ether, diethyl ether and tetrahydrofuran dioxane; thioethers such as diethylthioether and tetrahydrothiophene; esters such as ethylbenzoate; nitriles such as acetonitrile and benzonitrile. And the like.

Also, M^TwoAnd M^ThreeAs a specific example,
B, Al, Si, P, As, Sb, etc., M^FourExamples of
Li, Na, Ag, Cu, Br, I, I_ThreeWhat
Th, M^FiveAs specific examples of Mn, Fe, Co, Ni,
Zn and the like can be mentioned. Z¹~ Z ^eAs a specific example,
For example, a dimethylamino group as a dialkylamino group,
Diethylamino group; an alkoxy group having 1 to 20 carbon atoms
Methoxy group, ethoxy group, n-butoxy group, carbon number 6
A phenoxy group as an aryloxy group,
-Dimethylphenoxy group, naphthyloxy group, carbon number 1
A methyl group, an ethyl group, an n-
Ropyl, iso-propyl, n-butyl, n-o
Octyl group, 2-ethylhexyl group, C 6-20
Reel, alkylaryl or arylalkyl
Phenyl, p-tolyl, benzyl,
Pentafluorophenyl group, 3,5-di (trifluoro
Tyl) phenyl group, 4-tert-butylphenyl
Group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group
Phenyl, 2,4-dimethylphenyl, 2,3-dimethyl
Tylphenyl group, 1,2-dimethylphenyl group, carbon number
P-fluoro as 1 to 20 halogen-substituted hydrocarbon groups
Phenyl group, 3,5-difluorophenyl group, pentac
Lorophenyl group, 3,4,5-trifluorophenyl
Group, pentafluorophenyl group, 3,5-di (trifur
Oromethyl) phenyl group, F, C as halogen atom
l, Br, I; pentamethylanti as an organic metalloid group
Mon group, trimethylsilyl group, trimethylgermyl group,
Diphenylarsine group, dicyclohexylantimony
And a diphenylboron group. R⁷, R^TenConcrete
Examples include those similar to those mentioned above.
R⁸And R⁹Specific examples of the substituted cyclopentadienyl group of
A methylcyclopentadienyl group, a butylcyclo
Pentadienyl group, pentamethylcyclopentadienyl
And those substituted with an alkyl group such as a group. This
Here, the alkyl group usually has 1 to 6 carbon atoms and is substituted.
The number of the substituted alkyl groups can be selected from an integer of 1 to 4.
You.

Among the compounds of the above general formulas (VII) and (VIII), those wherein M ² and M ³ are boron are preferred. Among the compounds of the general formulas (VII) and (VIII), the following compounds can be used particularly preferably. For example, compounds of the general formula (VII) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and methyltri (n-butyl) tetraphenylborate. Ammonium, benzyltriphenylborate tri (n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl (2-cyanopyridinium), trimethylsulfonium tetraphenylborate, benzyl tetraphenylborate Dimethylsulfonium, triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triphenylammonium tetra (pentafluorophenyl) borate, tetrabutylammonium tetra (pentafluorophenyl) borate , Tetra (pentafluorophenyl)
Tetraethylammonium borate, tetra (pentafluorophenyl) borate [methyltri (n-butyl) ammonium] borate, tetra (pentafluorophenyl) borate [benzyltri (n-butyl) ammonium], methyldiphenylammonium tetra (pentafluorophenyl) borate, Methyltriphenylammonium (pentafluorophenyl) borate, dimethyldiphenylammonium tetra (pentafluorophenyl) borate, anilinium tetra (pentafluorophenyl) borate, methylanilinium tetra (pentafluorophenyl) borate, dimethyl tetra (pentafluorophenyl) borate Anilinium, trimethylanilinium tetra (pentafluorophenyl) borate, dimethyl tetra (pentafluorophenyl) borate (m-d Roanilinium), dimethyl tetra (pentafluorophenylmethyl) borate (p-bromoanilinium), pyridinium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl) borate (p-cyanopyridinium), tetra (pentafluorophenyl) borate (N-methylpyridinium), tetra (pentafluorophenyl) borate (N-benzylpyridinium), tetra (pentafluorophenyl) borate (O
-Cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetra (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), tetra (pentafluorophenyl) ) Trimethylsulfonium borate, benzyldimethylsulfonium tetra (pentafluorophenyl) borate, tetrafelphosphonium tetra (pentafluorophenyl) borate, tetra (3,5-
And dimethylanilinium ditrifluoromethylphenyl) borate and triethylammonium tow hexafluoroarsenate.

On the other hand, compounds represented by the general formula (VIII) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (manganese tetraphenylporphyrin), ferrocenium tetra (pentafluorophenyl) borate, Decamethylferrocenium (pentafluorophenyl) borate, acetylferrocenium tetra (pentafluorophenyl) borate, formylferrocenium tetra (pentafluorophenyl) borate, cyanoferrocenium tetra (pentafluorophenyl) borate, tetra ( Silver pentafluorophenyl) borate, trityl tetra (pentafluorophenyl) borate, lithium tetra (pentafluorophenyl) borate, tetra (pentafluorophenyl)
Sodium borate, tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin manganese), tetra (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) borate (zinc tetraphenylporphyrin), silver tetrafluoroborate , Silver hexafluoroarsenate, silver hexafluoroantimonate and the like. As compounds other than the general formulas (VII) and (VIII), for example, tri (pentafluorophenyl) boric acid, tri [3,5-di (trifluoromethyl) phenyl] boric acid, triphenylboric acid and the like are also used. be able to.

In the present invention, an organometallic compound can be used as the component (d), if desired, together with the catalyst (A) or the catalyst (B). As the (d) organometallic compound optionally used, a compound represented by the general formula (IX) M ⁶ (R ¹² ) _r ... (IX) is used. In the general formula (IX), R ¹² is an alkyl group having 1 to 20 carbon atoms, 2 carbon atoms.
Alkenyl group having 20 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms or 7 to
And 20 aralkyl groups. Specifically, for example, methyl, ethyl, n-propyl, i-propyl, n-
Examples thereof include a butyl group, an i-butyl group, a hexyl group, a 2-ethylhexyl group, and a phenyl group. M ⁶ represents lithium, sodium, potassium, magnesium, zinc, cadmium, aluminum, boron, gallium, silicon or tin. R represents the valence of M ⁶ . There are various compounds represented by the general formula (IX). Specifically, for example, alkyllithium compounds such as methyllithium, ethyllithium, propyllithium, and butyllithium; alkylmagnesium compounds such as diethylmagnesium, ethylbutylmagnesium, and dinormalbutylmagnesium; dimethylzinc, diethylzinc, dipropylzinc, dibutyl Dialkyl zinc compounds such as zinc; alkyl gallium compounds such as trimethyl gallium, triethyl gallium, and tripropyl gallium; alkyl boron compounds such as triethyl boron, tripropyl boron and tributyl boron; alkyl tin compounds such as tetraethyl tin, tetrapropyl tin, and tetraphenyl tin And the like. Also, M
^{When 6} is aluminum, there are various compounds. Specifically, trimethyl aluminum,
Examples thereof include trialkylaluminum compounds such as triethylaluminum, triisopropylaluminum, triisobutylaluminum, trin-hexylaluminum, and trioctylaluminum.

The proportion of each component used in the catalyst used in the present invention varies depending on the type and concentration of the styrene monomer serving as a graft chain and the polymerizable unsaturated bond serving as a graft point, and is not generally defined. In the (A) catalyst, the molar ratio of the aluminum in the component (b) to the transition metal (for example, titanium) in the component (a) is 1 to 10;
⁶ , It is desirable to use the components (a) and (b) in such a ratio that preferably falls within the range of 10 to 10 ⁴ . on the other hand,
In the catalyst (B), the component (a) and the component (c) are used in such a ratio that the molar ratio of the component (c) to the component (a) is in the range of 0.01 to 100, preferably 1 to 10. It is desirable to use. In this case, the component (a) and the component (c) may be brought into contact with each other in advance, and the treated product may be separated and washed before use, or may be brought into contact in a polymerization system. Further, (d) used as desired in the catalyst (A) or the catalyst (B).
The amount of the component is usually 0 to 1 mol of the component (a).
It is selected in the range of 100 mol. By using the component (d), the polymerization activity can be improved.
The effect corresponding to the added amount does not appear even if it is used too much. The component (d) may be used in contact with the component (a), the component (c) or a contact product of the component (a) and the component (c). This contact may be carried out in advance, or may be carried out by sequentially adding the components into the polymerization system.

In the present invention, a styrene monomer and
Raft precursor (having a polymerizable carbon-carbon double bond in the side chain)
Of ethylene / α-olefin copolymer)
Is the styrene monomer / graft point in the graft precursor
Molar ratio of 1 to 10⁶, Preferably 2 to 10^FiveIn the range
It is desirable to choose. In addition, with styrene monomer
The proportion of the catalyst used is not particularly limited, but is usually
The molar ratio of the thylene monomer / transition metal compound is 10 to 10
¹², Preferably 10 ^Two-10⁸Selected to be in the range of
It is. In the polymerization reaction in the present invention, generally,
The polymerization temperature is in the range of 0 to 120 ° C, preferably 10 to 80 ° C.
, The polymerization time may be selected in the range of 1 second to 10 hours.
No. Polymerization methods include bulk, solution, and suspension polymerization
It is possible. In the case of solution polymerization, usable solution
Aliphatic solvents such as pentane, hexane and heptane
Hydrocarbons, cycloaliphatic hydrocarbons such as cyclohexane, ben
Aromatic hydrocarbons such as benzene, toluene and xylene
is there. Among them, aliphatic hydrocarbons and aromatic hydrocarbons
Is preferred. In this case, the monomer / solvent (volume ratio) is optional.
You can choose at will. In addition, the graft point forming thing
The vinyl styrene represented by the above general formula (I)
When using a precursor compound, the reaction rate during
High and the amount of unreacted monomer at the end of the reaction is low.
By adding the catalyst component, the graft copolymerization
It is possible.

On the other hand, when the vinyl styrene compound represented by the general formula (II) is used, the reaction rate at the time of producing the precursor is low, and the amount of unreacted monomer at the end of the reaction is large. When the graft copolymerization is performed, it is preferable to remove unreacted monomers by an operation such as washing in order to prevent side reactions such as crosslinking. In order to prevent a crosslinking reaction, the vinyl styrene content of the precursor is preferably in the range of 10 ^-4 to 2 mol%. Furthermore, when a low-boiling diene compound such as 1,3-butadiene or isoprene is used as a graft point-forming monomer, it is easy to remove unreacted monomers after the production of the precursor, and it is possible to continue graft copolymerization. . Thus, the olefin copolymer of the present invention is obtained. The molecular weight of the olefin-based copolymer of the present invention was 0.05 g measured in 1,2,4-trichlorobenzene at a temperature of 135 ° C.
0.05 to 25 deciliters / g, preferably 0.1 to 10 deciliters / g, in reduced viscosity at a concentration of
g or a melt index measured at 300 ° C. under a load of 2.16 kg in the range of 0.001 to 500 g / 10 min, preferably 0.005 to 300 g / 10 min. If the reduced viscosity is less than 0.05 deciliter / g or the melt index exceeds 500 g / 10 min, the mechanical strength is insufficient. If the reduced viscosity is more than 25 deciliter / g, or less than 0.001 g / 10 min. In this case, the moldability becomes poor, which is not preferable.

Further, the olefin-based copolymer of the present invention comprises
It has a syndiotactic structure in which the stereoregularity of the chain composed of styrene monomer units is high. That is, the syndiotacticity is 75
%, Preferably 85% or more, 3% in racemic pentad.
0% or more, preferably 50% or more. Further, the content of the chain composed of this styrene monomer unit is 0.1 to 9
0% by weight, preferably in the range of 0.1 to 50% by weight.
When the content is usually in the range of 0.1 to 90% by weight, the graft precursor can have high elasticity, high strength and high heat resistance, and can be used as a thermoplastic elastomer. It can also be used as a solubilizer. If the content is less than 0.1% by weight, the chain composed of the styrenic monomer units does not function sufficiently as a frozen layer, so that sufficient mechanical strength cannot be obtained. On the other hand, if the content exceeds 90% by weight, the soft phase is reduced and the elastomer has no physical properties. The olefin copolymer has a tensile strength of 200 to 500 kg / c.
m ² , tensile elongation is 100 to 600%, tensile modulus is 1.0
It is an olefin copolymer having a mechanical strength of 100 to 20,000 kg / cm ² and high mechanical properties such as high strength and high elongation.

[0037]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Glass container of Example 1 (1) of methylaluminoxane prepared purged with argon inner volume 500 ml, 200 ml of toluene, copper sulfate pentahydrate _{(CuSO 4 · 5H 2 O)} 17.7g (71 mmol) and trimethyl aluminum Twenty-four milliliters (250 mmoles) were added and reacted at 40 ° C. for 8 hours. afterwards,
From the solution obtained by removing the solid components, toluene was further distilled off under reduced pressure to obtain a contact-treated product (methylaluminoxane) 6.
7 g were obtained. Its molecular weight measured by freezing point depression method was 610. Also, Japanese Patent Application Laid-Open No. 62-32539
High magnetic field components by ¹ H-NMR measurement based on No. ¹
That is, observing the proton nuclear magnetic resonance spectrum at room temperature the toluene solution (Al-CH ₃₎ methyl proton signal based on the binding seen in the range of 1.0 to-0.5 ppm in tetramethylsilane standard. The proton signal of tetramethylsilane (0 ppm) is Al-
Because of the observation area based on the methyl proton based on the CH ₃ bond, it is measured based on the methyl proton signal 2.35ppm toluene methyl proton signal based on the Al-CH ₃ bonds in tetramethylsilane standard, high magnetic field component When divided into (-0.1 to -0.5 ppm) and other magnetic field components (i.e., 1.0 to -0.1 ppm), the high magnetic field component was 43% of the whole.

(2) Preparation of solid catalyst component 150 ml of dehydrated and purified n-heptane was placed in a well-dried four-neck flask having a capacity of 500 ml, and then 10.0 g (88 mg) of magnesium diethoxide was added.
Mmol), 1.06 g (17.5 mmol) of isopropyl alcohol was added with stirring, and the mixture was heated to 80 ° C. for 1 hour. Next, the temperature was lowered to room temperature, the supernatant was extracted, 150 ml of n-heptane was added, the mixture was stirred, and the extraction was repeated twice to wash. After that, 150 ml of n-heptane and 2.63 g of ethyl benzoate were washed.
(17.5 mmol) and 83 g (440 mmol) of titanium tetrachloride were introduced, heated to the boiling point, and reacted for 2 hours. After the reaction, the temperature was lowered to 80 ° C., the mixture was left standing, the supernatant was taken out, 150 ml of n-heptane was newly added, and washing, standing, and draining were repeated twice to perform washing.
After that, 83 g of titanium tetrachloride was added again, and
The reaction was allowed to proceed for a period of time. After standing, the liquid was drained. Further, n-heptane was added, and the mixture was repeatedly washed with stirring, standing, and draining until chlorine ions were not detected, thereby obtaining a solid catalyst component.
When the Ti in the obtained solid catalyst component was measured by a colorimetric method, the supported amount was 48 mg-Ti / g carrier.

(3) Production of Ethylene / α-Olefin Copolymer (Graft Precursor) 600 ml of toluene, 3 mmol of triisobutylaluminum, 3 mg of triisobutylaluminum, degassed and purified in a dry, 1 liter pressure-resistant autoclave, p- (3-butenyl) ) Styrene 1
0 mmol was added, the temperature was raised to 50 ° C., and stirring was started.
Then, after propylene was saturated at a pressure of 3 kg / cm ² G, the supply was stopped, and ethylene was further stopped at 7 kg / cm ² G.
And saturated. Next, 0.015 mmol of the solid catalyst prepared in the above (2) as a titanium atom was added and copolymerization was carried out for 1 hour. During this time, the total pressure was 10 kg / cm ^{2 with} ethylene.
The reaction pressure was adjusted to G. After the completion of the reaction, unreacted gas was removed, and the polymer was washed with methanol to obtain 156 g of 15 white powders.

(4) Production of olefin copolymer (graft copolymer) 44.4 g of the graft precursor obtained in the above (3) was dissolved in about 600 ml of toluene in a separable flask equipped with a 1-liter stirring device. Then, toluene was distilled off under reduced pressure at 50 ° C. Freshly dissolved in 400 ml of dry toluene, 200 ml of styrene, 10 mmol of triisobutylaluminum, methylaluminoxane 1
0 mmol was added and kept at 50 ° C. for 5 minutes. Thereafter, pentamethylcyclopentadienyltitanium trimethoxide {Cp ^* Ti (OMe) ₃ } of 50 micromol was added to start graft polymerization. In the reaction system, the polymerization proceeded by the addition of the catalyst, and changed from a solution state to a heterogeneous state. After polymerization was performed for 10 minutes, methanol was added to stop the polymerization, and methanol washing was performed to obtain 82 g of a graft copolymer.

(5) Analysis of graft copolymer The following shows that the graft polymer obtained in the above (4) is a graft. Infrared absorption spectrum analysis Fig. 1 shows the graft precursor (A in the figure) (3) and (4)
The IR absorption spectrum of the graft copolymer (B in the figure) is shown. The graft precursor, the 1,630cm ^-1 p- (3
Stretching vibration of a carbon-carbon double bond based on -butenyl) styrene unit was observed, but disappeared in the graft copolymer. Therefore, it was found that the graft copolymerization proceeded through the styrene residue of p- (3-butenyl) styrene. Analysis of Graft Chain When the styrene chain was measured by ¹³ C-NMR, 145.2 pp due to syndiotactic polystyrene was measured.
A sharp signal of the quaternary carbon of the m aromatic ring was detected.
Further, the melting point of the graft copolymer was measured by a differential scanning calorimeter (DSC). From the above results, the graft copolymer produced in the above (4) is a graft copolymer having a syndiotactic polystyrene as a graft chain. The reduced viscosity of this graft copolymer was 1.9 deciliter / g, and the content of p- (3-butenyl) styrene unit in the copolymer (graft precursor) was determined to be 0.1% by infrared absorption spectroscopy. It was 15% by weight. The molar ratio of ethylene units / propylene units was 65:35 according to ¹ H-NMR. Further, the styrene unit content in the graft copolymer was 45.8% by weight. The melt index (MI) at 300 ° C. under a load of 2.16 kg was 3.2 g / 10 minutes. Then, the graft copolymer obtained for measuring mechanical properties was hot-pressed at 280 ° C., and the tensile strength characteristics were measured using the formed film. As a result, the tensile strength is 320 k
g / cm ² , tensile elongation 380%, tensile modulus 12.0
It was 00 kg / cm ² .

Example 2 In Example 1 (4), 39.6 g of the graft precursor of Example 1 (3) was used, and 50 ml of styrene, 2 mmol of triisobutylaluminum, 2 mmol of methylaluminoxane, Methylcyclopentadienyl titanium trimethoxide @ Cp ^* Ti (O
Me) ₃ ｝ 10 μmol, and graft copolymerization was carried out for 12 minutes. As a result, the yield of the graft copolymer was 41.6 g, and the styrene unit content in the graft copolymer was 4.8% by weight. The reduced viscosity was 1.9 deciliter / g, and the MI was 0.74 g / 10 minutes. The tensile strength was 260 kg / cm ² , the tensile elongation was 580%, and the tensile modulus was 3,800 kg / cm ² .

Example 3 In Example 1 (4), the graft precursor of Example 1 (3) was changed to 32.8 g, and styrene (200 ml), triisobutylaluminum (1 mmol), methylaluminoxane (10 mmol), cycloalkyl as cyclopentadienyl titanium trichloride {CpTiCl _3} 50 micromolar, was carried out graft copolymerization for 30 minutes. As a result, the yield of the graft copolymer was 39.4 g, and the styrene unit content in the graft copolymer was 16.8% by weight. The reduced viscosity is 1.6 deciliter / g.
And the MI was 2.8 g / 10 min. The tensile strength was 300 kg / cm ² , the tensile elongation was 420%, and the tensile modulus was 7,000 kg / cm ² .

Examples 4 to 7 and Comparative Example Ethylene-propylene-p- (3-butenyl) styrene was prepared in the same manner as in (3) and (4) of Example 1, using 600 ml of toluene and 3 mmol of isobutylaluminum. A graft copolymer was produced. Table 1 shows the production conditions, and Table 2 shows the results of measuring the physical properties of the obtained graft copolymer.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

The graft copolymer of the present invention retains the excellent heat resistance, chemical resistance and electric properties inherent in syndiotactic polystyrene, and has good toughness.
It has both tensile strength, tensile elongation and tensile elasticity, and has improved compatibility with other olefin-based resins and diene-based resins, making it an effective material for composite materials and heat-resistant elastomers. Used.

[Brief description of the drawings]

FIG. 1 is an IR absorption spectrum of a graft precursor and a graft copolymer obtained in Example 1.

[Explanation of symbols]

 A: IR absorption spectrum of graft precursor B: IR absorption spectrum of graft copolymer

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 255/00-255/10

Claims (3)

(57) [Claims] 1. An ethylene / α-olefin copolymer having a polymerizable carbon-carbon double bond in a side chain obtained by graft copolymerizing a styrene-based monomer, wherein a styrene-based monomer unit is provided. Having a highly syndiotactic structure with a stereoregularity of 0.1 to 90% by weight
In 1,2,4-trichlorobenzene, 1
Reduced viscosity at a concentration of 0.05 g / dL measured at a temperature of 35 ° C. of 0.05 to 25 dL / g, or 3
The melt index measured at 00 ° C. under a load of 2.16 kg is 0.001 to 500 g / 10 min, the tensile strength is 200 to 500 kg / cm ² , and the tensile elongation is 100 to 6
00% and tensile modulus of 1,000 to 20,000 kg / c
m ² olefin copolymer. 2. The olefin copolymer according to claim 1, wherein the ethylene / α-olefin copolymer has an ethylene component of 40 to 98 mol% and an α-olefin component of 60 to 2 mol%. 3. A side chain double bond of an ethylene / α-olefin copolymer having a polymerizable carbon-carbon double bond in a side chain has a general formula: [Wherein, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ³ is a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 8 carbon atoms. Group, m
Represents 0 or an integer of 1 to 4, and when m is 2 or more, a plurality of R ² may be the same or different. And a vinyl styrene compound represented by the formula:
The olefin-based copolymer according to the above.