JPH10292076A - Styrene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a styrene resin compsn. which has excellent resistances to heat and chemical and a good toughness and is useful as a material for composites or as a heat-resistant elastomer by compounding a thermoplastic resin with a syndiotactic polystyrene graft copolymer formed from a styrene monomer and an olefinic macromer having terminals modified with a styrene deriv. SOLUTION: This compsn. comprises 0.1-99.9 wt.% thermoplastic resin (A) and 99.9-0.1 wt.% graft copolymer (B) which is formed from a styrene monomer (a) and an olefinic marcromer (b) having terminals modified with a styrene deriv. and represented by the formula (wherein R is H or 1-20C alkyl; X is H, halogen, or a group contg. carbon, Sn, and Si; (n) is 1-4; (m) is 0 or a natural number; and Z is an olefin polymer chain). Examples of an olefin monomer constituting the macromer (b) are ethylene, propylene, and norbornene. The graft copolymer (B) comprises 99.9-0.1 wt.% polymer segments derived from the styrene monomer (a) and 0.1-99.9 wt. % polymer segments derived from the macromer (b).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrenic resin composition, and more particularly, it has excellent heat resistance, chemical resistance and the like, has good toughness, and is used as a material for composite materials and a heat-resistant elastomer. The present invention relates to a styrene-based resin composition which is extremely useful in the fields of electrical equipment, electronic equipment, and the like.

[0002]

2. Description of the Related Art The research group of the present inventors has previously succeeded in developing a styrenic polymer having a high syndiotacticity and further obtained a syndiotactic polymer obtained by copolymerizing this styrenic monomer with other components. Styrene-based copolymers have been developed (JP-A-62-104818, JP-A-63-104818).
2410009). However, these styrenic polymers or copolymers having a syndiotactic structure are excellent in heat resistance, chemical resistance, etc., but have insufficient toughness and poor compatibility with other resins, and are not suitable for applications. I could not escape being limited. In order to improve such toughness and elongation, as well as compatibility with other resins, a graft copolymer obtained by graft copolymerizing a styrene-based monomer with a polymer having a double bond in the side chain, or polymerizing at the terminal A block copolymer in which a styrene-based monomer is block-copolymerized with a macromonomer having an active vinyl group has been proposed (JP-A-05-247147 and JP-A-05-295056).
No.).

However, in the styrene-based graft copolymers and block copolymers specifically disclosed therein, a reactive group is randomly present in the olefin-based segment, and thus a styrene-based monomer is copolymerized. At the same time, cross-linking occurs at the same time, and there is a problem that formation of an effective graft copolymer is inhibited, and toughness and, furthermore, those which are sufficiently satisfactory in compatibility with other resins have been obtained. There is no present.

[0004]

Under such circumstances, the present invention has excellent heat resistance, chemical resistance, etc., and has good toughness.
An object of the present invention is to provide a styrene-based resin composition comprising a syndiotactic polystyrene graft copolymer and a thermoplastic resin, which is extremely useful in the fields of home appliances, electric devices, and electronic devices.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, it has been found that a repeating unit of a styrene monomer and an olefin monomer is modified with a styrene derivative. (A) a graft copolymer with a terminal styrene derivative-modified olefin-based macromer having a high degree of stereoregularity of a chain derived from a styrene-based monomer (A);
And a styrene-based resin composition comprising the thermoplastic resin (B) and the thermoplastic resin (B) have excellent heat resistance, chemical resistance, and the like, and have good toughness, elongation, and compatibility. The present invention has been completed based on such findings.

That is, the present invention provides the following. (1) A copolymer of a styrene monomer (a) and an olefin macromer (b) modified with a terminal styrene derivative represented by the following general formula (1), wherein the styrene monomer has a high degree of stereoregularity. Graft copolymer (A) having a syndiotactic structure of 99.9
A styrene-based resin composition comprising 0.1 to 9% by weight of a thermoplastic resin (B) other than (A) and 0.1 to 99.9% by weight.

[0007]

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[Wherein, R is a hydrogen atom or a carbon atom having 1 to 20 carbon atoms.
Wherein each R may be the same or different. X represents any of the following: Hydrogen atom,
A substituent containing at least one selected from a halogen atom, a carbon atom, a tin atom and a silicon atom;
n represents an integer of 1 to 4, and when n is 2 or more, each X
May be the same or different. Further, m is 0 or a natural number, and Z represents a chain portion derived from an olefin-based monomer. (2) The graft copolymer (A) according to (1) above,
A polymer segment comprising 99.9 to 0.1% by weight of a polymer segment derived from a styrene-based monomer (a) and 0.1 to 99.9% by weight of a polymer segment derived from a styrene-terminal-modified olefin-based macromer (b). (1)
The styrene-based resin composition according to 1. (3) The graft copolymer (A) according to (1) above,
Terminal styrene derivative-modified olefin macromer (b)
Is dissolved in a styrene-based monomer (a) or a solvent containing the styrene-based monomer (a), and then (I) a transition metal compound, (II) (a) a general formula (2)

[0009]

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(Wherein R ^{1 to} R ⁵ each have 1 to 1 carbon atoms)
8 represents an alkyl group, which may be the same or different; Y ^{1 to} Y ³ each represent a Group 13 element of the periodic table; they may be the same or different; Represents a number from 0 to 50, respectively, and a +
b is 1 or more. ) And / or general formula (3)

[0011]

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(Wherein R ⁶ and R ⁷ each have 1 carbon atom)
To 8 alkyl groups, which may be the same or different, and Y ⁴ and Y ⁵ each represent
Represents a group 3 element, which may be the same or different, c and d each represent a number of 0 to 50,
c + d is 1 or more. An oxygen-containing compound represented by
And / or (ii) a copolymer produced by copolymerizing (a) and (b) using a catalyst comprising a compound capable of reacting with the transition metal compound of the component (I) to form an ionic complex. (1) or (2) above,
Styrene resin composition described in

[0013]

Embodiments of the present invention will be described below. 1. Styrenic resin composition The styrenic resin composition according to the present invention has a graft copolymer (A) having a specific structure of 99.9 to 0.1% by weight.
And thermoplastic resin (B) other than (A) 0.1 to 99.
It consists of 9% by weight. (1) Graft copolymer (A) The graft copolymer (A), which is one component of the styrene resin composition according to the present invention, comprises a styrene monomer (a)
And a styrene-terminal-modified olefin-based macromer (b) represented by the general formula (1), which has a high degree of stereoregularity of a chain derived from a styrene-based monomer and has a high syndiotactic structure. It is.

Styrene monomer (a) The styrene monomer used in the present invention is a compound represented by the general formula (4).

[0015]

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[Wherein, X represents any of the following: A substituent containing at least one selected from a hydrogen atom, a halogen atom, and a carbon atom, a tin atom and a silicon atom; n represents an integer of 1 to 5, and when n is 2 or more, each X may be the same or different. ]
The compound represented by is used. Specifically, styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene
Alkyl styrene such as dimethyl styrene, p-ethyl styrene, m-ethyl styrene, p-tert-butyl styrene; vinyl benzene such as p-divinyl benzene, m-divinyl benzene, tridivinyl benzene; p-chloro styrene, m-chloro Halogenated styrenes such as styrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene , Methoxystyrene, ethoxystyrene, t-butoxystyrene, and other alkoxystyrenes, vinyl biphenyls, vinyl phenyl naphthalenes, vinyl phenyl anthracenes, halogenated vinyl biphenyls, trialkylsilyl vinyl biphenyls, halo Down-substituted alkyl styrene, alkyl silyl styrenes, phenyl group-containing silyl styrenes,
Examples include halogen-containing silyl styrenes, silyl group-containing silyl styrenes, or a mixture of two or more thereof.

(B) (i) Examples of the olefin monomer include ethylene;
Propylene; butene-1; pentene-1; hexene-
1; heptene-1; octene-1; nonene-1; decene-1; 4-phenylbutene-1; 6-phenylhexene-1; 3-methylbutene-1; 4-methylpentene-
1; 3-methylpentene-1; 3-methylhexene-
1; 4-methylhexene-1; 5-methylhexene-
1, 3,3-dimethylpentene-1; 3,4-dimethylpentene-1; 4,4-dimethylpentene-1; α-olefin such as vinylcyclohexane, hexafluoropropene; tetrafluoroethylene; 2-fluoropropene; 1,3-difluoroethylene; 3-fluoropropene; trifluoroethylene;
Halogen-substituted α-olefins such as 3,4-dichlorobutene-1, cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; One or more olefinic monomers such as cyclic olefins such as -methylnorbornene; 5,5,6-trimethylnorbornene; 5-phenylnorbornene; and 5-benzylnorbornene are used. As the macromer (b) having an olefin-based monomer as a repeating unit, one having one kind of the above-mentioned olefin-based monomer as a repeating unit, or one in which two or more kinds are linked by random or block copolymerization are also suitable. No. (ii) The terminal styrene derivative-modified olefin macromer (b) is represented by the following general formula (1), and the terminal of the repeating unit of the olefin monomer is modified with a styrene derivative. is necessary.

[0018]

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In the formula, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and is preferably hydrogen. Each R may be the same or different. X represents any of the following: A substituent containing at least one selected from a hydrogen atom, a halogen atom, and a carbon atom, a tin atom and a silicon atom; Specifically, hydrogen, chlorine,
Halogen atoms such as bromine and fluorine, methyl groups, ethyl groups,
Alkyl group such as tertiary butyl group, alkoxy group such as methoxy group, ethoxy group, t-butoxy group, vinyl group, vinylphenyl group, halogen-substituted alkyl group, alkylsilyl group, phenyl group-containing silyl group, halogen-containing silyl group And a silyl group-containing silyl group. n
Represents an integer of 1 to 4, but when n is 2 or more, that is, when X is plural, each X may be the same or different. Further, m is 0 or a natural number, and Z represents a chain portion derived from the olefin-based monomer. In the styrene derivative portion present at the terminal of the structure represented by the general formula (1), the position where a vinyl group (when R is a hydrogen atom) or an alkyl-substituted vinyl group (when R is an alkyl group) is attached: Any of the ortho, meta and para positions may be used, but the para position is preferably used. (iii) The method for producing the olefin macromer (b) modified with a terminal styrene derivative represented by the general formula (1) is not particularly limited, and is, for example, a known method disclosed in JP-A-06-122711. Specifically, it can be obtained by performing living polymerization of olefins using a catalyst comprising a specific vanadium compound and an organoaluminum compound, and reacting with a styrene derivative at the end of the polymerization.

The graft copolymer (A) in the present invention
Is obtained by copolymerizing the styrene-based monomer (a) and the styrene-terminal-modified olefin-based macromer (b) represented by the general formula (1). In the graft copolymer, preferably, the polymer segment derived from the styrene monomer (a) has 99.9 to
0.1% by weight, more preferably 99.0 to 1.0% by weight, further preferably 95.0 to 5.0% by weight, the terminal styrene derivative-modified olefin-based macromer (b) represented by the general formula (1) 0.1 to 9 of the polymer segment derived from
9.9% by weight, more preferably 1.0 to 99.0% by weight, and even more preferably 5.0 to 95.0% by weight.
Further, it has a syndiotactic structure in which the stereoregularity of the chain derived from the styrene-based monomer is high.
That is, 75% or more, preferably 85% by racemic dyad.
% Or more, 30% or more in racemic pentad, preferably 5%
0% or more. When a mixture of two or more types of monomers is used as the styrene-based monomer, the segment derived from the styrene-based monomer may be a random copolymer or a block copolymer of the plurality of monomers. (2) Method for Producing Graft Copolymer (A) The method for producing the graft copolymer (A), which is one component of the styrene resin composition according to the present invention, is not particularly limited. For example, simply adding the powdery styrene-terminated olefin-based macromer (b) to a syndiotactic polystyrene powder obtained by synthesis and giving a heat history to the reaction to start the reaction to obtain the graft copolymer. It is possible. Preferably, the terminal styrene derivative-modified olefin macromer (b) is converted to a styrene monomer (a)
Or, after being dissolved in a solvent containing a styrene-based monomer (a), (I) a transition metal compound, (II) (A) an oxygen-containing compound described below, and / or (B) a transition metal compound of the component (I). A compound capable of forming an ionic complex by reacting with
And, if necessary, copolymerization using a catalyst comprising an alkylating agent (III). In this case, since the reaction can be performed uniformly,
The styrene-terminated olefin-based macromer (b) is converted into a styrene-based monomer (a) or a styrene-based monomer (a).
Is preferably used. The solvent is not particularly limited and includes toluene, benzene,
Hydrocarbon solvents such as ethylbenzene are preferably used. The catalysts preferably used for copolymerization are as follows.

Various components of the catalyst (I) Transition metal compound (I) As the transition metal compound, various compounds can be used, and usually represented by the following general formula (5) or (6). Compounds are used. _{^{MR 8 a R 9 b R 10}} c R 11 4- (a + b + c) ··· (5) MR 8 d R 9 e R 10 3- (d + e) ··· (6) wherein , M represents a metal belonging to Groups 3 to 6 of the periodic table or a lanthanum-based metal, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ represent an alkyl group, an alkoxy group, an aryl group, an alkylaryl group, an arylalkyl group, Aryloxy, acyloxy, cyclopentadienyl, alkylthio,
Represents an arylthio group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, an amino group, an amide group, an acyloxy group, a phosphide group, a halogen atom, or a chelating agent; Represents an integer of 4 to 4, and d and e are each 0 to 3
Indicates an integer. Any two of R ^{8 to} R ¹¹ are CH
₂ or a complex cross-linked with Si (CH ₃ ) ₂ or the like. As the metal of Group 3 to 6 or the lanthanum-based metal represented by M, a Group 4 metal, particularly, titanium, zirconium, hafnium or the like is preferably used.

Preferred titanium compounds include those represented by the general formula (7) TiRXYZ (7) wherein R is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group X, Y and Z each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
0 alkoxy group, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, 6 to 20 carbon atoms
Aryloxy group, an acyloxy group having 1 to 20 carbon atoms, an amino group, an amide group, a phosphide group, an alkylthio group, an arylthio group, or a halogen atom having 1 to 50 carbon atoms. ] The compound represented by these. here,
Compounds in which one of X, Y and Z and R are cross-linked by CH ₂ , SiR ₂ or the like are also included.

Among these titanium compounds, compounds containing no halogen atom are preferable, and in particular, titanium compounds having one π-electron ligand as described above are preferable.
Further, as the titanium compound, a compound represented by the general formula (8)

[0024]

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[Wherein, R ¹² and R ¹³ each represent a halogen atom, an alkoxy group having 1 to 20 carbon atoms, or an acyloxy group, and k represents 2 to 20. ] May be used. Further, as the above titanium compound, a compound which forms a complex with an ester or an ether may be used. Other transition metal compounds as component (a) include transition metal compounds having two ligands having conjugated π electrons, for example, a general formula (9) M ¹ R ¹⁴ R ¹⁵ R ¹⁶ R ^17. 9) [wherein, M ¹ represents titanium, zirconium or hafnium, R ¹⁴ and R ¹⁵ each represent a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹⁶ and R ¹⁶ Reference numeral ¹⁷ denotes a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, or a thioalkoxy group having 1 to 20 carbon atoms. Where R
¹⁴ and R ¹⁵ are a hydrocarbon group having 1 to 5 carbon atoms,
It may be cross-linked by an alkylsilyl group having 20 and 1 to 5 silicon atoms or a germanium-containing hydrocarbon group having 1 to 20 carbon atoms and 1 to 5 germanium. At least one compound selected from the group consisting of transition metal compounds represented by the formula:

Further, as the transition metal compound of the component (I), a general formula (10) R'MX ' _p-1 L ¹ _q (10) wherein R' is a π ligand, A condensed polycyclic cyclopentadienyl group in which at least one of the multi-membered rings to which the cyclopentadienyl group is condensed is a saturated ring, M is the same as described above, and X ′ represents a σ ligand , A plurality of X ′ may be the same or different, and may be bonded via an arbitrary group. L ¹ is a Lewis base, p
Represents the valence of M, q represents 0, 1 or 2, and when L ¹ is plural, each L ¹ may be the same or different. ]
There is at least one compound selected from the group consisting of transition metal compounds having the structure represented by

In the above general formula (10), R ′ is a π ligand, and at least one of the multi-membered rings to which the cyclopentadienyl group is fused is a condensed polycyclic cyclopentadienyl. Represents a group. Examples of such a condensed polycyclic cyclopentadienyl group include compounds represented by general formulas (11) to (13)

[0028]

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[Wherein R ¹⁸ , R ¹⁹ and R ²⁰ each represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a carbon atom 1
Alkoxy group having 20 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, thioalkoxy group having 1 to 20 carbon atoms, carbon group having 6 to 2 carbon atoms
0 thioaryloxy group, an amino group, an amide group, a carboxyl group or an alkylsilyl group, each of R ^18, each R ¹⁹
And each R ²⁰ may be the same or different, and w, x, y and z each represent an integer of 1 or more. Selected from the condensed polycyclic cyclopentadienyl groups represented by the following formulas, and among these, 4,5,5
6,7-Tetrahydroindenyl groups are preferred.

Specific examples of R ′ include 4, 5, 6,
7-tetrahydroindenyl group; 1-methyl-4,5,
6,7-tetrahydroindenyl group; 2-methyl-4,
5,6,7-tetrahydroindenyl group; 1,2-dimethyl-4,5,6,7-tetrahydroindenyl group;
1,3-dimethyl-4,5,6,7-tetrahydroindenyl group; 1,2,3-trimethyl-4,5,6,7-
Tetrahydroindenyl group; 1,2,3,4,5,6
7-heptamethyl-4,5,6,7-tetrahydroindenyl group; 1,2,4,5,6,7-hexamethyl-
4,5,6,7-tetrahydroindenyl group;
4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyl group; octahydrofluorenyl group;
1,2,3,4-tetrahydrofluorenyl group; 9-methyl-1,2,3,4-tetrahydrofluorenyl group;
And a 9-methyl-octahydrofluorenyl group.

M represents a metal belonging to Groups 3 to 6 of the periodic table or a lanthanum metal, and examples thereof include titanium, zirconium, hafnium, lanthanoid metals, niobium, and tantalum. Among them, titanium is preferred from the viewpoint of catalytic activity. X ′ represents a σ ligand, specifically, a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, ~ 2
An alkoxy group having 0, an aryloxy group having 6 to 20 carbon atoms,
A thioalkoxy group having 1 to 20 carbon atoms, a thioaryloxy group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxyl group, an alkylsilyl group and the like;
May be the same or different, and may be bonded via an arbitrary group.

As the transition metal compound represented by the general formula (10), a compound containing a compound arbitrarily selected from R ′ and X ′ described above can be preferably used. Further, as the transition metal compound, a general formula (14) R ²¹ MX _a-1 L _b (14) wherein R ²¹ represents a hexahydroazulenyl group represented by the following general formula (15) . M represents a transition metal, X represents a σ ligand, and a plurality of Xs may be the same or different, and may be bonded to each other via an arbitrary group. L is a Lewis base, a is a valence of M, b is 0, 1 or 2
And when L is plural, each L may be the same or different from each other. ] Can also be used.

[0033]

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[Wherein R ²² is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a carbon atom having 6 to 2 carbon atoms.
0 aromatic hydrocarbon group, C1-C20 alkoxy group, C6-C20 aryloxy group, C1-C20
A thioalkoxy group, a thioaryloxy group having 6 to 20 carbon atoms, an amino group, an amide group, a carboxyl group or an alkylsilyl group, which may be the same or different. Specifically, R ²² is a hexahydroazulenyl group, a 1-methylhexahydroazulenyl group, a 2-methylhexahydroazulenyl group, a 1,2-dimethylhexahydroazulenyl group, a 1,3- Examples include a dimethylhexahydroazulenyl group and a 1,2,3-trimethylhexahydroazulenyl group. M is a transition metal compound, and titanium, zirconium, hafnium, a lanthanoid metal,
Examples include niobium and tantalum. X represents a σ ligand, specifically, a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and a 1 to 20 carbon atoms. An alkoxy group having 6 carbon atoms
-20 aryloxy groups, C1-20 thioalkoxy groups, C6-20 thioaryloxy groups, amino groups, amide groups, carboxyl groups, alkylsilyl groups, and the like. They may be the same or different, and may be linked via an arbitrary group. Further, specific examples of X include a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a benzyl group, a phenyl group, a trimethylsilylmethyl group, a methoxy group, an ethoxy group, a phenoxy group, a thiomethoxy group, and a thiophenoxy group. Dimethylamino group, diisopropylamino group and the like. L represents a Lewis base, a is the valence of M, and b is 0, 1 or 2. (II) (a) Compound capable of forming an ionic complex by reacting with an oxygen-containing compound and / or (b) a transition metal compound The component (II) of the polymerization catalyst used in the present invention is shown below. , (A) a compound capable of forming an ionic complex by reacting with an oxygen-containing compound and / or (b) a transition metal compound. (A) Oxygen-containing compound as a component Compound represented by the following general formula (2)

[0035]

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And / or general formula (3)

[0037]

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An oxygen-containing compound represented by the formula: In the above general formulas (2) and (3), R ^{1 to} R ⁷ each represent an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups. Groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. R ^{1 to} R ⁵ may be the same or different, and R ⁶ and R ⁷ may be the same or different. Y ^{1 to} Y ⁵ each represent a Group 13 element of the periodic table, and specifically, B, Al,
Ga, In, and Tl are mentioned, and among them, B and Al are preferable. Y ^{1 to} Y ³ may be the same or different, and Y ⁴ and Y ⁵ may be the same or different. Also, a to d are numbers of 0 to 50, respectively, and (a + b) and (c + d) are each 1 or more. Each of a to d is preferably in the range of 1 to 20, and particularly preferably in the range of 1 to 5.

[0039] Suitable examples of oxygen containing compounds, in particular alkyl aluminoxane used as such a catalyst component, ¹
H-NMR aluminum methyl group (Al-CH ₃₎ observed in the spectral high magnetic field component in the methyl proton signal region based on the binding is of 50% or less. That is, when the ¹ H-NMR spectrum of the above contact product in a toluene solvent at room temperature was observed, it was found that “Al
The methyl proton signal based on “—CH ₃ ” is 1.0 to −0.5 ppm based on tetramethylsilane (TMS).
Seen in the range. TMS proton signal (0pp
Since m) is in the methyl protons observation area based on the "Al-CH _3", the methyl proton signal based on the "Al-CH _3", high measured based on the methyl proton signal 2.35ppm toluene in TMS standard When divided into a magnetic field component (i.e., 0.1 to -0.5 ppm) and another magnetic field component (i.e., 1.0 to -0.1 ppm), the high magnetic field component is 50% or less of the whole, preferably The one having 45 to 5% can be suitably used as a catalyst component. (B) Compound capable of forming an ionic complex by reacting with a transition metal compound Examples of the compound capable of forming an ionic complex by reacting with a transition metal compound include an anion and a cation having a plurality of groups bonded to a metal. Or a Lewis acid. There are various coordination complex compounds comprising an anion and a cation having a plurality of groups bonded to a metal. For example, a compound represented by the following general formula (16) or (17) is preferably used. it can.

([L ¹ -H] ^{g +} ) _h ([M ² X ¹ X ² ... X ⁿ ] ^(nm)- ) _i ... (16) ([L ² ] ^{g +} ) _h ([M ³ X ¹ X ² ... X ⁿ ] ^(nm)- ) _i ... (17) [In the formula (16) or (17), L ² represents M ⁴ , R ²³ R ²⁴ described later.
M ⁵ or R ²⁵ ₃ C, L ¹ is a Lewis base, M ² and M ³ are metals selected from groups 5 to 15 of the periodic table, respectively, and M ⁴ is a group 1 and 8 of the periodic table. A metal selected from Group 12; M ⁵ is a metal selected from Groups 8 to 10 of the periodic table; X ^{1 to} X ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, and a carbon atom of 1 to 20;
, An aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organic metalloid group, or a halogen atom. R ²³ and R ²⁴
Represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ²⁵ represents an alkyl group. m is an integer of 1 to 7 in valence of M ² and M ³ , n is an integer of 2 to 8, g is an integer of 1 to 7 in ionic valence of L ¹ -H, L ² , and h is 1 or more. Integer, i = h × g /
(Nm). Specific examples of M ² and M ³ include B, Al, Si, P, A
Specific examples of each atom such as s and Sb and M ⁴ are Ag, C
Each of atoms such as u, Na and Li, and specific examples of M ⁵ are F
e, Co, Ni and the like. X ^{1 to} X ⁿ
Specific examples of the above include, for example, a dimethylamino group, a diethylamino group or the like as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group or the like as an alkoxy group, a phenoxy group, a 2,6-dimethylphenoxy group as an aryloxy group, 1 carbon atom such as naphthyloxy group
And an alkyl group having 6 to 20 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an n-octyl group, and a 2-ethylhexyl group. Examples of the alkyl group include phenyl, p-tolyl, benzyl, pentafluorophenyl, 3,5-di (trifluoromethyl) phenyl, 4-tert-butylphenyl, 2,6-dimethylphenyl, Examples of halogen such as 5-dimethylphenyl group, 2,4-dimethylphenyl group, and 1,2-dimethylphenyl group include F, Cl, Br,
I. Examples of the organic metalloid group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. Specific examples of the substituted cyclopentadienyl group represented by each of R ²³ and R ²⁴ include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

In the present invention, a plurality of groups are bonded to a metal.
As the anion, specifically, B (C₆F_Five)_Four ^-, B
(C₆HF_Four)_Four ^-, B (C₆H_TwoF_Three)_Four ^-, B (C_{6 2})
_Four ^-, B (C₆H_FourF)_Four ^-, B (C₆CF_Three F_Four)_Four ^-,
B (C₆H_FiveF_Four ^-, PF₆ ^- , P (C₆F_Five)₆ ^-, Al
(C₆HF_Four)_Four ^-And others. Also, with metal cations
So, Cp_TwoFe⁺, (MeCp)_TwoFe⁺, (TB
uCp)_TwoFe⁺, (Me_TwoCp)_TwoFe⁺, (Me_Three
Cp)_TwoFe⁺, (Me_FourCp)_TwoFe⁺, (Me_FiveC
p)_TwoFe⁺, Ag⁺, Na⁺, Li⁺Etc.
And other cations include pyridinium, 2,2
4-dinitro-N, N-diethylanilinium, dife
Nil ammonium, p-nitroanilinium, 2,5-
Dichloroaniline, p-nitro-N, N-dimethylani
Linium, quinolinium, N, N-dimethylanilinium
Nitrogen-containing compounds such as N, N, N-diethylanilinium
, Triphenylcarbenium, tri (4-methylphen
Nil) carbenium, tri (4-methoxyphenyl) ca
Carbenium compounds such as rubenium, CH_ThreeP
H _Three ⁺, C_TwoH_FivePH_Three ⁺, C_ThreeH₇PH_Three ⁺, (CH
_Three)_TwoPH_Two ⁺, (C_TwoH _Five)_TwoPH_Two ⁺, (C
_ThreeH₇)_TwoPH_Two ⁺, (CH_Three)_ThreePH⁺, (C
_TwoH_Five) _ThreePH⁺, (C_ThreeH₇)_ThreePH⁺, (CF_Three)
_ThreePH⁺, (CH_Three)_FourP⁺, (C_TwoH_Five)_FourP⁺,
(C_ThreeH₇)_FourP⁺Alkylphosphonium ion such as
And C₆H_FivePH_Three ⁺, (C₆H_Five)_TwoPH_Two ⁺,
(C₆H_Five)_ThreePH⁺, (C ₆H_Five)_FourP⁺, (C_TwoH
_Five)_Two(C₆H_Five) PH⁺, (CH_Three) (C₆H_Five) P
H_Two ⁺, (CH_Three)_Two(C₆H_Five) PH⁺, (C
_TwoH_Five) _Two(C₆H_Five)_TwoP⁺Such as arylphosph
And the like.

Among the compounds of the general formulas (16) and (17),
Specifically, the following can be particularly preferably used. Examples of the compound represented by the general formula (16) include triethylammonium tetraphenylborate and triphenylammonium tetraphenylborate (n).
-Butyl) ammonium, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium hexafluoroarsenate, tetrakis (pentafluorophenyl) borate Pyridinium, pyrrolium tetra (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate N, N
-Dimethylanilinium, methyldiphenylammonium tetrakis (pentafluorophenyl) borate and the like. On the other hand, as the compound of the general formula (17), for example, ferrocenium tetraphenylborate, dimethylferrocenium tetrakis (pentafluorophenyl) borate,
Ferrocenium tetrakis (pentafluorophenyl) borate, decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate,
Cyanofersenium tetrakis (pentafluorophenyl) borate, silver tetraphenylborate, silver tetrakis (pentafluorophenyl) borate, trityl tetraphenylborate, trityl tetrakis (pentafluorophenyl) borate, silver hexafluoroarsenate, hexafluoroantimonate Silver and silver tetrafluoroborate are exemplified.

As the Lewis acid, for example, B (C ₆ F
₅ ) ₃ , B (C ₆ HF ₄ ) ₃ , B (H ₂ F ₃ ) ₃ , B (C ₆ H ₃
F ₂ ) ₃ , B (C ₆ H ₄ F) ₃ , B (C ₆ CF ₃ FPF ₅ , P
(C ₆ F ₅ ) ₅ , Al (C ₆ HF ₄ ) _{3 and the} like can also be used. In the polymerization catalyst of the present invention, the above (B)
As the component, only the oxygen-containing compound of the component (a) may be used alone or in combination of two or more, or only the compound which can react with the transition metal compound of the component (b) to form an ionic complex may be used. Alternatively, two or more kinds may be used in combination. Alternatively, the component (a) and the component (b) may be used in an appropriate combination. As the (III) alkylating agents Alkylating agents There are a variety of, for example, the general formula _{^{(18) R 26 m Al (}} OR 27) n X 3-mn ··· (18) wherein, R ²⁶ And R ²⁷ each represent an alkyl group having 1 to 8, preferably 1 to 4 carbon atoms, and X represents a hydrogen atom or a halogen atom. Also, m is 0 <m ≦ 3, preferably 2 or 3, and most preferably 3. n is 0 ≦ m ≦ 3.
n <3, preferably 0 or 1. Alkyl group-containing aluminum compounds or general formula _{^{(19) R 28 2 Mg ···}} (19) wherein represented by], R ²⁸ is as defined above. Alkyl group-containing magnesium compound represented by], yet the general formula _{^{(20) R 28 2 Zn ···}} (20)
Wherein R ²⁸ is the same as described above. And the like.

Among these alkyl group-containing compounds, alkyl group-containing aluminum compounds, particularly trialkylaluminum and dialkylaluminum compounds, are preferred. The method for preparing the catalyst The contacting method between the component (I) and the component (II) and the optional component (III) in the catalyst used for the polymerization is, for example, a contact mixture of the component (I) and the component (II). Is added to component (III) to form a catalyst, and the monomer to be polymerized, ie, in the present invention, the macromer (b)
With a styrene-based monomer (a) or a solution containing the styrene-based monomer (a).
A method in which component (I) is added to a contact mixture of components (II) and (III) to form a catalyst and contact with a monomer to be polymerized, and a contact mixture of components (I) and (III) is added to (II)
A method in which the components are added to form a catalyst and contact with the monomer to be polymerized; (I), (II),
The method of separately contacting the component (III), the contact mixture of the monomer component to be polymerized and the component (III),
And contacting the catalyst.

The contact between the above-mentioned components (I), (II) and optionally used component (III) can be carried out not only at the polymerization temperature but also in the range of -20 to 200 ° C. . A catalyst to be used for polymerization, which comprises the above components (I) and (II), or a combination of the components (I), (II) and (III), and in addition to this, other catalyst components are added. Is also possible. The mixing ratio of each catalyst component varies depending on various conditions and cannot be unambiguously determined. Usually, when the component (II) is an oxygen-containing compound, the component (I)
The molar ratio of the component (II) to the component (II) is preferably from 1: 1 to 1: 1.
0000, more preferably in the range of 1: 1 to 1: 1,000, a compound in which the component (II) can react with the transition metal compound to form an ionic complex, the component (I) and ( The molar ratio to the component (II) is preferably selected in the range of 0.1: 1 to 1: 0.1. When the component (III) is used, (I)
The molar ratio of component to component (III) is preferably from 1: 0.1 to
1: Selected in the range of 1,000.

Before introducing each component of the catalyst, an organic aluminum such as triisobutylaluminum may be added to trap impurities. Polymerization Method The polymerization method may be bulk polymerization, which is carried out in an aliphatic hydrocarbon such as pentane, hexane or heptane, an alicyclic hydrocarbon such as cyclohexane or an aromatic hydrocarbon solvent such as benzene, toluene, xylene or ethylbenzene. You may. The polymerization temperature is not particularly limited, but is generally 0 to 200 ° C, preferably 20 to 100 ° C.

The obtained graft copolymer (A) contains a polymer segment derived from a styrene-based monomer and a polymer segment derived from a styrene-terminal-modified olefin-based macromer represented by the general formula (1). Regarding the ratio, the macromer (b) to be subjected to polymerization
And the amount of the styrene-based monomer (a) can be appropriately controlled. (3) Thermoplastic resin (B) The thermoplastic resin (B), which is a component of the styrenic resin composition according to the present invention, is not particularly limited, and may be other than the above graft copolymer (A). Anything is fine.
Although only one type of thermoplastic resin may be used, two or more types may be used in combination depending on the purpose. Specifically, the following are mentioned. Styrene polymer having syndiotactic structure (SPS) Styrene polymer having syndiotactic structure (SPS)
The tacticity in PS) is quantified by nuclear magnetic resonance ( ¹³ C-NMR) using isotope carbon.
A styrene polymer having a syndiotactic structure is usually 75% or more, preferably 85% or more in racemic dyad, or 30% or more in racemic pentad,
Preferably, it refers to a styrene polymer having a syndiotacticity of 50% or more. Examples of the monomer to be subjected to the polymerization include the above-mentioned styrene-based monomers, and include a homopolymer obtained by homopolymerization of the monomer or a copolymer obtained by copolymerizing two or more monomers, or a hydrogenated polymer thereof or a hydrogenated polymer thereof. A mixture or a copolymer containing these as a main component is referred to. Particularly preferred styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), poly (p-chlorostyrene), and poly (m-chlorostyrene). Styrene), poly (p-fluorostyrene), hydrogenated polystyrene and copolymers containing these structural units.

The styrenic polymer can be used alone or in combination of two or more. Although the molecular weight of the styrene polymer is not particularly limited, the weight average molecular weight is preferably 10,000 or more, more preferably 50,000 or more. Furthermore, the molecular weight distribution is not limited in its width, and various types can be applied.

Such a styrenic polymer having a syndiotactic structure can be produced by a known method (for example, Japanese Patent Application Laid-Open No. 62-187708,
JP-A-1-46912, JP-A-1-178505
No.). In the thermoplastic resin (B), which is one component of the styrene resin composition according to the present invention, the mixing ratio with the styrene polymer having the above syndiotactic structure, the following thermoplastic resin, and the following rubber-like elastic material May be appropriately selected depending on the purpose. Thermoplastic resins other than SPS can be arbitrarily selected from known resins, and specifically, for example, linear high-density polyethylene, linear low-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic Polyolefin resins including tic polypropylene, block polypropylene, random polypropylene, polybutene, 1,2-polybutadiene, cyclic polyolefin, poly-4-methylpentene, polystyrene, HIPS, ABS, AS
And polystyrene resins such as polycarbonate, polyethylene terephthalate and polybutylene terephthalate, polyamide resins such as polyamide 6, polyamide 6, and 6, polyphenylene ether, and polyphenylene sulfide. Others In addition, a rubber-like elastic body can also be cited as one type of thermoplastic resin.

For example, natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulfide rubber, thiochol rubber, acrylic rubber, urethane rubber, silicone rubber, shrimp chlorohydrin rubber, styrene-butadiene block copolymer (SBR), hydrogenated Styrene-butadiene block copolymer (SEB),
Styrene-butadiene-styrene block copolymer (S
BS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer Copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEP)
S), ethylene propylene rubber (EPR), ethylene propylene diene rubber (EPDM), or butadiene-acrylonitrile-styrene-core-shell rubber (AB
S), methyl methacrylate-butadiene-styrene-
Core shell rubber (MBS), methyl methacrylate-butyl acrylate-styrene-core shell rubber (MA
S), octyl acrylate-butadiene-styrene-
Core shell rubber (MABS), alkyl acrylate-
Core-shell type particle-like elastic materials such as butadiene-acrylonitrile-styrene core-shell rubber (ABS), butadiene-styrene-core-shell rubber (SBR), and siloxane-containing core-shell rubber such as methyl methacrylate-butyl acrylate siloxane; Rubber and the like.

Among these, in particular, SBR, SEB, S
BS, SEBS, SIR, SEP, SIS, SEPS,
Core-shell rubber, EPR, EPDM, or rubber modified from these are preferably used. In addition, these rubber-like elastic bodies can be used alone or in combination of two or more. (4) The styrenic resin composition according to the present invention is composed of the graft copolymer (A) and a thermoplastic resin (B) other than (A). (A) 99.9-0.1% by weight, preferably 9
0 to 2% by weight, further 80 to 4% by weight, and 0.1 to 99.9% by weight, preferably 10 to 9% by weight of the thermoplastic resin (B).
-98% by weight, more preferably 20-96% by weight. (5) The styrenic resin composition according to the present invention contains various additive components, for example, as long as the object of the present invention is not impaired.
Additives such as inorganic fillers, antioxidants, nucleating agents, plasticizers, release agents, flame retardants, flame retardant aids, and antistatic agents can be added.

Various inorganic fillers such as fibrous, granular, and powdery materials are used. For example, examples of the fibrous inorganic filler include glass fiber, carbon fiber, and whisker. As the shape of the fibrous inorganic filler,
The whisker itself is available in addition to the cloth, mat, bundle cut, and short fiber shapes. Examples of the granular or powdery inorganic filler include talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, barium sulfate, oxysulfate, tin oxide, Examples include alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, and glass beads. Among such inorganic fillers, glass fillers such as glass powder, glass flake, glass beads, glass filament, glass fiber, glass lobing, and glass mat are particularly preferable.

The inorganic filler preferably has been subjected to a surface treatment with a coupling agent such as a silane coupling agent or a titanium coupling agent in order to improve the adhesion to the resin. Used. Such an inorganic filler may be used alone, but may be used in combination of two or more if necessary.

As a nucleating agent, aluminum di (pt-
Butyl benzoate), metal salts of phosphoric acid such as sodium methylenebis (2,4-di-t-butylphenol) acid phosphate, talc, phthalocyanine derivatives, and the like. Can be selected and used. As the plasticizer, any known plasticizer such as polyethylene glycol, polyamide oligomer, ethylene bisstearamide, phthalic acid ester, polystyrene oligomer, polyethylene wax, mineral oil, and silicone oil can be used.

As the release agent, polyethylene wax,
Any known materials such as silicone oil, long-chain carboxylic acid, and long-chain carboxylate can be used. As the antioxidant, any of known antioxidants such as phosphorus-based, phenol-based, and sulfur-based can be used. The flame retardant may be any of known brominated aromatic compounds such as brominated polystyrene, brominated syndiotactic polystyrene, brominated polymers such as brominated polyphenylene ether, brominated diphenylalkane, and brominated diphenyl ether. Can be selected and used. In addition, as the flame retardant auxiliary, antimony compounds such as antimony trioxide, and others can be arbitrarily selected and used, respectively, one type alone may be used alone, or two or more types may be used in combination. Can also be used. (6) The method for producing the styrenic resin composition according to the present invention is not particularly limited, and conditions such as the order of addition and the mixing method can be arbitrarily set. The composition also includes those obtained by mixing and then kneading the components. The method of melt-kneading is not particularly limited, and a conventionally known method can be used.

[0056]

[Production Example 1]

Preparation of terminal styrene-modified ethylene-propylene copolymer grafted syndiotactic polystyrene (A) Synthesis of terminal styrene-modified olefin-based macromer (b) 500 ml of toluene was placed in a 1-liter separable flask equipped with a stirrer and a thermometer. -6
After cooling to 0 ° C., a solution of 25 mmol of diethylaluminum chloride in n-heptane and 1.5 mmol of a solution of 1.5 mmol of tris (2-methyl-1,3-butanedionato) vanadium in toluene were added at that temperature. Next, 700 mmH
g, and a mixed gas of ethylene and propylene (40/60 molar ratio) was continuously supplied for 2 hours to copolymerize ethylene and propylene. Next, after adding a toluene solution of 100 mmol of divinylbenzene cooled to -60 ° C, the temperature of the reaction system was raised to -40 ° C over 1 hour, and the mixture was further stirred for 0.5 hour. The obtained reaction product was added to 5 liters of a methanol mixture containing a trace amount of hydrochloric acid to precipitate a polymer, and then filtration and washing with 3 liters of methanol for 0.5 hours were repeated twice. The obtained polymer was dried under reduced pressure at 30 ° C. for 12 hours, and 8.5 g was obtained.
Was obtained. Analysis of this polymer gave the following results. According to GPC measurement, the weight average molecular weight was 32.
000, and Mw / Mn = 1.21. Also, H
By NMR, C ₂ / C was determined from the ratio of secondary H to tertiary H.
₃ = 49/51 (mol / mol), and based on the molecular weight of the ethylene-propylene copolymer and the proton intensity of the methylene portion of the terminal vinyl group of divinylbenzene, the styrene structural unit at the end of the ethylene-propylene copolymer is about 2 Turned out to be individual. Furthermore, from FT-IR, 1630 cm ^-1
In addition, absorption of a terminal vinyl group was confirmed.

Synthesis of Terminal Styrene-Modified Ethylene-Propylene Copolymer Graft Syndiotactic Polystyrene (A) The terminal-styrene-modified ethylene-propylene copolymer synthesized above was placed in a 100 ml three-necked flask equipped with a stirrer and a thermometer. After weighing 2.0 g of the combined product, the mixture was sufficiently degassed and replaced with nitrogen. Subsequently, 50 ml of sufficiently dehydrated toluene was added, and at 50 ° C.
After dissolving the terminal styrene-modified ethylene-propylene copolymer synthesized in (1), 10 ml of a sufficiently dehydrated styrene monomer was added, the temperature was raised to 70 ° C., and 0.15 mmol of triisobutylaluminum and 0.15 mmol of triisobutylaluminum were added. 0.012 mmol of triethylaluminum was added and 5
Stirred for minutes. Subsequently, methylaluminoxane / triisobutylaluminum / pentamethylcyclopentadienyltitanium trimethoxide = 75/25/1 (molar ratio,
2.5 mL of a toluene solution of Ti = 1 mmol / L) was added, and polymerization was performed for 1 hour.

The reaction product was poured into 1 liter of a hydrochloric acid / methanol solution to precipitate a polymer. After filtration, 1
Two 0.5 liter washes were performed with 1 liter of methanol. The obtained polymer was dried under reduced pressure at 30 ° C. for 12 hours to obtain 7.4.
g of polymer were obtained. The dried polymer was then subjected to Soxhlet extraction with cyclohexane for 12 hours to remove unreacted ethylene-propylene copolymer, and then dried under reduced pressure at 80 ° C for 12 hours to obtain 7.2 g of a polymer.

The polymer was analyzed and the following results were obtained. According to GPC measurement, the weight average molecular weight was 352,000.
And Mw / Mn = 2.85. Also, H-NM
By R, syndiotactic polystyrene part / ethylene-propylene copolymer part = 75/25 (wt / wt). Further, the absorption of the terminal vinyl group at 1630 cm ^-1 had disappeared by FT-IR. [Production Example 2] Syndiotactic polystyrene (SP
Production of S) 200 ml of fully dehydrated toluene and styrene monomer were charged into a sufficiently dry 1 liter separable flask. Subsequently, 9.9 × 10 ^-5 mol of triisobutylaluminum (TI
BA) and 9.9 × 10 ⁻⁵ mol of triethylaluminum (TEA) were added, and the temperature was raised to 70 ° C.

Next, a previously prepared catalyst mixture (methylaluminoxane / triisobutylaluminum / pentamethylcyclopentadienyltitanium trimethoxide = 75)
1.7 ml of a toluene solution of / 25/1 (molar ratio, Ti = 3 mmol / l) was added, and polymerization was carried out for 2 hours. Add the polymerization contents to 5 liters of methanol,
The polymer component was precipitated. After washing once more, the mixture was filtered, dried under reduced pressure at 200 ° C. for 3 hours, and dried at 27.1.
g of polymer were obtained.

The polymer was analyzed and the following results were obtained. According to GPC measurement, the weight average molecular weight was 250,000.
And Mw / Mn = 3.0. [Example 1] Ethylene-propylene rubber (trade name "EP-07P" (ethylene content: 80 mol%) manufactured by Nippon Synthetic Rubber Co., Ltd.) was added to 100 parts by weight of the SPS obtained in Production Example 2 above.
15 parts by weight, and 5 parts by weight of a terminal styrene-modified ethylene-propylene copolymer-grafted syndiotactic polystyrene (A) obtained in Production Example 1 (namely, 4.2% by weight of component (A), This is a styrene resin composition comprising 95.8% by weight of a thermoplastic resin component (B) comprising SPS and ethylene-propylene rubber. In the thermoplastic resin component (B), 87% by weight of SPS and ethylene-propylene rubber 13 %) Is kneaded using a twin-screw extruder (32φ, manufactured by Nippon Steel Works) at 290 ° C. with a charge rate of 200 rpm and 20 kg / hour to obtain about 300 g of pellets. Was.

The pellets were converted into a small injection molding machine (injection molding machine manufactured by Niigata Iron and Steel Works: MIN-7, cylinder temperature 290).
C. and a mold temperature of 150.degree. C.) to produce a dumbbell (ASTM No. 4) for a tensile test. The tensile elongation at break was measured according to JIS K7113 and found to be 15%. [Example 2] The procedure of Example 1 was repeated, except that the amount of the component (A) was changed to 20 parts by weight. That is, the component (A) was 14.8% by weight, and the thermoplastic resin component (B) comprising SPS and ethylene-propylene rubber was 85.2%.
It is a styrene-based resin composition consisting of 87% by weight of SPS and 13% by weight of ethylene-propylene rubber in the thermoplastic resin component (B). The measured tensile elongation at break was 20%. Example 3 In Example 1, polypropylene (made by Idemitsu Petrochemical Co., Ltd.) was used instead of ethylene-propylene rubber.
The procedure was performed in the same manner as in Example 1 except that the trade name was changed to "Idemitsu Polypropylene J723". That is, (A) component is 4.2
% Of the thermoplastic resin component (B) composed of SPS and polypropylene is 95.8% by weight. In the thermoplastic resin component (B), SPS is used.
87% by weight and 13% by weight of polypropylene. The measured tensile elongation at break was 10%. Example 4 The procedure of Example 1 was repeated, except that the high-density polyethylene (trade name “Idemitsu Polyethylene 110J” manufactured by Idemitsu Petrochemical Co., Ltd.) was used instead of the ethylene-propylene rubber. That is, it is a styrenic resin composition in which the component (A) is 4.2% by weight and the thermoplastic resin component (B) composed of SPS and polyethylene is 95.8% by weight. In the thermoplastic resin component (B), , SP
S 87% by weight and polyethylene 13% by weight. The measured tensile elongation at break was 12%. Example 5 In Example 1, a linear low-density polyethylene (LLDP) was used instead of the ethylene-propylene rubber.
E) (made by Idemitsu Petrochemical Co., Ltd.
2024G "), except that the procedure was as in Example 1. That is, (A) component is 4.2% by weight, SPS and LLDP
A thermoplastic resin component (B) composed of E is a styrene-based resin composition composed of 95.8% by weight. In the thermoplastic resin component (B), 87% by weight of SPS and LLDPE13 are used.
% By weight. When the tensile elongation at break was measured, 13%
Met. Example 6 In Example 1, 40 parts by weight of a styrene-modified ethylene-propylene copolymer-grafted syndiotactic polystyrene (A) obtained in Production Example 1 and 60 parts by weight of SPS (B) obtained in Production Example 2 The procedure was performed in the same manner as in Example 1 except that the composition was changed to parts. That is, when the component (A) is 40
The styrene resin composition is composed of 60% by weight and 60% by weight of the component (B). When the tensile elongation at break was measured, 15
%Met. Example 7 In Example 1, 60 parts by weight of the terminal styrene-modified ethylene-propylene copolymer grafted syndiotactic polystyrene (A) obtained in Production Example 1 and 40 parts by weight of SPS (B) obtained in Production Example 2 The procedure was performed in the same manner as in Example 1 except that the composition was changed to parts. That is, the component (A) is 60
It is a styrene-based resin composition composed of 40% by weight of the component (B). When the tensile elongation at break was measured, 22
%Met. [Example 8] In Example 1, 80 parts by weight of the terminal styrene-modified ethylene-propylene copolymer grafted syndiotactic polystyrene (A) obtained in Production Example 1 and 20 parts by weight of SPS (B) obtained in Production Example 2 The procedure was performed in the same manner as in Example 1 except that the composition was changed to parts. That is, the component (A) is 80
It is a styrenic resin composition comprising 20% by weight of the component (B) and 20% by weight. When the tensile elongation at break was measured, 27
%Met. [Comparative Example 1] In Example 1, the S obtained in Production Example 2 was used.
Only PS was used. When the tensile elongation at break was measured,
%Met. [Comparative Example 2] The SP obtained in the above Production Example 2 in Example 1 without using the terminal styrene-modified ethylene-propylene copolymer grafted syndiotactic polystyrene (A).
S100 parts by weight of ethylene-propylene rubber (trade name “EP-07P” manufactured by Nippon Synthetic Rubber Co., Ltd. (ethylene content
80 mol%)) A mixture consisting of only 15 parts by weight was used. The measured tensile elongation at break was 5%. [Comparative Example 3] The same procedure as in Example 3 was carried out except that the terminal styrene-modified ethylene-propylene copolymer grafted syndiotactic polystyrene (A) was not used.
For S100 parts by weight, a mixture consisting of only 15 parts by weight of polypropylene (trade name "Idemitsu Polypropylene J723" manufactured by Idemitsu Petrochemical Co., Ltd.) was used. The measured tensile elongation at break was 3%.

[0063]

The styrenic resin composition of the present invention has excellent heat resistance, chemical resistance and the like, has good toughness and compatibilizing ability, and is useful as a material for a composite material or a heat-resistant elastomer.

Claims (4)

[Claims] 1. A copolymer of a styrene monomer (a) and a terminal styrene derivative-modified olefin macromer (b) represented by the following general formula (1), wherein a stereoregularity of a chain derived from the styrene monomer is obtained. Is a graft copolymer (A) 9 having a high syndiotactic structure
A styrenic resin composition comprising 9.9 to 0.1% by weight and a thermoplastic resin (B) other than (A) 0.1 to 99.9% by weight. Embedded image [Wherein, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and each R may be the same or different. X represents any of the following: A substituent containing at least one selected from a hydrogen atom, a halogen atom, and a carbon atom, a tin atom and a silicon atom; n represents an integer of 1 to 4, and when n is 2 or more, each X may be the same or different. Further, m is 0 or a natural number,
Z represents a chain portion derived from the olefin-based monomer. ] 2. The graft copolymer (A) according to claim 1, wherein the styrene-based monomer-modified olefin-based macromer (99.9 to 0.1% by weight) is derived from a styrene-based monomer (a). The styrenic resin composition according to claim 1, comprising 0.1 to 99.9% by weight of a polymer segment derived from b). 3. The graft copolymer (A) according to claim 1, wherein the terminal styrene derivative-modified olefin macromer (b) is dissolved in a styrene monomer (a) or a solvent containing the styrene monomer (a). After that, (I) a transition metal compound, (II) (a) a general formula (2) (Wherein, R ^{1 to} R ⁵ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, Y ^{1 to} Y ³ each represent a Group 13 element of the periodic table,
They may be the same or different, a and b each represent a number of 0 to 50, and a + b is 1 or more. ) And / or general formula (3) (Wherein, R ⁶ and R ⁷ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, Y ⁴ and Y ⁵ each represent a Group 13 element of the periodic table, They may be the same or different, c
And d each represent a number from 0 to 50, and c + d is 1 or more. And / or (b) a catalyst comprising a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (I).
The styrenic resin composition according to claim 1 or 2, which is produced by copolymerizing (a) and (b). 4. The graft copolymer (A) according to claim 1, wherein the terminal styrene derivative-modified olefin macromer (b) is dissolved in a styrene monomer (a) or a solvent containing the styrene monomer (a). After that, (I) a transition metal compound, (II) (A) a general formula (2) (Wherein, R ^{1 to} R ⁵ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, Y ^{1 to} Y ³ each represent a Group 13 element of the periodic table,
They may be the same or different, a and b each represent a number of 0 to 50, and a + b is 1 or more. ) And / or general formula (3) (Wherein, R ⁶ and R ⁷ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, Y ⁴ and Y ⁵ each represent a Group 13 element of the periodic table, They may be the same or different, c
And d each represent a number from 0 to 50, and c + d is 1 or more. And / or (b) a compound capable of reacting with the transition metal compound of the component (I) to form an ionic complex, and (III) a catalyst comprising an alkylating agent. 3. The styrene resin composition according to claim 1, wherein the styrene resin composition is produced by copolymerizing (a) and (b).