JPH05320449A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. excellent in adhesive properties, impact resistance, etc., by compounding a specific graft copolymer with a highly syndiotactic styrene polymer, a thermoplastic resin, a filler, etc. CONSTITUTION:A styrenic monomer (e.g. p-methylstyrene) is grafted onto a high-molecular polymer having polymerizable carbon-carbon double bonds in its side chains (e.g. propylene-divinylbenzene copolymer) to give a graft copolymer wherein molecular chains comprising units derived from the monomer are highly syndiotactic. The content of the graft component in the graft copolymer is pref. 0.005-99wt.%. The graft copolymer is compounded with a highly syndiotactic styrenicpolymer and at least one thermoplastic resin and/or inorg. and org. fillers to give a resin compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel resin composition, and more specifically, it has excellent heat resistance, high crystallinity, easy moldability, chemical stability, etc. inherent in a styrene resin having a syndiotactic structure. The present invention relates to a thermoplastic resin composition that retains the characteristics and is imparted with compatibility, adhesiveness, and impact resistance and has a balanced physical property.

[0002]

2. Description of the Related Art Styrene-based polymers conventionally produced by radical polymerization or the like are molded into various shapes by various molding methods, and are used for household appliances, office equipment, household products, packaging containers, toys, It is widely used as furniture, synthetic paper, and other industrial materials, but its three-dimensional structure has an atactic structure, which has the drawback of poor heat resistance and chemical resistance. The research group of the present inventors has succeeded in developing a styrene-based polymer having a high syndiotactic structure so far by solving such drawbacks of the styrene-based polymer having an atactic structure. A styrenic copolymer prepared by copolymerizing a styrenic monomer and other components has also been developed (JP-A-62-10481).
No. 8 and No. 62-187708, No. 63-24.
No. 1009). These polymers 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 poor compatibility with other resins, have almost no adhesiveness to metals, and have insufficient impact resistance. By the way, a copolymer of olefin and syndiotactic polystyrene, or a copolymer of unsaturated carboxylic acid ester and the like and syndiotactic polystyrene is known (JP-A-3-770).
No. 5, Japanese Patent Application Nos. 2-251360 and 2-3143.
27, 3-89509). However, these copolymers have high crystallinity when the content of comonomer is low. However, when the content of comonomer is increased, an amorphous polymer is formed and syndiotactic polystyrene Mechanical properties, thermal properties, and chemical properties cannot be fully utilized. Therefore, in order to maintain a high degree of syndiotacticity, there is a limit to the amount of comonomer that can be copolymerized, and materials that utilize the characteristics of syndiotactic polystyrene by combining with other thermoplastic resins and fillers can be used. It has the drawback that it cannot be obtained over a wide area. It is also possible to use a resin compatibilizer as the third component, but the molding temperature of syndiotactic polystyrene is high, and there is no suitable one, and the addition of the third component may lead to a decrease in performance. Not preferable.

[0003]

Under the above circumstances, the present invention has characteristics such as excellent heat resistance, high crystallinity, easy moldability, and chemical stability that the styrene resin having a syndiotactic structure originally has. The object of the present invention is to provide a thermoplastic resin composition which is held, and is provided with compatibility, adhesiveness, and impact resistance and in which physical properties are well balanced.

[0004]

Means for Solving the Problems As a result of intensive studies to develop a thermoplastic resin composition having the above-mentioned preferable properties, the present inventors have found that a specific graft copolymer and styrene having a syndiotactic structure are obtained. It has been found that the object can be achieved by a resin composition containing a system polymer or another thermoplastic resin and / or an inorganic filler or an organic filler. The present invention has been completed based on this finding.
That is, the present invention is a polymer obtained by graft-copolymerizing a styrene-based monomer to a high molecular polymer having a polymerizable carbon-carbon double bond in the side chain (A), which is a styrene-based monomer unit. A graft copolymer having a syndiotactic structure with a high degree of stereoregularity of a chain consisting of (B), a styrene-based polymer having a high syndiotactic structure, and at least one selected from other thermoplastic resins. The present invention provides a resin composition containing one kind and / or (C) at least one kind selected from an inorganic filler and an organic filler.

In the composition of the present invention, the high molecular polymer having a polymerizable carbon-carbon double bond in the side chain used as the precursor of the graft copolymer as the component (A) is particularly limited. Instead, various polymers can be used. A preferred polymer is composed of an olefinic monomer unit and a diene monomer unit,
Examples of the olefin-based monomer unit include ethylene, α-olefin, halogen-substituted α-olefin, cyclic olefin and the like. 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. Examples of the halogen-substituted α-olefin include hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; fluoroethylene; 1,1-difluoroethylene. ;
3-fluoropropene; trifluoroethylene; 3,4
-Dichlorobutene-1 and the like. Examples of cyclic olefins include norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 5-ethylnorbornene.

In this precursor, the olefinic monomer may be used alone or in combination of two or more kinds. On the other hand, the diene-based monomer is used for introducing a double bond into a side chain, and is, for example, carbon such as 1,3-butadiene; chloroprene; isoprene; 1,3-hexadiene; 1,3-heptadiene. Conjugated diene compounds of formulas 4 to 20, cyclic olefins such as vinyl norbornene, and general formula (I) or (II)

[0007]

[Chemical 1]

[In the formula, 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 1 to 8 carbon atoms.
Hydrocarbon group, m is 0 or an integer of 1 to 4, and m is 2
In the above cases, a plurality of R ² may be the same or different. Examples of the vinyl styrene compound represented by the formula] are preferred, and among these, the vinyl styrene compound represented by the 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) is a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Group, 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 vinyl styrene 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-
Examples include butenyl) biphenyl, m- (3-butenyl) -α-methylstyrene, o- (3-butenyl) -α-methylstyrene, p-3-butenyl) -α-methylstyrene.

On the other hand, examples of the vinyl styrene compound represented by the general formula (II) include the compounds exemplified in the above general formula (I) in which the α-olefin residue is substituted with a vinyl group. . As a specific example,
Examples include divinylbenzene, divinyltoluene and isopropenylstyrene. In this precursor, the diene-based monomer may be used alone or in combination of two or more. The polymer having a polymerizable carbon-carbon double bond in the side chain, which is the precursor of the graft copolymer used in the present invention, has a grafting point in order to widely control the grafting efficiency and the graft chain length. Is advantageously a styrenic unsaturated double bond. In order to produce such a high molecular weight polymer, a catalyst containing a transition metal compound and an organometallic compound (particularly trialkylaluminum) as a main component or a supported transition metal compound and an organometallic compound as a main component is used as a catalyst. If at least one selected from the above olefinic monomers and one selected from the vinylstyrene compounds represented by the general formulas (I) and (II) are copolymerized Good. Thereby, the styrenic double bond can be introduced into the side chain.

When a graft initiation point is produced using the vinylstyrene compound represented by the general formula (II),
A crosslinked product is easily generated, a sufficient reaction rate cannot be obtained, and unreacted monomers remain, so that production is easily restricted.
On the other hand, when the vinyl styrene compound represented by the general formula (I) is used to generate the graft initiation point, crosslinking is difficult to occur and the reaction rate is high. Further, although it is possible to produce a graft body even with an α-olefinic double bond, it is difficult to widely control the graft chain length and the graft efficiency. 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. Further, the copolymerization mode may be random type or 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%. Regarding 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 20 deciliter / g. In addition, it is also possible to use, as long as the graft copolymer can be produced, a resin partially containing an insoluble component. In such a case, 300 ℃,
Melt index measured with a load of 2.16 kg is 0.00
It is preferably in the range of 1 to 500 g / 10 minutes. The styrenic monomer to be grafted onto the polymer having a polymerizable carbon-carbon double bond on the side chain has the general formula (III)

[0011]

[Chemical 2]

[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, and when n is plural, , Each R ⁴ may be the same or different, and R ^4
4 may form a condensed ring with the benzene ring. ] It is a compound represented by these. Examples of such compounds include styrene; p-methylstyrene; o-methylstyrene; m-methylstyrene; 2,4-dimethylstyrene; 2,5-dimethylstyrene; 3,4-dimethylstyrene; Dimethyl styrene; alkyl styrenes such as p-tert-butyl styrene, p-chlorostyrene; m-chlorostyrene; o-chlorostyrene; p-bromostyrene; m-bromostyrene; o-bromostyrene; p-fluorostyrene; -Fluorostyrene; o-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) -naphth Len; 1- (3-vinylphenyl) - naphthalene; 2
-(3-Vinylphenyl) -naphthalene; 1- (2-vinylphenyl) -naphthalene; vinylphenylnaphthalenes such as 2- (2-vinylphenyl) naphthalene, 1
2- (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-vinylphenyl) -anthracene; 2- (2
-Vinylphenyl) -anthracene; vinylphenylanthracenes such as 9- (2-vinylphenyl) -anthracene, 1- (4-vinylphenyl) -phenanthrene; 2- (4-vinylphenyl) -phenanthrene; 3
4- (4-vinylphenyl) -phenanthrene; 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-vinylphenyl) -phenanthrene; 2-
(2-Vinylphenyl) -phenanthrene; 3- (2-
Vinylphenyl) -phenanthrene; 4- (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-
Terphenyl; 2-vinyl-m-terphenyl; vinyl terphenyls such as 2-vinyl-o-terphenyl,
Vinylphenyl terphenyls such as 4- (4-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 4-vinyl-2-fluorobiphenyl; 4-vinyl-3-fluorobiphenyl; 4-vinyl-4'-chlorobiphenyl;4-vinyl-3'-chlorobiphenyl; 4
-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, trialkylsilyl vinyl biphenyls such as 4-vinyl-4′-trimethylsilyl biphenyl, 4-vinyl-4′-trimethylstannyl biphenyl; 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; m-
Triethylsilylstyrene; o-triethylsilylstyrene; alkylsilylstyrenes such as p-dimethyltert-butylsilylstyrene; p-dimethylphenylsilylstyrene; p-methyldiphenylsilylstyrene; phenyl groups such as p-triphenylsilylstyrene Containing silylstyrenes, p-dimethylchlorosilylstyrene; p-methyldichlorosilylstyrene; p-trichlorosilylstyrene; p-dimethylbromosilylstyrene; halogen-containing silylstyrenes such as p-dimethyliodosilylstyrene, p- (p -Trimethylsilyl)
Examples thereof include silyl group-containing silylstyrenes such as dimethylsilylstyrene. These styrene-based monomers may be used alone or in combination of two or more.

There are various methods for producing the graft copolymer. For example, as a catalyst, (a) a transition metal compound (a) and (b) an aluminoxane as a main component, or (b) A compound containing, as a main component, a compound capable of reacting with (a) a transition metal compound and (c) a transition metal compound to form an ionic complex is used. There are various transition metal compounds of the above-mentioned component (a), but it is preferable to use the general formula M ¹ R ⁵ ... R ^k (IV) [wherein M ¹ is Ti, Zr, Cr, V, Nb, Ta or Hf is shown, 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; 20 aryl groups, alkylaryl groups or arylalkyl groups;
C1-C20 acyloxy group, allyl group, substituted allyl group, acetylacetonato group, substituted acetylacetonato group, substituent containing silicon atom, or carbonyl, oxygen molecule, nitrogen molecule, Lewis base, chain unsaturated Ligands such as hydrocarbons or cyclic unsaturated hydrocarbons, cyclopentadienyl groups, substituted cyclopentadienyl groups, indenyl groups, substituted indenyl groups, tetrahydroindenyl groups,
A substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is shown. Further, k represents a valence of a metal and usually represents an integer of 2 to 5].

Examples of the substituted cyclopentadienyl group include methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group,
Tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group Examples thereof include 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,
Iodine atom; As the alkyl group having 1 to 20 carbon atoms, a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, octyl group, 2-ethylhexyl group, etc. The alkoxy group is a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group or the like, and the aryl group having 6 to 20 carbon atoms, the alkylaryl group or the arylalkyl group is a phenyl group, a tolyl group, a xylyl group, or benzyl. Examples of the acyloxy group having 1 to 20 carbon atoms such as a group include a heptadecylcarbonyloxy group, a substituent including a silicon atom such as a trimethylsilyl group and a (trimethylsilyl) methyl group, and a Lewis base including 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;
Examples of chain unsaturated hydrocarbons include amines such as 2,2′-bipyridine and phenanthroline, and phosphines such as triethylphosphine and triphenylphosphine.
Examples of cyclic unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and their derivatives include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene and cyclooctatetraene. Examples thereof include ene and derivatives thereof. Examples of the covalent bond include methylene bridge, dimethylmethylene bridge,
Examples include ethylene crosslinks, dimethylsilylene crosslinks, and dimethylstannylene crosslinks.

Specific examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium and tetra-n.
-Butoxy titanium, tetraisopropoxy titanium, titanium tetrachloride, titanium trichloride, titanium dichloride, titanium hydride, cyclopentadienyltrimethyl titanium, cyclopentadienyl triethyl titanium, cyclopentadienyl tripropyl titanium, cyclopentadi Phenyltributyltitanium, methylcyclopentadienyltrimethyltitanium, 1,2-dimethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltripropyl Titanium, pentamethylcyclopentadienyltributyltitanium, cyclopentadienylmethyltitanium dichloride, cyclopentadienylethyltitanium dichloride, pentamethylcyclopen 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 Phenyl methoxy titanium dichloride, cyclopentadienyl dimethoxy titanium chloride, pentamethyl cyclopentadienyl methoxy titanium 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 and tetra. Phenylzirconium, cyclopentadienylzirconium trimethoxide, pentamethylcyclopentadienylzirconium trimethoxide, cyclopentadienyltribenzylzirconium,
Pentamethylcyclopentadienyltribenzylzirconium, bisindenylzirconium dichloride, zirconium dibenzyldichloride, zirconium tetrabenzyl, tributoxyzirconium chloride, triisopropoxyzirconium chloride, (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethyl Cyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) trichlorozirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) trichlorozirconium, (Cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethylzyl , (Methylcyclopentadienyl) triphenylzirconium, (Methylcyclopentadienyl) tribenzylzirconium, (Methylcyclopentadienyl) trichlorozirconium, (Methylcyclopentadienyl) dimethyl (methoxy) zirconium, (Dimethylcyclopentadienyl) Pentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, bis (cyclopentadienyl) dimethylzirconium, bis ( Cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) dibenzyl Zirconium,
Bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) ) Dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium , Bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (pentamethylcyclo) N-dienyl) 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) dimethylzirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutyl (9-fluorenyl) (cyclo Pentadienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,3)
5-trimethylcyclopentadienyl) dimethyl zirconium and the like can be mentioned.

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 dicyclopentadienylmethyl vanadium. Specific examples of the niobium compound include niobium pentachloride, tetrachloromethyl niobium, dichlorotrimethyl niobium, dicyclopentadienyl niobium dichloride, dicyclopentadienyl niobium trihydride, pentabtoxiniob and the like. Specific examples of the tantalum compound include tantalum pentachloride, dichlorotrimethyltantalum, dicyclopentadienyltantalum trihydride, pentabtoxniobium, and the like, and specific examples of the chromium compound include chromium trichloride, tetrabutoxychromium, and tetramethyl. Examples include chromium, dicyclopentadienyl chromium, dibenzene chromium and the like.

Further, as other transition metal compounds,
It is possible to use the transition metal compound supported on a carrier such as a magnesium compound or a silicon compound,
A compound obtained by modifying the above transition compound with an electron donating compound can also be used. Particularly preferable among these transition metal compounds are titanium compounds and zirconium compounds. For the (a) catalyst, (b) aluminoxane is used together with the (a) transition metal compound. This aluminoxane is obtained by contacting an organoaluminum compound with a condensing agent, and has the general formula (V)

[0019]

[Chemical 3]

[In the formula, 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. ] Chain aluminoxane represented by the general formula (VI)

[0021]

[Chemical 4]

[Wherein R ⁶ is the same as above and q is 2
-50, preferably 5-30. ] Cyclic aluminoxane represented by Examples of the organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, etc. Among them, trimethylaluminum is preferable. Also,
As the condensing agent, water can be mentioned as a typical one, but in addition to this, various substances such as trialkylaluminum that undergoes a condensation reaction, such as copper sulfate pentahydrate, water adsorbed to an inorganic substance or an organic substance, can be used. Can be mentioned.

Generally, the contact product of an organoaluminum compound such as trialkylaluminum with water is a mixture of unreacted trialkylaluminum and various condensation products together with the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane, and Are molecules in which these are intricately associated with each other, and they are various products depending on the contact conditions of the trialkylaluminum and water as the condensing agent. At this time, the method of contacting the alkylaluminum compound and water 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 brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization and water is added later, and a metal salt is contained There is a method of reacting water of crystallization, water adsorbed to an inorganic substance or an organic substance with an organoaluminum compound. The water may contain up to about 20% of ammonia, amine such as ethylamine, sulfur compound such as hydrogen sulfide, phosphorus compound such as phosphite. Although this reaction proceeds in the absence of a solvent, it is preferably carried out in a solvent, and preferable solvents include hexane, heptane,
Examples thereof include aliphatic hydrocarbons such as decane and aromatic hydrocarbons such as benzene, toluene and xylene.

In this aluminoxane (for example, alkylaluminoxane), when a hydrous compound or the like is used after the above-mentioned catalytic reaction, the solid residue is filtered off, and the filtrate is heated under normal pressure or reduced pressure at a temperature of 30 to 200 ° C. Preferably 40
At a temperature of up to 150 ° C. for 20 minutes to 8 hours, preferably 30
What was heat-treated while distilling off the solvent in the range of 5 minutes to 5 hours is preferable. In this heat treatment, the temperature may be appropriately determined depending on various situations, but it is usually performed in the above range. Generally, at a temperature of less than 30 ° C., the effect does not appear,
Further, when the temperature exceeds 200 ° C., thermal decomposition of the alkylaluminoxane itself occurs, which is not preferable. Then, depending on the treatment conditions of the heat treatment, the reaction product is obtained in the form of a colorless solid or solution. The product thus obtained can be used as a catalyst solution by dissolving or diluting it with a hydrocarbon solvent, if necessary.

A suitable example of an aluminoxane, which is a contact product of an organoaluminum compound used as such a catalyst component and a condensing agent, is an alkylaluminoxane, and an aluminum-methyl group (Al- The high magnetic field component in the methyl proton signal region based on CH ₃ ) bond is 50% or less. That is, when the proton nuclear magnetic resonance ( ¹ H-NMR) spectrum of the above contact product is observed in a toluene solvent at room temperature, the methyl proton signal based on “Al—CH ₃ ” is a tetramethylsilane (TMS) standard. In the range of 1.0 to -0.5 ppm. TMS
Of the proton signal (0 ppm) in the methyl proton observation region based on “Al—CH ₃ ”,
Methyl proton signal based on -CH ₃ ", TMS
Toluene's methyl proton signal 2.35 in reference
High magnetic field component (i.e., -0.1 to -0.
5 ppm) and other magnetic field components (ie 1.0 to -0.1 pp)
When it is divided into m), the high magnetic field component of 50% or less, preferably 45 to 5%, can be suitably used as the catalyst component.

As the (b) catalyst, a compound capable of reacting with the (c) transition metal compound to form an ionic complex is used together with the (a) transition metal compound. The compound is not particularly limited, but the compound consisting of a cation and an anion in which a plurality of groups are bound to an element, that is, compound (c) is a group IIIB, VB, VIB, VIIB, VI of the periodic table.
A cation containing an element selected from the group II, the group IA, the group IB, the group IIA, the group IIB, the group IVA, and the group VIIA, and a plurality of groups are VB group, VIB group, VIIB group, VIII group, IB group of the periodic table. , IIB group, IIIA
A compound composed of an anion bonded to an element selected from Group IVA group and VA group, particularly a coordination complex compound composed of a cation and an aonine having a plurality of groups bonded to the element, can be preferably used. For example, general formula (VII) or (VIII) ([L ¹ -R ⁷ ] ^{U +} ) _V (M ² Z ¹ Z ² ... Z ^e ) ^(ef)- ) _W ... (VII) or ([L ² ] ^{U +} ) _V (M ³ Z ¹ Z ²・ ・ ・ Z ^e ) ^(ef)- ) _W・ ・ ・ (VIII) (However, L ² is M ⁴ , R ⁸ R ⁹ M ⁵ , R ¹⁰ ₃ C Or R ¹¹
M ⁵ ) (wherein L ¹ is a Lewis base, M ² and M ³
Are the VB group, VIB group, VIIB group, and VIII of the periodic table, respectively.
An element selected from Group I, Group IB, Group IIB, Group IIIA, Group IVA and Group V, M ⁴ and M ⁵ are Group IIIB of the periodic table,
Group IV, Group V, Group VIB, Group VIIB, Group VIII, Group I, Group IB,
Elements selected from IIA group, IIB group and VIIA group, Z ^{1 to} Z
^e is a hydrogen atom, dialkylamino group, alkoxy group, alkoxy group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms
Aryloxy group, C1-C20 alkyl group, C6-C20 aryl group, alkylaryl group, arylalkyl group, C1-C20 halogen-substituted hydrocarbon group, C1-C20 acyloxy A group, an organic metalloid group or a halogen atom, and two or more of Z ^{1 to} Z ^e may be bonded to each other to form a ring. R ⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms
Represents an aryl group, an alkylaryl group or an arylalkyl group, wherein R ⁸ and R ⁹ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹⁰ is an alkyl group having 1 to 20 carbon atoms. Represents a group, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. f is M ² , M
^{3 has} an valence of 1 to 7, e is an integer of 2 to 8, u is an integer of 1 to 7 as an ionic valence of [L ¹ -R ⁷ ], [L ² ], and v is an integer of 1 or more. , W = (v × u) / (ef). ] It is a compound represented by these.

Specific examples of the Lewis base represented by L ¹ are ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, tri-n-butylamine, N. , N-dimethylaniline, methyldiphenylamine, pyridine; 2,
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 so on.

As specific examples of M ² and M ³ ,
Specific examples of M ⁴ , such as B, Al, Si, P, As, and Sb, are Li, Na, Ag, Cu, Br, I, and I ₃ , and specific examples of M ⁵ are Mn, Fe, and Co. , Ni,
Zn etc. are mentioned. Specific examples of Z ^{1 to} Z ^e include:
For example, a dimethylamino group as the dialkylamino group,
Diethylamino group; methoxy group, ethoxy group, n-butoxy group, carbon number 6 as alkoxy group having 1 to 20 carbon atoms
A phenoxy group as the aryloxy group of -20, 2,6
-Dimethylphenoxy group, naphthyloxy group, carbon number 1
To 20 alkyl groups such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, n-octyl group, 2-ethylhexyl group, aryl group having 6 to 20 carbon atoms, alkylaryl group or As an arylalkyl group, a phenyl group, a p-tolyl group, a benzyl group, a pentafluorophenyl group, a 3,5-di (trifluoromethyl) phenyl group, a 4-tert-butylphenyl group, a 2,6-dimethylphenyl group, 3 , 5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group, 1,2-dimethylphenyl group, p-fluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 3 , 5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group Group, 3,5-di (trifluoromethyl) phenyl group, F as the halogen atom, C
l, Br, I; pentamethylantimony group, trimethylsilyl group, trimethylgermyl group as an organic metalloid group,
Examples thereof include diphenylarsine group, dicyclohexylantimony group, and diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include the same as those mentioned above.
Specific examples of the substituted cyclopentadienyl group for R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Be done. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected by an integer of 1 to 4.

Among the compounds of the above general formulas (VII) and (VIII), those in which M ² and M ³ are boron are preferable. Among the compounds of the general formulas (VII) and (VIII), the following can be used particularly preferably. For example, as the compound of the general formula (VII), there are triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) tetraphenylborate. Ammonium, benzyltri (n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetraphenylborate Methyl (2-cyanopyridinium), trimethylsulfonium tetraphenylborate, benzyl tetraphenylborate Rumethylsulfonium, 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], tetra (pentafluorophenyl) borate [benzyltri (n-butyl) ammonium], tetra (pentafluorophenyl) borate methyldiphenylammonium, tetra 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-ni Roanilinium), dimethyl (p-bromoanilinium) tetra (pentafluorophenylmethyl) borate, 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-
Examples thereof include dimethylanilinium ditrifluoromethylphenyl) borate and triethylammonium tow hexafluoroarsenate.

On the other hand, examples of the compound of the general formula (VIII) include ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin manganese), ferrocenium tetra (pentafluorophenyl) borate and tetra 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) boric acid (tetraphenylporphyrin iron chloride), tetra (pentafluorophenyl) boric acid (tetraphenylporphyrin zinc), silver tetrafluoroborate , Silver hexafluoroarsenate, silver hexafluoroantimonate, and the like. And 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, etc. are also used. be able to.

In the present invention, an organometallic compound can be used as the component (d) together with the catalyst (a) or the catalyst (b) if desired. As the organometallic compound (d) which is optionally used in combination, a compound represented by the general formula M ⁶ (R ¹² ) _r ... (IX) is used. In this general formula (IX), R ¹² is an alkyl group having 1 to 20 carbon atoms and 2 carbon atoms.
˜20 alkenyl group, C 3-20 cycloalkyl group, C 6-20 aryl group or C 7 ˜
20 aralkyl groups are shown. 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. Further, 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. Such as dialkylzinc compounds, alkylgallium compounds such as trimethylgallium, triethylgallium and tripropylgallium, alkylboron compounds such as triethylboron, tripropylboron and tributylboron, alkyltin compounds such as tetraethyltin, tetrapropyltin and tetraphenyltin And so on. In addition, there are various compounds when M ⁶ is aluminum. Specific examples thereof include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and trioctylaluminum.

The proportion of each component used in the above catalyst varies depending on the type and concentration of the styrenic monomer that becomes the graft chain and the polymerizable unsaturated bond that becomes the grafting point, and is not categorically determined. ) In the catalyst, the molar ratio of aluminum in the component (b) to the transition metal (for example, titanium) in the component (a) is 1 to 10 ⁶ , and preferably 10 to 10.
It is desirable to use the components (a) and (b) in such a ratio as to fall within the range of 10 ⁴ . On the other hand, in the (b) catalyst, the molar ratio of the component (c) to the component (a) is 0.01-
It is desirable to use the component (a) and the component (c) at a ratio of 100, preferably in the range of 1 to 10. In this case, the component (a) and the component (c) may be contacted with each other in advance and the contact-treated product may be separated and washed before use, or may be contacted within the polymerization system. In addition, in the catalyst (a) or the catalyst (b), the amount of the component (d) used as desired is usually selected in the range of 0 to 100 mol with respect to 1 mol of the component (a). By using this component (d), the polymerization activity can be improved, but even if it is used in too large an amount, the effect equivalent to the amount added is not exhibited. In addition, this (d)
The component may be used in contact with the contact-treated product of the component (a), the component (c) or the component (a) and the component (c).
This contact may be carried out in advance, or may be sequentially added into the polymerization system for contact.

The above styrenic monomer and graft precursor
(Polymer polymerization with polymerizable carbon-carbon double bond in the side chain
Styrene monomer / graft precursor
The grafting point molar ratio in the body is 1 to 10⁶, Preferably 2
10^FiveIt is desirable to choose to be within the range. In addition,
There is no particular restriction on the usage ratio of the ethylene monomer and the catalyst.
However, it is usually a styrene monomer / transition metal compound model.
10 to 10¹², Preferably 10 ²-10⁸Range of
Be chosen as in. In the graft polymerization reaction,
Generally, the polymerization temperature is 0 to 120 ° C., preferably 10 to
Select a polymerization time in the range of 80 ° C and 1 second to 10 hours.
You can set it. Polymerization methods include bulk, solution, and suspension polymerization.
Either of these is possible. For solution polymerization,
Solvents that can be used include pentane, hexane, and heptane.
Alicyclic carbonization such as aliphatic hydrocarbons, cyclohexane
Aromatic carbonization of hydrogen, benzene, toluene, xylene, etc.
There is hydrogen. Among these, aliphatic hydrocarbons and aromas
Group hydrocarbons are preferred. In this case, the monomer / solvent (body
The product ratio) can be arbitrarily selected. In addition, graft
As the point-forming monomer, a vinyl represented by the above general formula (I) is used.
When using a nylstyrene-based compound, when manufacturing the precursor
Has a high reaction rate and the amount of unreacted monomer at the end of the reaction is low.
Then, by adding the catalyst component,
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 producing the precursor is low, and the amount of unreacted monomer is large at the end of the reaction, so the catalyst is continuously added. 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. Furthermore, in the case of divinylbenzene having the same polymerization reactivity, the vinylstyrene content of the precursor is set to 10 in order to prevent the crosslinking reaction.
It is preferably in the range of ^{-4 to} 2 mol%. Furthermore, when a low-boiling-point diene compound such as 1,3-butadiene or isoprene is used as the graft-point-forming monomer, the unreacted monomer can be easily removed after the precursor is produced, and the graft copolymerization can be continued. is there. In this way
The graft copolymer of the present invention is obtained. The molecular weight of the graft copolymer used in the present invention is 0.01 in terms of reduced viscosity at a concentration of 0.05 g / deciliter measured in 1,2,4-trichlorobenzene (TCB) at a temperature of 135 ° C.
-20 to 20 deciliters / g, preferably 0.05 to 15 deciliters / g, or a melt index of 0.001 to 500 g / 10 minutes measured at 300 ° C. under a load of 2.16 kg,
It is preferably in the range of 0.005 to 300 g / 10 minutes. This reduced viscosity is 0.01 deciliter / g
If the melt index is less than 500 g / 10 min, the mechanical strength will be insufficient, and if it exceeds 20 deciliter / g or less than 0.001 g / 10 min, the moldability will be poor.

The graft copolymer used in the present invention has a syndiotactic structure having a high degree of stereoregularity of the chain composed of styrene-based monomer units. That is, the racemic diad is 75% or more, preferably 85%
As described above, 30% or more, preferably 50% in racemic pentad
% Or more. Further, the content of the chain composed of this styrene-based monomer unit is 0.005 to 99% by weight, preferably
It is preferably in the range of 0.5 to 99% by weight. The graft copolymer having this content in the range of usually 0.005 to 50% by weight has high elasticity and high strength and can be used as a thermoplastic elastomer or a resin compatibilizer. On the other hand, the graft copolymer whose content is usually in the range of 50 to 99% by weight can harden and impart toughness to a styrene-based polymer having a syndiotactic structure, and is also used as a resin compatibilizer. it can. In the composition of the present invention, at least one selected from (B) a styrene-based polymer having a high syndiotactic structure and another thermoplastic resin together with the graft copolymer which is the (A) component. At least one selected from the group consisting of one kind and / or (C) an inorganic filler and an organic filler is used.

The syndiotactic structure in the styrene polymer as the component (B) is syndiotactic in stereochemical structure, that is, a phenyl group which is a side chain with respect to the main chain formed from carbon-carbon bonds, It has a three-dimensional structure in which substituted phenyl groups are alternately located in opposite directions, and its tacticity is determined by nuclear magnetic resonance method using isotope carbon (
¹³ C-NMR method). ^The tacticity measured by the ¹³ C-NMR method is the proportion of a plurality of continuous constitutional units, for example, in the case of two, diad,
The case of three can be indicated by a triad, and the case of five can be indicated by a pentad. The styrenic polymer having a high syndiotactic structure referred to in the present invention is, in the chain of styrenic repeating units, preferably 75% or more by racemic dyad, more preferably 85% or more, or preferably racemic pentad. Indicates those having a syndiotacticity of 30% or more, more preferably 50% or more. However, the degree of syndiotacticity varies slightly depending on the type of substituent. Although the molecular weight of this styrene-based polymer varies depending on the polymerization conditions, the weight average molecular weight is usually 5,000 to 4.5 million,
It is preferably 10,000 or more.

The styrenic polymer having such a highly syndiotactic structure is obtained by adding the styrenic monomer represented by the general formula (III) to the graft copolymer of the component (A). It can be obtained by polymerizing by a method such as bulk polymerization, solution polymerization or suspension polymerization using the same catalyst as that used for graft copolymerizing the styrene-based monomer. The polymerization method may be either continuous polymerization or discontinuous polymerization. When a solvent is used, aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, benzene,
A halogenated hydrocarbon such as toluene or xylene can be used. Two or more kinds of these solvents may be combined. The monomer / solvent ratio is arbitrary. Further, the polymerization conditions are not particularly limited, but the polymerization temperature is -10.
The polymerization time is preferably 0 to 250 ° C., preferably 0 to 80 ° C., and the polymerization time is 5 minutes to 24 hours, preferably 1 hour or more. The polymerization pressure is not particularly limited, but in order to control the molecular weight. It is effective to carry out in the presence of hydrogen.

Specific examples of the styrene polymer represented by the general formula (III) used in this case include the same ones as exemplified above. These styrenic monomers may be used alone, or may be used in combination of two or more kinds, and may be copolymerized, and the properties of the styrenic polymer or the syndiotactic structure in the chain of repeating units may be improved. The third component, for example, an olefin-based monomer or a polar monomer may be used for copolymerization within a range not significantly impairing. As the other thermoplastic resin, various kinds of resins such as polyolefin resin, polystyrene resin, condensation type high molecular polymer, addition polymerization type high molecular polymer and the like can be mentioned. Specific examples of the polyolefin resin include high density polyethylene, low density polyethylene, poly-3-methyl-butene-1; poly-4-methyl-pentene-1, or butene-1 as a comonomer component; hexene-1;
Linear low density polyethylene obtained by using octene-1; 4-methylpentene-1; 3-methylbutene-1, etc., ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene-acryl Examples thereof include acid copolymers, ethylene-acrylic acid ester copolymers and ethylene-based ionomer polypropylene. Specific examples of polystyrene resin include general-purpose polystyrene,
Examples include isotactic polystyrene and high-impact polystyrene (rubber modified). Specific examples of the condensation type polymer include polyacetal resin, polycarbonate resin, polyamide resin such as nylon 6, nylon 6.6, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyphenylene oxide resin, polyimide resin, polysulfone resin. , Polyethersulfone resin, polyphenylene sulfide resin and the like. Examples of the addition polymerization type high molecular weight polymer include, for example, a polymer obtained from a polar vinyl monomer or a polymer obtained from a diene type monomer, specifically, polymethylmethacrylate, polyacrylonitrile, acrylonitrile-butadiene copolymer, Examples thereof include an acrylonitrile-butadiene-styrene copolymer, a diene polymer in which a diene chain is hydrogenated, and a thermoplastic elastomer. The thermoplastic resin as the component (B) may be used alone or in combination of two or more kinds.

There are no particular restrictions on the shape of the inorganic or organic filler of component (C) in the composition of the present invention.
Any shape such as granular, plate-like, fibrous, and whisker-like can be used. As the inorganic filler, an inorganic filler, a metal-based filler, a ceramic-based filler, or the like can be used. Examples of the inorganic filler include oxides such as silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice and pumice balloons, hydroxides such as aluminum hydroxide, magnesium hydroxide and basic magnesium carbonate, calcium carbonate, Magnesium carbonate,
Carbonates such as dolomite and dawsonite, sulfates or sulfites such as calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass balloons, glass beads, calcium kenate, montmorillonite, bentonite Silicates, carbon black, graphite, carbon fibers, carbons such as carbon hollow spheres, molybdenum sulfide, boron fibers, zinc borate, barium metaborate,
Examples thereof include calcium borate and sodium borate.

As the metallic filler, metallic elements,
Powders or granules of metal compounds or alloys, or metal fibers or metal whiskers are used. Specifically, metal elements such as zinc, copper, iron, lead, aluminum, nickel, chromium, titanium, manganese, tin, platinum, tungsten, gold, magnesium, cobalt, strontium, oxides of these metals, and stainless steels. , Alloys such as solder and brass, aluminum fiber, stainless fiber, copper fiber, brass fiber, nickel fiber, potassium titanate fiber and other simple metal fibers, metal fibers such as alloy fibers, and corresponding metal whiskers Can be mentioned. Further, examples of the ceramic filler include powders such as silicon carbide, silicon nitride, zirconia, aluminum nitride, and titanium carbide, granules, fibers,
Whiskers can be mentioned. On the other hand, examples of the organic filler include shell fiber such as fir shell, wood powder, cotton,
Jute, paper strip, cellophane strip, aromatic polyamide fiber, polyimide fiber, cellulose fiber, nylon fiber,
Examples thereof include polyester fiber, ultra high molecular weight polyethylene fiber, polypropylene fiber, and thermosetting resin powder. These fillers may be used alone or in combination of two or more.

In the composition of the present invention, various additives such as heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifog agents, lubricants, foaming agents, dyes, pigments are added as desired. , Natural oil, synthetic oil, wax and the like can be blended, and the blending amount is appropriately selected. Specific examples of the stabilizer include tetrakis [methylene-3 (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate] methane; β- (3,5-di-t-butyl-4)
-Hydroxyphenyl) propionic acid alkyl ester; 2,2'-oxamide bis [ethyl-3 (3,5-
Di-t-butyl-4-hydroxyphenyl)] propionate and other phenolic antioxidants, zinc stearate, calcium stearate, fatty acid metal salts such as 12-hydroxycalcium stearate, glycerin monostearate, glycerin monolaurate, glycerin Examples thereof include polyhydric alcohol fatty acid esters such as distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. They are,
They may be blended alone or in combination, for example tetrakis [methylene-3 (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
A combination of methane with zinc stearate and glycerin monostearate is preferred.

In the composition of the present invention, the blending ratio of the graft copolymer of the component (A) and the thermoplastic resin of the component (B) is usually 0.5: 99.5 to 99.5: 0 by weight. .5, preferably in the range of 1:95 to 99: 5. On the other hand, when the graft copolymer of the component (A) and the inorganic or organic filler of the component (C) are blended, the weight ratio of the component (A) to the component (C) is 20:80 or more. 95: 5,
It is desirable to mix them so that the ratio is preferably 40:60 to 90:10. In addition, in the resin composition of the present invention, the graft copolymer of the component (A) can be blended with the thermoplastic resin of the component (B) and an inorganic filler or an organic filler of the component (C). However, in this case, (A)
The resin component comprising the component and the component (B) and the component (C) have a weight ratio of 20:80 to 95: 5, preferably 4
It is desirable to mix them so as to be 0:60 to 90:10. The method for preparing the resin composition of the present invention is not particularly limited, but the melt-kneading method conventionally used in conventional thermoplastic resin compositions is suitable. This melt-kneading method can be carried out using a known means such as a Banbury mixer, a single-screw or twin-screw extruder, a kneader, a continuous mixer, and a mixing roll. Alternatively, a solution blending method using a good solvent may be used.

[0043]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Production Example 1 (Production of Graft Copolymer) (1) Preparation of Methylaluminoxane 200 ml of toluene, copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) 17. 7 g (71 mmol) and 24 ml (250 mmol) of trimethylaluminum 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 was obtained. The molecular weight of this product measured by the freezing point depression method was 610. Also, JP-A-62-32539
High magnetic field component by ¹ H-NMR measurement based on Japanese Patent 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 (ie, -0.1 to -0.5 ppm) and other magnetic field components (ie, 1.0 to -0.1 ppm), the high magnetic field component was 43% of the whole.

(2) Preparation of solid catalyst component In a well-dried 500 ml four-necked flask, 150 ml of dehydrated and purified n-heptane was placed, and then magnesium diethoxide (10.0 g, 88)
1.06 g (17.5 mmol) of isopropyl alcohol was added with stirring, and the temperature was raised 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, and stirring and extraction were repeated twice to wash, and then 150 ml of n-heptane and 2.63 g of ethyl benzoate were added.
(17.5 mmol) and titanium tetrachloride (83 g, 440 mmol) were introduced, the temperature was raised to the boiling point, and the mixture was reacted for 2 hours. After the reaction, the temperature was lowered to 80 ° C., the mixture was allowed to stand, the supernatant was extracted, 150 ml of n-heptane was newly added, and stirring, standing and draining were repeated twice to wash.
Then, again add 83 g of titanium tetrachloride to bring the boiling point to 1
After reacting for a period of time, the solution was allowed to stand and then drained, then n-heptane was added, and the mixture was stirred, allowed to stand and drained repeatedly until chlorine ions were no longer detected, to obtain a solid catalyst component.
When 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 Copolymer (Graft Precursor) 600 ml of deaerated and purified toluene, 3 mmol of isobutylaluminum, and 10 mmol of p- (3-butenyl) styrene were put into a dried 1 liter pressure autoclave. The temperature was raised to 70 ° C. and stirring was started. After propylene was saturated with propylene at a pressure of 7 kg / cm ² G, ethylene was changed to 3 kg / cm ² G. Next, using the solid catalyst prepared in (2) above as a titanium atom, 0.01
5 mmol was added and copolymerization was carried out for 1 hour. During this period, the reaction pressure was adjusted with ethylene so that the total pressure was 10 kg / cm ² 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) Preparation of graft copolymer In a separable flask equipped with a 1-liter stirrer, 39.6 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. It was distilled off under reduced pressure. It was newly dissolved in 400 ml of dry toluene, 200 ml of styrene, 2 mmol of triisobutylaluminum and 2 mmol of methylaluminoxane were added, and the mixture was kept at 70 ° C for 5 minutes. Then, 10 μmol of pentamethylcyclopentadienyltitanium trimethoxide {Cp ^* Ti (OMe) ₃ } was added to initiate graft polymerization. After polymerizing for 12 minutes, methanol was added to the reaction system to terminate the polymerization, and after washing with methanol, 40.3 g of a graft copolymer was obtained.
The styrene unit content of this product was 2.0 wt%, and the reduced viscosity was 1.41 deciliter / g (0.05 g / deciliter in TCB at 135 ° C.).

Production Example 2 (Production of Copolymer) In Production Example 1 (3), the titanium catalyst component was 0.005.
Mmol, propylene was 3.0 kg / cm ² G, ethylene was 1.5 kg / cm ² G, p- (3-butenyl) styrene was 10 mmol, and the polymerization temperature was 17 ° C. 22.7 g of polymer was obtained. Furthermore, 20 g of this copolymer was used to prepare 50 ml of styrene and 10 parts of triisobutylaluminum in (4) of Production Example 1.
Mmol, methylaluminoxane 10 mmol, {Cp
^* Add Ti (OMe) ₃ } 20 μmol and add 70 ° C.
Graft copolymerization was carried out for 3 hours to obtain 40.1 g of a graft copolymer. The styrene unit content of this product is 49.
8 wt% and the reduced viscosity is (135 ° C, TCB
Medium, 0.05 g / deciliter) 1.23 deciliter / g
Met.

Examples 1 to 3 and Comparative Example 1 Using a Labo Plastomill manufactured by Toyo Seiki Co., Ltd. having an internal volume of 100 ml, the resins blended in the proportions shown in Table 1 were melt-kneaded at 280 ° C. and 50 rpm for 8 minutes. A resin composition was prepared. The compatibilized state of this resin composition is shown in electron micrographs (300 times) of FIGS. 1 to 4.

[0049]

[Table 1]

Next, the melt-kneaded resin composition and S
The PS is hot pressed to a thickness of 2 mm at 300 ° C,
Plates were made by cooling in a cooling press. Then, this was cut to prepare an Izod impact test piece, and the Izod impact strength (with notch) was obtained. The measurement results are shown in Table 2.

[0051]

[Table 2]

Examples 4 and 5 100 parts by weight of the resin compositions obtained in Examples 1 and 2 were mixed with 30 parts by weight of glass fiber (length 3 mm) and talc, respectively, to prepare a resin composition of Example 1. Obtained accordingly. When a fracture surface of a test piece obtained by similarly compression-molding this composition was observed with an electron microscope, the interface between the resin and the filler showed good bonding.

[0053]

The resin composition of the present invention has excellent heat resistance originally possessed by a styrene resin having a syndiotactic structure,
While maintaining characteristics such as high crystallinity, easy moldability, and chemical stability, compatibility, adhesion, and impact resistance are imparted, and the physical properties are balanced at a high level, especially heat resistance and impact resistance. It is preferably used as a material in required fields such as a bicycle field and an electric / electronic field.

[Brief description of drawings]

1 is an electron micrograph of the resin composition obtained in Example 1. FIG.

2 is an electron micrograph of the resin composition obtained in Example 2. FIG.

FIG. 3 is an electron micrograph of the resin composition obtained in Example 3.

FIG. 4 is an electron micrograph of a resin composition obtained in Comparative Example 1.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C08L 101/00 LSZ 7242-4J

Claims (2)

[Claims] 1. A polymer obtained by graft-copolymerizing a styrenic monomer to a high molecular polymer having a polymerizable carbon-carbon double bond in a side chain (A), comprising a styrenic monomer unit. At least one selected from the group consisting of a graft copolymer having a syndiotactic structure with a high degree of stereoregularity of a chain, and (B) a styrene-based polymer having a high syndiotactic structure and other thermoplastic resins And / or (C) a resin composition containing at least one selected from an inorganic filler and an organic filler. 2. The graft copolymer has a graft component content in the range of 0.005 to 99% by weight, and is measured in 1,2,4-trichlorobenzene at a temperature of 135.degree. The reduced viscosity at a concentration of 05 g / deciliter
0.01-20 deciliters / g or 300 ° C, 2.16k
Melt index measured by g-load is 0.001-50
The resin composition according to claim 1, which is 0 g / 10 minutes.