JP3121095B2 - Graft copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel graft copolymer and a method for producing the same. More specifically, the present invention provides syndiotactic polystyrene which is excellent in heat resistance, chemical resistance, and electrical properties, has good toughness, elongation, and compatibilizing ability, and is useful as a material for composite materials or a heat-resistant elastomer. The present invention relates to a graft copolymer having a chain as a graft component and a method for efficiently producing the same.

[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 succeeded in developing a styrenic polymer with high syndiotacticity first, and further developed a syndiotactic styrenic polymer in which this styrene monomer and other components were copolymerized. (JP-A-62-104818, 63-24109)
No.). These syndiotactic polymers or copolymers are excellent in heat resistance, chemical resistance and electrical properties, and are expected to be applied in various fields. However, the above polymers, especially syndiotactic polystyrene, have insufficient toughness and elongation, and have poor compatibility with other resins, so that their use has been 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. Since the soft segment does not have a structure sandwiched between the hard segments composed of styrene chains, there is a drawback that 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-1-11885).
Nos. 10 and 1-123811), and no examples of syndiotactic polystyrene graft-copolymerized using this olefin-based graft precursor have 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, elongation and elongation. An object of the present invention is to provide a syndiotactic polystyrene-based resin which has improved compatibility with an olefin-based resin or a diene-based resin, and is useful as a material of a composite material or a heat-resistant elastomer.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to develop a syndiotactic polystyrene-based resin having the above-mentioned preferable properties, and as a result, have found that a polymerizable carbon-carbon double bond is present in the side chain. A styrene-based monomer obtained by graft copolymerizing a styrene-based monomer at a specific ratio to a high-molecular polymer having a highly syndiotactic structure having a high stereoregularity, and having a reduced viscosity or melt index within a specific range. A certain graft copolymer can achieve its purpose, and it can be obtained by grafting a styrene monomer to a polymer having a carbon-carbon double bond in the side chain in the presence of a specific catalyst. It has been found that it can be easily obtained by polymerization. The present invention has been completed based on such findings. That is, the present invention is a polymer obtained by graft copolymerizing a styrene monomer to a polymer having a polymerizable carbon-carbon double bond in a side chain, and comprising a chain composed of styrene monomer units. Has a high syndiotactic structure with a stereoregularity of from 0.1 to 99.
And a reduced viscosity of 0.01 to 30 deciliters / liter at a concentration of 0.05 g / deciliter in 1,2,4-trichlorobenzene measured at a temperature of 135 ° C.
g, or a graft copolymer having a syndiotactic polystyrene chain as a graft component, wherein the melt index measured at 300 ° C. under a load of 2.16 kg is 0.001 to 500 g / 10 min. is there. Further, the graft copolymer reacts with (A) a catalyst containing (a) a transition metal compound and (b) aluminoxane as main components or (B) a (a) transition metal compound and (c) a transition metal compound. By graft-copolymerizing a styrene-based monomer to a polymer having a polymerizable carbon-carbon double bond in the side chain in the presence of a catalyst containing a compound capable of forming an ionic complex as a main component Can be manufactured.

The polymer having a polymerizable carbon-carbon double bond in the side chain in the present invention is not particularly limited, and various polymers can be used. A preferred polymer is composed of an olefin-based monomer unit and a diene-based monomer unit. Examples of the olefin-based monomer unit include ethylene, α-olefin, halogen-substituted α-olefin, And cyclic olefins. As the α-olefin, 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 halogen-substituted α- Examples of the olefin include hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; fluoroethylene; 1,1-difluoroethylene; 3-fluoropropene; trifluoroethylene; 3,4-dichlorobutene-1 and the like. Examples of the cyclic olefin include, for example, norbornene; 5-methylnorbornene;
-Ethylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 5-ethylnorbornene and the like.

[0006] In the present invention, the olefin-based monomer may be used alone or in combination of two or more. On the other hand, diene-based monomers are used to introduce a double bond into a side chain, and include, for example, carbons such as 1,3-butadiene; chloroprene; isoprene; 1,3-hexadiene; and 1,3-heptadiene. A conjugated diene compound represented by Formulas 4 to 20, a cyclic olefin such as vinyl norbornene, 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)
M represents 0 or an integer of 1 to 4, and m represents 2
In the above case, a plurality of R ² may be the same or different. And the like. Of these, a vinylstyrene-based compound represented by the above general formula (I) or (II) is particularly preferable.
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 is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, m
Represents 0 or an integer of 1 to 4. Specific examples of the vinylstyrene-based compound represented by the general formula (I) include 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.

On the other hand, examples of the vinylstyrene-based compound represented by the general formula (II) include the compounds exemplified by the above-mentioned general formula (I) in which an α-olefin residue is substituted with a vinyl group. . As a specific example,
Examples thereof include divinylbenzene, divinyltoluene, and isopropenylstyrene. In the present invention, one type of the diene monomer may be used, or two or more types may be used in combination. The polymer having a polymerizable carbon-carbon double bond in the side chain used in the present invention has a graft point of a styrenic unsaturated double bond in order to control graft efficiency and graft chain length in a wide range. Advantageously there is. In order to produce such a high-molecular polymer, a catalyst mainly composed of a transition metal compound and an organometallic compound (particularly, trialkylaluminum), or a catalyst mainly composed of a supported transition metal compound and an organometallic compound is used. And copolymerizing at least one selected from the above olefin monomers and one selected from the vinylstyrene compounds represented by the general formulas (I) and (II). Good. 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 polymer having a polymerizable carbon-carbon double bond in the side chain thus obtained 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. Furthermore, the unsaturated group content is 1 × 1
0 ^-5 to 15 mol%, preferably 1 × 10 ^-4 to 10 mol%
It is desirable to be within the range. For the molecular weight,
The reduced viscosity at a concentration of 0.05 g / deciliter, measured at a temperature of 135 DEG C. in 2,4-trichlorobenzene, is 0.01.
It is preferably in the range of ~ 30 deciliters / g. In addition,
To the extent that the graft copolymer can be produced, those containing a component partially insoluble in a solvent can also be used. The styrene monomer used in the present invention has a general formula

[0011]

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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. Such compounds include, for example, styrene; p-methylstyrene; o-methylstyrene; m-methylstyrene; 2,4-dimethylstyrene;
2,5-dimethylstyrene; 3,4-dimethylstyrene; 3,5-dimethylstyrene; alkylstyrene such as p-tert-butylstyrene, p-chlorostyrene; m-chlorostyrene; o-chlorostyrene; Styrene; m-bromostyrene; o-bromostyrene; p-fluorostyrene; m-fluorostyrene;
Halogenated styrene such as o-methyl-p-fluorostyrene, 4-vinylbiphenyl;
3-vinylbiphenyl; vinylbiphenyls such as 2-vinylbiphenyl, 1- (4-vinylphenyl) -naphthalene; 2- (4-vinylphenyl) -naphthalene;
-(3-vinylphenyl) -naphthalene; 2- (3-vinylphenyl) -naphthalene; 1- (2-vinylphenyl) -naphthalene; vinylphenylnaphthalenes such as 2- (2-vinylphenyl) naphthalene; (4-vinylphenyl) -anthracene; 2- (4-vinylphenyl) -anthracene; 9- (4-vinylphenyl)-
Anthracene; 1- (3-vinylphenyl) -anthracene; 2- (3-vinylphenyl) -anthracene; 9
-(3-vinylphenyl) -anthracene; 1- (2-
2- (2-vinylphenyl) -anthracene; 9- (2-vinylphenyl)
-Vinylphenylanthracenes such as anthracene,
1- (4-vinylphenyl) -phenanthrene; 2-
(4-vinylphenyl) -phenanthrene; 3- (4-
4- (4-vinylphenyl) -phenanthrene; 9- (4-vinylphenyl) -phenanthrene; 1- (3-vinylphenyl)-
Phenanthrene; 2- (3-vinylphenyl) -phenanthrene; 3- (3-vinylphenyl) -phenanthrene; 4- (3-vinylphenyl) -phenanthrene; 9
-(3-vinylphenyl) -phenanthrene; 1- (2
-(2-vinylphenyl) -phenanthrene; 3- (2-vinylphenyl) -phenanthrene; 4- (2-vinylphenyl)
-Phenanthrene; vinylphenylphenanthrenes such as 9- (2-vinylphenyl) -phenanthrene;
-(4-vinylphenyl) -pyrene; 2- (4-vinylphenyl) -pyrene; 1- (3-vinylphenyl) -pyrene; 2- (3-vinylphenyl) -pyrene; 1- (2
-Vinylphenyl) -pyrene; vinylphenylpyrenes such as 2- (2-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-terphenyl; 2-vinyl-m-terphenyl; 2-vinyl-o-
Vinyl terphenyls such as terphenyl;
Vinylphenyl terphenyls such as vinylphenyl) -p-terphenyl, 4-vinyl-4'-methylbiphenyl;4-vinyl-3'-methylbiphenyl;4-vinyl-2'-methylbiphenyl; 2-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; 4-vinyl-
2-vinyl-2-chlorobiphenyl; 4-vinyl-3-chlorobiphenyl; 4-vinyl-4'-bromobiphenyl;4-vinyl-3'-bromobiphenyl; 4-vinyl-2 '-Bromobiphenyl;
4-vinyl-2-bromobiphenyl; 4-vinyl-3-
Halogenated vinyl biphenyls such as bromobiphenyl; trialkylsilylvinyl biphenyls such as 4-vinyl-4'-trimethylsilylbiphenyl;4-vinyl-4'-trimethylstannylbiphenyl;4-vinyl-4'-tributylstannyl Trialkylstannylvinyl biphenyls such as biphenyl, 4-vinyl-
Trialkylsilylmethylvinylbiphenyls such as 4′-trimethylsilylmethylbiphenyl, 4-vinyl-
4′-trimethylstannylmethylbiphenyl; trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4′-tributylstannylmethylbiphenyl, p-chloroethylstyrene; m-chloroethylstyrene; o-chloroethylstyrene A halogen-substituted alkyl styrene, p-trimethylsilyl styrene; m-
O-trimethylsilylstyrene; p-triethylsilylstyrene; m-triethylsilylstyrene; o-triethylsilylstyrene; p-
Alkyl silyl styrenes such as dimethyl tertiary-butyl silyl styrene, p-dimethyl phenyl silyl styrene; p-methyl diphenyl silyl styrene; phenyl group-containing silyl styrenes such as p-triphenyl silyl styrene, p-dimethyl chloro silyl styrene; p-
P-Trichlorosilylstyrene; p-dimethylbromosilylstyrene; halogen-containing silylstyrenes such as p-dimethyliodosilylstyrene, and silyl group-containing silylstyrenes such as p- (p-trimethylsilyl) dimethylsilylstyrene. And the like. These styrene monomers may be used alone or in combination of two or more.

There are various methods for producing the graft copolymer of the present invention. According to the method of the present invention, (A) (a) a transition metal compound and (b) aluminoxane are mainly used as catalysts. What is used as a component or what has as a main component the compound which can form 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 as the component (a), and preferably, the general formula M ¹ R ⁵ ... R ^k (IV) (where M ¹ is Ti, Zr, Represents Cr, V, Nb, Ta or Hf, and R ^{5 to} R ^k are each 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, and 6 carbon atoms. To 20 aryl groups, alkylaryl groups or arylalkyl groups;
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,
An iodine atom; examples of 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.

Further, 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, and the like.
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

[0019]

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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). , General formula

[0021]

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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. Also,
Typical examples of the condensing agent include water, and any other condensing agent capable of condensing trialkylaluminum, such as copper sulfate pentahydrate, water adsorbed on inorganic and organic substances, and the like. No.

In general, the contact product of an organoaluminum compound such as trialkylaluminum and water is mixed with the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane, as well as a mixture of unreacted trialkylaluminum and various condensation products, 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 a water-containing compound or the like is used after the above-mentioned contact reaction, 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 40
At a temperature of で 150 ° C. for 20 minutes to 8 hours, preferably 30 minutes
Those heat-treated while distilling off the solvent in the range of minutes to 5 hours are preferred. 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.

The catalyst (B) in the present invention includes the above
(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.
General formula ([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^Three
Are the VB, VIB, VIIB, and VIII of the periodic table, respectively.
Selected from group IV, group IB, group IIB, group IIIA, group IVA and group V
Element, M^FourAnd M^FiveIs the IIIB group of the periodic table,
IV, V, VIB, VIIB, VIII, I, IB,
An element selected from Group IIA, IIB and VIIA, Z¹~ Z
^eAre hydrogen, dialkylamino, alkoxy
Si group, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkyl group having 1 to 20 carbon atoms, charcoal
Aryl group, alkylaryl group, ant having a prime number of 6 to 20
Alkyl group, halogen-substituted hydrocarbon having 1 to 20 carbon atoms
Element group, acyloxy group having 1 to 20 carbon atoms, organic metalloy
Z or a halogen atom;¹~ Z^eHaha 2 or more
The upper portions may be bonded to each other to form a ring. R⁷Is water
Elemental atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Aryl, alkylaryl or arylalkyl
And R represents⁸And R⁹Are cyclopentadie
Nyl group, substituted cyclopentadienyl group, indenyl group or
Is a fluorenyl group, R^TenIs alkyl having 1 to 20 carbon atoms
Group, aryl group, alkylaryl group or arylal
Represents a kill group. R¹¹Is tetraphenylporphyrin,
Shows macrocyclic ligands such as tarocyanines. f is M^Two, M
^ThreeIs an integer of 1 to 7, e is an integer of 2 to 8, and u is
[L¹-R⁷], [L ^Two] With an ionic valence of 1 to 7
The number, v is an integer of 1 or more, w = (v × u) / (ef)
is there. ] It is a compound represented by these.

[0027] 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 formulas (VII) and (VIII), those in which 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 of the general formula (VIII) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, manganese tetraphenylborate (tetraphenylporphyrin manganese), 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 (B). As the organometallic compound (d) optionally used in combination, a compound represented by the general formula 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 group, ethyl group, n-propyl group, i-propyl group, n
-Butyl group, i-butyl group, hexyl group, 2-ethylhexyl group, phenyl group and the like. And 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, alkyllithium compounds such as methyllithium, ethyllithium, propyllithium and butyllithium; alkylmagnesium compounds such as diethylmagnesium, ethylbutylmagnesium and dinormalbutylmagnesium; dimethylzinc, diethylzinc, dipropylzinc and dibutylzinc Dialkyl zinc 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. When M ⁶ is aluminum, there are various compounds. Specific examples include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-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-based monomer serving as a graft chain and the polymerizable unsaturated bond serving as a graft point, and cannot be unconditionally determined. 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 styrenic monomer and
Raft precursor (having a polymerizable carbon-carbon double bond in the side chain)
Of the styrene monomer /
The graft point molar ratio in the graft precursor is 1 to 10⁶, Good
Preferably 2-10^FiveIt is desirable to choose to be in the range of
No. In addition, the usage ratio of styrene monomer and catalyst
Is not particularly limited, but usually styrene monomer / transition gold
The molar ratio of the genus compound is 10 to 10¹², Preferably 10 ^Two~
10⁸Is chosen to be in the range Heavy in the present invention
In the combined reaction, the polymerization temperature is generally 0 to 120.
° C, preferably in the range of 10 to 80 ° C, the polymerization time is 1 second
What is necessary is just to select within the range of 10 hours. As the polymerization method
Any of bulk, solution and suspension polymerization is possible. In addition,
In liquid polymerization, pentane,
Aliphatic hydrocarbons such as hexane and heptane, cyclohexene
Alicyclic hydrocarbons such as sun, benzene, toluene, xy
There are aromatic hydrocarbons such as ren. Among these
Aliphatic hydrocarbons and aromatic hydrocarbons are preferred. This place
In this case, the monomer / solvent (volume ratio) can be arbitrarily selected.
it can. In addition, the above-mentioned general
Using a vinylstyrene compound represented by the formula (I)
In some cases, the reaction rate during the production of the precursor is high, and
Since the amount of reactive monomer is low, continue adding catalyst components
By doing so, graft copolymerization 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 production of the precursor is low, and the amount of unreacted monomer is large at the end of the reaction. When the graft copolymerization is carried out, it is preferable to remove unreacted monomers by an operation such as washing in order to prevent side reactions such as crosslinking. Further, in order to prevent a crosslinking reaction, the vinylstyrene 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. is there. Thus, the graft copolymer of the present invention is obtained. The molecular weight of the graft copolymer of the present invention is 0.01 to 30 deciliter / g, preferably reduced viscosity at a concentration of 0.05 g / deciliter, measured in 1,2,4-trichlorobenzene at a temperature of 135 ° C. The melt index measured at 0.05 to 25 deciliters / g or at 300 ° C. under a load of 2.16 kg is 0.001 to 500 g / 10 min, preferably 0.0.
It is necessary to be in the range of 0.05 to 300 g / 10 minutes. If the reduced viscosity is less than 0.01 deciliter / g or the melt index is more than 500 g / 10 min, the mechanical strength is insufficient, and
If the amount exceeds g, or if it is less than 0.001 g / 10 minutes, the moldability will be poor.

Further, the graft copolymer of the present invention has a syndiotactic structure having a high stereoregularity of a chain composed of styrene monomer units. That is, it is 75% or more, preferably 85% or more in racemic dyad, and 30% or more, preferably 50% or more in racemic pentad. Further, the content of the chain composed of the styrene-based monomer unit is in the range of 0.1 to 99.9% by weight, preferably 0.5 to 99% by weight. This content is usually 0.1 to 50% by weight
Those having the range described above can increase the elasticity, strength and heat resistance of the graft precursor, can be used as a thermoplastic elastomer, and can also be used as a resin compatibilizer. On the other hand, those whose content is usually in the range of 50 to 99.9% by weight can be used for softening or toughening of syndiotactic polystyrene as a graft component and can also be used as a resin compatibilizer.

[0036]

Next, the present invention will be described in more detail by way of 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.
Thereafter, 83 g of titanium tetrachloride is added again, and the reaction is carried out at the boiling point for 1 hour. After standing, the liquid is drained. Further, n-heptane is added, and stirring, standing, and draining are performed until chlorine ions are not detected. Washing was repeated to obtain 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) Preparation of Copolymer (Graft Precursor) Dried 600 ml of toluene, 3 mmol of triisobutylaluminum, p- (3-butenyl) styrene 1
0 mmol was added, the temperature was raised to 70 ° C., and stirring was started.
To this, supply of propylene was stopped after propylene was saturated at a pressure of 7 kg / cm ² G, and ethylene was further added at 3 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 completion of the reaction, unreacted gas was removed, and the polymer was washed with methanol to obtain 222 g of a white powder.

(4) Production of Graft Copolymer In a separable flask equipped with a 1-liter stirring device, 44.4 g of the graft precursor obtained in the above (3) was dissolved in about 600 ml of toluene, and toluene was added at 70 ° C. The solvent was distilled off under reduced pressure. 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 70 ° 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 was washed to obtain 113 g of a graft copolymer.

(5) Analysis of graft copolymer The following shows that the 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 1630cm ^-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 polymer 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. 15w
t%. The molar ratio of ethylene units / propylene units was 35:65 based on ¹ H-NMR. Further, the styrene unit content in the graft copolymer was 60.7% by weight. The melt index (MI) at 300 ° C. under a load of 2.16 kg was 3.2 g / 10 minutes.

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 40.3 g, and the styrene unit content in the graft copolymer was 2.0% by weight. The reduced viscosity was 1.9 deciliter / g, and the MI was 0.74 g / 10 minutes.

Examples 3 to 6 Ethylene-propylene-p- (3-butenyl) 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 styrene-based graft copolymer was produced. The production conditions and the results obtained are shown in Tables 1 (1), (2) and (3).

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

Example 7 (1) Production of propylene-p- (3-butenyl) styrene copolymer (graft precursor) In Example 1, (3), p- (3-butenyl) styrene was replaced with 8 and mmol, instead of triisobutylaluminum, triethylaluminum 2.0 mmol, ethylene propylene without is continuous fed at 7 kg / cm ² G, except that hydrogen 0.2 kg / cm ² G introduced prior propylene introduced The operation was performed in the same manner as in Example 1, (3). After completion of the copolymerization, the mixture was deactivated with methanol and washed to give 150
g of polymer was obtained.

(2) Production of graft copolymer In Example 2, 29 g of the graft precursor of (1) above
The reaction was carried out in the same manner except that the reaction time was changed to 1 hour. The reaction proceeded in a slurry state. As a result, the yield of the graft copolymer was 36.5 g, and the styrene unit content in the graft copolymer was 20.5 wt%. When the melting point was measured by a differential scanning calorimeter, the melting point based on isotactic polypropylene was found to be 268 ° C.
C. A melting point based on syndiotactic polystyrene was observed. Further, the boiling heptane insoluble portion was 92% by weight. The MI was 0.005 g / 10 minutes.

Example 8 In Example 1, (3), 400 ml of toluene, 5 mmol of p- (3-butenyl) styrene, 0.02 mmol of a titanium catalyst component, a hydrogen pressure of 7 kg / cm ² G without using propylene were used. After introducing ethylene, 3 kg /
The copolymerization was carried out at 80 ° C. while continuously feeding at cm ² G. The copolymer yield was 42 g. Using 20 g of this copolymer, graft copolymerization was carried out in the same manner as in Example 2. The graft copolymerization time was 1 hour. The reaction is
It proceeded in a slurry state. As a result, the yield of the graft copolymer was 25.2 g, and the styrene unit content in the graft copolymer was 20.6 wt%. When the melting point was measured by a differential scanning calorimeter, a melting point based on polyethylene was found at 134 ° C., and a melting point based on syndiotactic polystyrene was found at 268 ° C. The reduced viscosity of the graft copolymer was 0.92 deciliter / g. The MI was 3.2 g / 10 minutes.

Examples 9 and 10 In Example 1 (4), the graft copolymer was used under the following conditions, using the amount of the graft precursor shown in Table 2 and the type and amount of the styrene monomer shown in Table 2. Polymerization was performed.
Table 2 shows the results. Reaction conditions Toluene: 400 ml Triisobutylaluminum: 3 mmol Methylaluminoxane: 3 mmol Cp ^* Ti (OMe) ₃ : 10 micromol Temperature: 70 ° C Time: 1 hour

[0050]

[Table 4]

Example 11 (1) Tri-n-tetra (pentafluorophenyl) borate
Preparation of butylammonium pentafluorophenyllithium prepared from bromopentafluorobenzene (152 mmol) and butyllithium (152 mmol) is reacted with 45 mmol of boron trichloride in hexane to give tri (pentafluorophenyl) boron in white. Obtained as a solid. By reacting 41 mmol of this tri (pentafluorophenyl) boron with 41 mmol of lithium pentafluorophenyl,
Lithium tetra (pentafluorophenyl) boron was isolated as a white solid. Next, by reacting 16 mmol of lithium tetra (pentafluorophenyl) boron with 16 mmol of tri-n-butylamine hydrochloride in water, tetra (pentafluorophenyl) boron tri-n-
12.8 mmol of butylammonium could be obtained as a white solid.

(2) Production of graft copolymer Using 20 g of the graft precursor produced in (3) of Example 1, the boron compound 5 prepared in the above (1) was used in place of 1 mmol of triisobutylaluminum and aluminoxane.
0 micromolar and pentamethylcyclopentadienyltrimethyl (Cp ^* Ti (OMe) ₃ ) instead of Cp ^* Ti (OMe) _3.
^* 10 μmol of TiMe ₃ ) was added and the reaction time was 3
Graft copolymerization was carried out in the same manner except that the time was 0 minutes. After completion of the reaction, after deactivation and washing with methanol,
54.3 g of the graft copolymer was obtained. The styrene content in the graft copolymer was 63.1 wt%, and the reduced viscosity was 3.
It was 0 deciliter / g.

Example 12 50 n-heptane was placed in a 1-liter pressure-resistant autoclave.
0 ml, divinylbenzene (Tokyo Chemical Co., Ltd.)
20 ml, a mixture of m- and p-forms, divinylbenzene content 55 wt%), 2 mmol of diethylaluminum chloride, and 100 mg of titanium trichloride (TOB-04, manufactured by Toyo Stouffer Co., Ltd.) were introduced in this order. And hydrogen at 0.2 kg / cm ² G to initiate copolymerization of propylene and divinylbenzene. The copolymerization was performed at a propylene pressure of 7 kg / cm ² G at 65 ° C. for 3 hours. After completion of the copolymerization, residual monomers were purged, and the polymer slurry was separated by filtration to obtain 112 g of a copolymer powdered polymer. Using 39 g of this copolymer, graft copolymerization was carried out under the conditions shown in Example 2 for 1 hour. The reaction proceeded in a slurry state. As a result, the graft copolymer yield was 41.8.
g, the styrene unit content occupied by the graft copolymer is 6.7.
wt%. When the melting points were measured by a differential scanning calorimeter, a melting point based on isotactic polypropylene was found at 163 ° C. and a melting point based on syndiotactic polystyrene was found at 268 ° C. The reduced viscosity of the graft copolymer was 2.0 deciliter / g. Further, the boiling heptane insoluble portion was 97% wt. The MI was 2.3 g / 10 minutes.

Example 13 600 ml of deaerated and purified toluene, 3 mmol of triisobutylaluminum, p- (3-butenyl) styrene 1 were placed in a dry 1 liter pressure autoclave.
5 mmol was added, the temperature was raised to 70 ° C., and stirring was started.
After propylene was saturated at a pressure of 7 kg / cm ² G, the supply was stopped, and the propylene was further saturated with 3 kg / cm ² G of ethylene. Next, 0.015 mmol of the solid catalyst prepared in the above (1) as a titanium atom was added and copolymerization was carried out for 1 hour. During this time, the reaction pressure was adjusted with ethylene so that the total pressure became 10 kg / cm ² G. After the completion of the reaction, unreacted gas was removed by depressurization, and then dry nitrogen was blown at 70 ° C. for 30 minutes to completely remove unreacted monomers. At this time, the solvent toluene was 200
Distilled out of the milliliter reaction system. Subsequently, 10 mmol of methylaluminoxane prepared in (1) of Example 1 was added, 200 ml of styrene was immediately added, and a graft reaction was carried out at 70 ° C. for 3 hours. After the completion of the reaction, 151 g of a graft copolymer was obtained by deactivating methanol and washing. The melting point was measured at 266 ° C. by a differential scanning calorimeter (DSC). The reduced viscosity of this graft copolymer was 3.0 deciliters / g, and the molar ratio of ethylene units / propylene units / styrene units was 33.2 / 61.6 / 5.2. Also, the infrared absorption spectrum of the graft copolymer has p- (3
No absorption at 1630 cm ^-1 based on -butenyl) styrene could be detected. The MI was 1.6 g / 10 minutes.

[0055]

The graft copolymer of the present invention retains the excellent heat resistance, chemical resistance and electrical properties inherent in syndiotactic polystyrene, and also has the toughness and elongation of the graft precursor. It has improved compatibility with other olefin-based resins and diene-based resins, and is effectively used as a material of a composite material or a heat-resistant elastomer.

[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

Claims (3)

(57) [Claims] 1. A polymer obtained by graft copolymerizing a styrene monomer to a high molecular polymer having a polymerizable carbon-carbon double bond in a side chain, wherein a chain of styrene monomer units is formed. It has a high stereoregular syndiotactic structure and its content is in the range of 0.1 to 99.9% by weight and was measured in 1,2,4-trichlorobenzene at a temperature of 135 ° C. The reduced viscosity at a concentration of 0.05 g / deciliter is 0.01 to 30 deciliter / g, or 300 ° C.
2. Melt index measured at 16 kg load is 0.00
A graft copolymer having a syndiotactic polystyrene chain as a graft component, which has a weight of 1 to 500 g / 10 min. 2. A high molecular polymer having a polymerizable carbon-carbon double bond in a side chain is composed of an olefin monomer unit and a diene monomer unit, and the side chain double bond is generally Formula 1 Wherein R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ² is a halogen or a hydrocarbon group having 1 to 8 carbon atoms, R ³ is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms , 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. The graft copolymer according to claim 1, which is derived from a vinylstyrene-based compound represented by the following formula: 3. (A) (a) a transition metal compound and (b)
Catalyst containing aluminoxane as a main component, or (B) (a)
In the presence of a catalyst mainly composed of a transition metal compound and (c) a compound capable of reacting with the transition metal compound to form an ionic complex, a polymer having a polymerizable carbon-carbon double bond in a side chain 3. The method for producing a graft copolymer according to claim 1, wherein a styrene-based monomer is graft-copolymerized.