JP3101028B2 - Graft copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graft copolymer and a method for producing the same. The present invention relates to a method for efficiently producing a styrene-based graft copolymer having excellent impact resistance and heat resistance by polymerization, and having good compatibility with other resins, and a novel styrene-based graft copolymer.

[0002]

2. Description of the Related Art Styrene-based polymers conventionally produced by a radical polymerization method or the like are molded into various shapes by various molding methods, and are used in household electric appliances, office equipment, household goods, packaging containers, toys, and the like. Although widely used as furniture, synthetic paper, and other industrial materials, it has a drawback that its three-dimensional structure has an atactic structure and is inferior in heat resistance and chemical resistance.

The present inventors have succeeded in developing a styrene-based polymer having a high syndiotactic structure as a solution to the above-mentioned drawbacks of the styrene-based polymer having an atactic structure. Furthermore, styrene-based copolymers obtained by copolymerizing the styrene-based monomer and other components have been developed (JP-A-62-104818, JP-A-62-187708, and JP-A-63-24109).

[0004] 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, and have little adhesion to other resins, metals, and the like. In addition, there is a problem that the impact resistance is insufficient. By the way, olefin polymerization by a cationic transition metal complex has been reported for a long time. For example, (1) Natta et al. Reported that ethylene is polymerized using titanocene dichloride / triethylaluminum as a catalyst (J. Pol)
ymer Sci., 26 , 120 (1964)). Breslow et al. Also reported the polymerization of ethylene by titanocene dichloride / dimethylaluminum chloride catalyst (J. Am. Chem.
Soc., 79 , 5072 (1957)). In addition, Dyachkovskii et al.
The polymerization activity of ethylene with titanocene dichloride / dimethylaluminum chloride catalyst suggests that it is a titanocene monomethyl cation (J. Polymer S
ci., 16 , 2333 (1967)). However, the ethylene activity in these methods is extremely low.

(2) Jordan et al. Synthesize and isolate [biscyclopentadienyl zirconium methyl (tetrahydrofuran)] [tetraphenylborate] by reacting zirconocene dimethyl with silver tetraphenylborate, and use the resulting ethylene. Has been reported (J. Am.
Chem. Soc., 108, 7410 (1986)). They also synthesized and isolated [biscyclopentadienyl zirconium benzyl (tetrahydrofuran)] [tetraphenylborate] by reacting zirconocene dibenzyl with ferrocenium tetraphenylborate (J. Am. Chem. Soc., 109, 4
111 (1987)). However, it was confirmed that ethylene was slightly polymerized in these catalysts, but the polymerization activity was extremely low.

(3) Turner et al. Use a metallocene compound-catalyzed boron complex containing a specific amine such as triethylammonium tetraphenylborate, triethylammonium tetratolylborate, triethylammonium tetra (pentafluorophenyl) borate as a catalyst. A polymerization method has been proposed (Japanese Unexamined Patent Publication No. 1-502036). However, application of catalyst systems such as (1) to (3)
-Limited to homopolymerization or copolymerization of olefins,
At present, it has not been developed into styrene monomers.

[0007]

SUMMARY OF THE INVENTION Accordingly, the present inventors
Eliminate the shortcomings of the above syndiotactic polystyrene,
Intensive research was conducted to develop a styrene-based polymer having excellent compatibility with other resins and adhesion to metals, and excellent impact resistance.

In the process, it has been found that a specific styrene-based copolymer obtained by graft-polymerizing an ethylenically unsaturated monomer has characteristics suitable for the above purpose. Therefore, the present inventors have further studied and developed a method for efficiently proceeding the graft polymerization and producing a styrene-based graft copolymer having excellent properties at an arbitrary graft ratio and high productivity. Succeeded.

[0009]

That is, the present invention provides a styrene monomer and a hydrocarbon group-containing styrene monomer having an unsaturated bond, comprising (A) a transition metal compound and (B) an organoaluminum compound and a condensing agent. Production of a styrene-based graft copolymer, characterized in that the copolymerization is carried out in the presence of a catalyst whose main component is the contact product of the above, and then the resulting styrene-based copolymer is graft-polymerized with an ethylenically unsaturated monomer. It provides a method. Further, the present invention provides a compound which reacts with the above-mentioned component (A) and (C) the above-mentioned transition metal compound to form an ionic complex, instead of the catalyst containing the above-mentioned components (A) and (B) as main components. Another object of the present invention is to provide a method for producing a styrene-based graft copolymer using a catalyst as a main component. Further, the present invention also provides a styrene-based graft copolymer obtained by graft-polymerizing an ethylenically unsaturated monomer onto a copolymer comprising a styrene-based monomer and a styrene-based monomer having a hydrocarbon group having an unsaturated bond. Things. Furthermore, the present invention comprises a novel copolymer which is a precursor of a graft copolymer, that is, a styrene monomer and an unsaturated hydrocarbon group-containing styrene monomer containing a styrene skeleton and an α-olefin skeleton in the same molecule. Another object of the present invention is to provide a styrene copolymer having a structure in which a double bond of a styrene skeleton of the unsaturated hydrocarbon group-containing styrene monomer remains.

The method of the present invention comprises the steps of producing a styrene-based copolymer by copolymerizing a styrene-based monomer and a styrene-based monomer having a hydrocarbon group having an unsaturated bond (step 1), and the styrene-based copolymer. And a step (step 2) of graft-polymerizing an ethylenically unsaturated monomer.

The styrenic monomer used in the above step 1 includes various types, and is usually represented by the following general formula [1]

[0012]

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[In the formula, R ¹ is any ^one of a hydrogen atom, a halogen atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom.
A substituent containing at least one species; m represents an integer of 1 to 3;
However, when m is plural, each R ¹ may be the same or different. A styrene monomer I represented by the following formula:
It is. The styrene monomer I is specifically styrene; p-methylstyrene; o-methylstyrene;
Methylstyrene; 2,4-dimethylstyrene; 2,5-
Dimethylstyrene; 3,4-dimethylstyrene; 3,5
P-chlorostyrene; m-chlorostyrene; o-chlorostyrene; p-bromostyrene; m-bromostyrene; o-bromostyrene; p-fluorostyrene; o-fluorostyrene; halogenated styrenes such as o-methyl-p-fluorostyrene, 4-vinylbiphenyl; 3-vinylbiphenyl; vinylbiphenyls such as 2-vinylbiphenyl, 1- (4-vinyl Phenyl) -naphthalene; 2
-(4-vinylphenyl) -naphthalene; 1- (3-vinylphenyl) -naphthalene; 2- (3-vinylphenyl) -naphthalene; 1- (2-vinylphenyl) -naphthalene; 2- (2-vinylphenyl) 1) vinylphenylnaphthalenes such as naphthalene, 1- (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-
2- (4-vinylphenyl) -phenanthrene; 3- (4-vinylphenyl) -phenanthrene; 4- (4-vinylphenyl)-
Phenanthrene; 9- (4-vinylphenyl) -phenanthrene; 1- (3-vinylphenyl) -phenanthrene; 2- (3-vinylphenyl) -phenanthrene;
-(3-vinylphenyl) -phenanthrene; 4- (3
-Vinylphenyl) -phenanthrene; 9- (3-vinylphenyl) -phenanthrene; 1- (2-vinylphenyl) -phenanthrene; 2- (2-vinylphenyl)
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; vinylphenylpyrenes such as 2- (2-vinylphenyl) -pyrene; 4-vinyl-p-terphenyl; 4-vinyl- m-terphenyl; 4-vinyl-o-terphenyl; 3-vinyl-p-terphenyl; 3-vinyl-m-terphenyl; 3-vinyl-o-
Terphenyl; 2-vinyl-p-terphenyl; 2-vinyl-m-terphenyl; vinyl terphenyls such as 2-vinyl-o-terphenyl; 4- (4-vinylphenyl) -p-terphenyl; Vinylphenyl terphenyls, 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;
Vinyl-2'-fluorobiphenyl; 4-vinyl-2-
4-vinyl-3-fluorobiphenyl; 4-vinyl-4'-chlorobiphenyl;4-vinyl-3'-chlorobiphenyl;4-vinyl-2'-chlorobiphenyl;4-vinyl-2-chlorobiphenyl; 4
-Vinyl-3-chlorobiphenyl; 4-vinyl-4'-
4-vinyl-3'-bromobiphenyl;4-vinyl-2'-bromobiphenyl;4-vinyl-2-bromobiphenyl; halogenated vinyl biphenyls such as 4-vinyl-3-bromobiphenyl; Trialkylsilylvinylbiphenyls such as vinyl-4'-trimethylsilylbiphenyl;4-vinyl-4'-trimethylstannylbiphenyl; trialkylstannylvinylbiphenyls such as 4-vinyl-4'-tributylstannylbiphenyl;-Vinyl-4'-trimethylsilylmethylbiphenyl and other trialkylsilylmethylvinylbiphenyls; 4-vinyl-4'-trimethylstannylmethylbiphenyl;4-vinyl-4'-
Trialkylstannylmethylvinylbiphenyls such as tributylstannylmethylbiphenyl, p-chloroethylstyrene; m-chloroethylstyrene; halogen-substituted alkylstyrenes such as o-chloroethylstyrene, p-trimethylsilylstyrene; m-trimethylsilylstyrene; o-trimethylsilylstyrene; p-triethylsilylstyrene; m-triethylsilylstyrene; o-triethylsilylstyrene; alkylsilylstyrenes such as p-dimethyltert-butylsilylstyrene; p-dimethylphenylsilylstyrene;
Methyldiphenylsilylstyrene; phenyl group-containing silylstyrenes such as p-triphenylsilylstyrene,
p-dimethylchlorosilylstyrene; p-methyldichlorosilylstyrene; p-trichlorosilylstyrene; p
-Dimethylbromosilylstyrene; halogen-containing silylstyrenes such as p-dimethyliodosilylstyrene,
Silyl group-containing silyl styrenes such as p- (p-trimethylsilyl) dimethylsilyl styrene, and a mixture of two or more thereof.

There are various styrene-based monomers having an unsaturated bond and having a hydrocarbon group.
Usually, the following general formula [2]

[0015]

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Wherein R ² represents a hydrocarbon group having an unsaturated bond, and n represents an integer of 1 or 2. R ¹ and m
Is the same as above. ] Is a styrenic monomer II represented by the formula: R ² in the above formula is preferably a hydrocarbon group having an unsaturated bond, particularly a hydrocarbon group having an unsaturated bond having 2 to 10 carbon atoms, for example, a vinyl group; an allyl group; a methallyl group; a homoallyl group; A decenyl group or the like; To give a specific example of this styrene monomer II,
p-divinylbenzene; m-divinylbenzene; trivinylbenzene, p-allylstyrene which is a monomer having a styrene skeleton and an α-olefin skeleton in the same molecule; m-allylstyrene; methallylstyrene; homoallylstyrene; Butenyl styrene; pentenyl styrene;
Examples include decenylstyrene and the like, or a mixture of two or more of these. In this case, when a monomer containing an α-olefin skeleton is used, the crosslinking reaction is suppressed even if the copolymerization ratio is relatively increased.

In step 1 of the method of the present invention, a styrene-based monomer having an unsaturated bond and a styrene-based monomer having an unsaturated bond, in particular, the styrene-based monomer I and the styrene-based monomer II are copolymerized. The catalyst is
The catalyst is mainly composed of a contact product of (A) a transition metal compound and (B) an organoaluminum compound with a condensing agent.
Here, there are various types of the transition metal compound (A), and the following general formulas [4], [5], [6] and [7] are preferable.

[0018]

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[Wherein, R^Three~ R¹⁴Is the hydrogen source
Child; a halogen atom; an alkyl group having 1 to 20 carbon atoms;
An alkoxy group having 1 to 20 carbon atoms; an aryl having 6 to 20 carbon atoms
Group; an arylalkyl group having 7 to 20 carbon atoms, 6 to 6 carbon atoms
20 aryloxy groups; acyloxy having 1 to 20 carbon atoms
A group; acetylacetonyl group; cyclopentadienyl
Group; substituted cyclopentadienyl group or indenyl group
Is shown. A, b, and c are respectively 0 ≦ a + b + c.
Represents an integer of 0 or more satisfying ≦ 4, and d and e are each 0
≦ d + e ≦ 3, an integer greater than or equal to 0, and f is 0 ≦ f
Represents an integer of 0 or more satisfying ≦ 2, and g and h are each 0 ≦ g
+ H ≤ 3 represents an integer of 0 or more. Further, M¹, M
^TwoIs titanium; zirconium; hafnium or vanadium
Um, M ^Three, M^FourRepresents vanadium. ]
At least one compound selected from transition metal compounds
It is a compound. Among these transition metal compounds,
M in general formula [4]¹Is titanium or zirconium
It is preferable to use one.

Here, among those represented by R ^{3 to} R ¹⁴ in the above formula, specific examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom. Further, the substituted cyclopentadienyl group has, for example, 1 to 1 carbon atoms.
A cyclopentadienyl group substituted by one or more alkyl groups, specifically a methylcyclopentadienyl group;
1,2-dimethylcyclopentadienyl group; pentamethylcyclopentadienyl group and the like.

R ^{3 to} R ¹⁴ in the above formula are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group,
Isobutyl, amyl, isoamyl, octyl,
2-ethylhexyl group), an alkoxy group having 1 to 20 carbon atoms (specifically, a methoxy group; an ethoxy group; a propoxy group; a butoxy group; a hexyloxy group; an octyloxy group; a 2-ethylhexyloxy group); 6-20
(Specifically, a phenyl group, a naphthyl group, etc.), an arylalkyl group having 7 to 20 carbon atoms (specifically, a benzyl group, a phenethyl group, a 9-anthrylmethyl group, etc.), a carbon number of 1 To 20 acyloxy groups (specifically, an acetyloxy group; a stearoyloxy group and the like). R ^{3 to} R ¹⁴ may be the same or different as long as the above conditions are satisfied.

Among the transition metal compounds represented by the general formulas [4] to [7], specific examples of the titanium compound include tetramethoxytitanium; tetraethoxytitanium; tetra-n-butoxytitanium; Propoxy titanium; cyclopentadienyl trimethyl titanium; titanium tetrachloride; titanium trichloride; dimethoxy titanium dichloride; methoxy titanium trichloride; trimethoxy titanium chloride; cyclopentadienyl triethyl titanium; cyclopentadienyl tripropyl titanium; cyclopentadi Methylcyclopentadienyltrimethyltitanium; Methylcyclopentadienyltribenzyltitanium; 1,2-dimethylcyclopentadienyltrimethyltitanium; Tetramethylcyclopentadienyltrimethyltitanium Pentamethylcyclopentadienyltrimethyltitanium; pentamethylcyclopentadienyltriethyltitanium; pentamethylcyclopentadienyltripropyltitanium; pentamethylcyclopentadienyltributyltitanium; pentamethylcyclopentadienyltitaniumtriphenyl; pentamethyl Cyclopentadienyltribenzyltitanium; cyclopentadienylmethyltitanium dichloride; cyclopentadienylethyltitanium dichloride; pentamethylcyclopentadienylmethyltitanium dichloride; pentamethylcyclopentadienylethyltitanium dichloride; cyclopentadienyldimethyl Titanium monochloride; cyclopentadienyl diethyl titanium monochloride; cyclopentadienyl titanium trimethoxide; cyclopentadie Cyclopentadienyl titanium tripropoxide; cyclopentadienyl titanium triphenoxide; pentamethylcyclopentadienyl titanium trimethoxide; pentamethylcyclopentadienyl titanium triethoxide; pentamethylcyclopentadiene Pentamethylcyclopentadienyl titanium tributoxide; pentamethylcyclopentadienyl titanium triphenoxide; cyclopentadienyl titanium trichloride; pentamethylcyclopentadienyl titanium trichloride; cyclopentadienyl methoxy titanium Dichloride; cyclopentadienyldimethoxytitanium chloride; pentamethylcyclopentadienylmethoxytitanium dichloride; cyclopentadienyltribenzyltitanium Cyclopentadienyldimethylmethoxytitanium;
Methylcyclopentadienyldimethylmethoxytitanium;
Pentamethylcyclopentadienylmethyldiethoxytitanium; indenyltitanium trichloride; indenyltitaniumtrimethoxide; indenyltitaniumtriethoxide;
Indenyltrimethyltitanium; indenyltribenzyltitanium and the like. Bis (cyclopentadienyl) dimethyltitanium; bis (cyclopentadienyl) diphenyltitanium; bis (cyclopentadienyl) diethyltitanium; bis (cyclopentadienyl) Dienyl)
Dibenzyltitanium; bis (methylcyclopentadienyl) dimethyltitanium; bis (pentamethylcyclopentadienyl) dimethyltitanium; bis (methyldicyclopentadienyl) dibenzyltitanium; bis (pentamethylcyclopentadienyl) di Benzyl titanium; bis (pentamethylcyclopentadienyl) chloromethyltitanium; bis (pentamethylcyclopentadienyl) hydridomethyltitanium and the like. Further, titanium compounds containing a cross-linkable ligand such as ethylene bis (indenyl) dimethyl titanium; ethylene bis (tetrahydroindenyl) dimethyl titanium; and dimethyl silylene bis (cyclopentadienyl) dimethyl titanium are also included. These transition metal compounds may be those which form a complex with a Lewis base.

Among these titanium compounds, in a catalyst system combined with the catalyst component (B), when it is necessary to increase the molecular weight of the styrenic polymer, an alkoxide,
A titanium compound having a substituted π-electron ligand is preferred. When the molecular weight is reduced, a titanium compound having a π-electron ligand and a halogen ligand is preferable.

Among the transition metal compounds represented by the general formulas [4] to [7], specific examples of the zirconium compound include cyclopentadienyl zirconium trimethoxide; pentamethylcyclopentadienyl zirconium trimethoxy. Cyclopentadienyl tribenzyl zirconium; pentamethylcyclopentadienyl tribenzyl zirconium; bisindenyl zirconium dichloride; zirconium dibenzyl dichloride; zirconium tetrabenzyl; tributoxy zirconium chloride; triisopropoxy zirconium chloride. Further, similarly, specific examples of the hafnium compound include cyclopentadienyl hafnium trimethoxide; pentamethylcyclopentadienyl hafnium trimethoxide; cyclopentadienyl tribenzyl hafnium; pentamethylcyclopentadienyl tribenzyl hafnium; Bisindenyl hafnium dichloride; hafnium dibenzyl dichloride; hafnium tetrabenzyl; tributoxy hafnium chloride; triisopropoxy hafnium chloride and the like.

Similarly, specific examples of the vanadium compound include vanadium trichloride; vanadyl trichloride; vanadium triacetylacetonate; vanadium tetrachloride; vanadium tributoxide; vanadyl dichloride; vanadyl bisacetylacetonate; Nart and the like.

On the other hand, the component (B) of the catalyst is a contact product of an organoaluminum compound and a condensing agent. Examples of the organic aluminum compound, usually, the general formula AlR ¹⁵ ₃ wherein, R ¹⁵ represents an alkyl group having 1 to 8 carbon atoms. And specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum. Of these, trimethylaluminum is preferable.

As the condensing agent, water is typically mentioned. In addition to the above, various agents such as copper sulfate pentahydrate, water adsorbed on inorganic or organic substances, and the like, which cause the above trialkylaluminum to undergo a condensation reaction. Is mentioned.

[0028] As used in the present invention, as a typical example of the contact product of an organoaluminum compound and a condensing agent as the component (B) of the catalyst is contacted with trialkyl aluminum and water, represented by the general formula AlR ¹⁵ ₃ Although there is a product, specifically, the following general formula [8]

[0029]

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[In the formula, q represents the degree of polymerization and is 0 to 50, and R ¹⁶ represents an alkyl group having 1 to 8 carbon atoms. Or a chain alkylaluminoxane represented by the following general formula:

[9]

[0031]

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Wherein R ¹⁶ is as defined above. And the like, and a cyclic alkylaluminoxane having a repeating unit represented by the formula (2-50).

In general, the contact product of aluminum and water such as trialkylaluminum is, together with the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane, a mixture of unreacted trialkylaluminum and various condensation products, These are complicatedly associated molecules, and these are various products depending on the contact conditions between the trialkylaluminum and the condensing agent water.

The reaction between the alkyl aluminum and the condensing agent at this time is not particularly limited, and may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization, and water is added later, and furthermore, a metal salt or the like is contained. There is a method of reacting water of crystallization, water adsorbed on inorganic or organic substances with an organoaluminum compound. Although this reaction proceeds even without solvent, it is preferable to carry out the reaction in a solvent. Suitable solvents include aliphatic hydrocarbons such as hexane, heptane and decane and aromatic hydrocarbons such as benzene, toluene and xylene. Can be mentioned. The water may contain up to about 20% of amines such as ammonia and ethylamine, sulfur compounds such as hydrogen sulfide, and phosphorus compounds such as phosphite.

In the present invention, the contact product (for example, alkylaluminoxane) of the organoaluminum compound and the condensing agent used as the component (B) of the catalyst may be a solid residue when a hydrated compound or the like is used after the above-mentioned contact reaction. And the solvent is distilled off under normal pressure or reduced pressure at a temperature of 30 to 200 ° C, preferably 40 to 150 ° C for 20 minutes to 8 hours, preferably 30 minutes to 5 hours. It is effective to heat-treat while heating.

In this heat treatment, the temperature may be appropriately determined according to various conditions, but is usually in the above range. In general, when the temperature is lower than 30 ° C., no effect is exhibited, and when the temperature is higher than 200 ° C., thermal decomposition of the alkylaluminoxane itself occurs, and both are not preferable.

The reaction product is obtained in the form of a colorless solid or solution depending on the conditions of the heat treatment. The product thus obtained can be dissolved or diluted with a hydrocarbon solvent, if necessary, and used as a catalyst solution.

Used as component (B) of such a catalyst
Contact products of organoaluminum compounds and condensing agents, especially
A preferred example of an alkylaluminoxane is proton nuclear magnetic
Aluminum-methyl group observed in resonance spectrum
(Al-CH_Three) Methyl proton signal based on bond
The high magnetic field component in the region is 50% or less. One
That is, the above contact product was dissolved in a toluene solvent at room temperature.
Proton nuclear magnetic resonance ( ¹H-NMR)
When measured, Al-CH_Three-Based methyl proton signal
Is 1.0 to 1.0 based on tetramethylsilane (TMS).
It is found in the range of -0.5 ppm. TMS proton sig
Null (0 ppm) is Al-CH_ThreeMethylproto based on
Al-CH_ThreeBased on
The proton signal to the toluene
Measured based on 2.35 ppm of methyl proton signal
The magnetic field component (i.e., -0.1 to -0.5 ppm) and other magnetic field components
(I.e., 1.0 to -0.1 ppm),
High magnetic field component is 50% or less of the whole, preferably 45 to 5%
Can be suitably used as the component (B) of the catalyst.

The catalyst used in the method of the present invention comprises the above-mentioned components (A) and (B) as main components. In addition to the above, another catalyst component (D) can be further added as desired. Thereby, the catalyst activity can be remarkably improved by adding the catalyst component (D).

The catalyst component (D) has the following general formula [10] R ¹⁷ _k AlY _3-k ... [10] wherein R ¹⁷ has 1 to 18 carbon atoms, preferably Y represents a hydrogen atom or a halogen atom, such as a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and an alkoxy group. k is in the range of 1 ≦ k ≦ 3. And an organoaluminum compound represented by the formula: Specific examples of the organoaluminum compound as the component (D) include trimethylaluminum, triethylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, and diethylaluminum ethoxide. Seed or 2
You can give more than seeds. Further, as long as the stereoregularity is not impaired, the general formula [11] W—R ¹⁸ — (P) _r —R ¹⁹ —W ′ (11) wherein R ¹⁸ and R ^{19 each} have 1 carbon atom -20 hydrocarbon groups, substituted aromatic hydrocarbon groups having 7-30 carbon atoms, or 6 carbon atoms having substituents containing heteroatoms such as oxygen, nitrogen and sulfur.
Represents a substituted aromatic hydrocarbon group having a carbon number of 1 to 40;
20 hydrocarbon groups,

[0041]

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R ²⁰ is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. W and W 'represent a hydroxyl group, an aldehyde group or a carboxyl group, and r represents 0 or an integer of 1 to 5; At least two hydroxyl or aldehyde groups represented by
Organic compounds having a carboxyl group can be added.

Specific examples of the organic compound represented by the above general formula [11] include, for example, 2,2'-dihydroxy-
3,3'-di-t-butyl-5,5'-dimethyldiphenyl sulfide; 2,2'-dihydroxy-3,3'-
Di-t-butyl-5,5'-dimethyldiphenyl ether and the like.

In the method of the present invention, the above (A),
When using a catalyst having the component (B) as a main component,
The proportion of each of these components varies depending on the type of each component, the type of the styrene-based monomer as the raw material, particularly the types of the styrene-type monomers I and II, and other conditions. The ratio of aluminum therein to the transition metal (for example, titanium) in the component (A), that is, aluminum / transition metal (molar ratio) is 1 to 10 ⁶ , preferably 10 to 10 ⁴ .

In the copolymerization of the styrene monomer and the hydrocarbon group-containing styrene monomer having an unsaturated bond, their use ratio is not particularly limited, and may be appropriately selected according to various situations. In general, in the next graft polymerization step (step 2), the number may be determined in accordance with the desired number of graft start points and the amount of grafting. The proportion of the hydrocarbon group-containing styrene-based monomer having styrene (such as styrene-based monomer II) may be increased. In the copolymerization of the styrene-based monomer I and the styrene-based monomer II, the ratio of the styrene-based monomer II to the total amount of the styrene-based monomers I and II is usually 1 × 10 ^-10 to
The concentration may be 50 mol%, preferably 1 × 10 ^{−8 to} 20 mol%, and more preferably 1 × 10 ⁻⁶ to 15 mol%.

The proportions of the starting monomers and the catalyst may be determined as appropriate, but usually the styrene monomers I and II are used.
In terms of the ratio of styrene monomer I and II / aluminum (molar ratio) to aluminum in the contact product which is the component (B) of the catalyst, ie, 1 to 10 ⁶ , preferably 10
It is a ^{2-10 4.}

The catalyst used in step (1) of the method of the present invention includes, in addition to (A) a transition metal compound and (B) a catalyst mainly composed of a contact product of an organoaluminum and a condensing agent,
A catalyst comprising (A) a transition metal compound and (C) a compound which reacts with the transition metal compound to form an ionic complex as a main component, or the above-mentioned components (A), (C) and (D) A catalyst as a main component is used. Here, the transition metal compound as the component (A) may be appropriately selected from those described above, and is preferably a compound represented by the general formula [4],
Transition metal compounds represented by [5], [6], and [7] may be used. More preferably, in the general formula [4], R ^{3 to} R ⁶ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, An alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 carbon atoms
Represents an aryloxy group, an arylalkyl group having 6 to 20 carbon atoms or a halogen atom, wherein at least one of R ^{3 to} R ^{6 is} a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a substituted indenyl group Is good. The organoaluminum compound as the component (D) may be appropriately selected from those described above, but is preferably a compound represented by the general formula [10].

The type of the component (C) is not particularly limited as long as it is a compound that reacts with the transition metal compound as the component (A) to form an ionic complex. Of the periodic table VB, VIB,
VIIB, VIII, IB, IIB, IIIA, IVA and VA
And a coordination complex compound comprising an anion bonded to an element selected from the group. As the component (C), a coordination complex compound represented by the following formula [12] or [13] can be suitably used. ([L ¹ -H] ^{u +} ) _v ([M ⁵ X ¹ X ² ... X ^s ] ^(st)- ) _i ... [12] or ([L ² ] ^{u +} ) _v ([M ⁶ X ¹ X ² ··· X ^{s] _(st) -)} i ··· [13] (wherein, L ² is ^{M 7, R 21 R 22 M} 8 or R ²³ ₃ C) [formula [12], In [13], L ¹ is a Lewis base, M ⁵ and M
⁶ are VB, VIB, VIIB, and VIII of the periodic table, respectively.
Group, Group IB, IIB group, IIIA group, an element selected from Group IVA or Group VA: M ⁷ group IB of the Periodic Table, IIB, Group metal selected from Group VIII, M ⁸ is VIII of the Periodic Table And X ^{1 to} X ^s are each a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, and a carbon atom of 1 to 20.
R ²¹ and R ²² represent an alkyl group, 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.
Represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ²³ represents a hydrocarbon group. t is an integer of 1 to 7 in valences of M ⁵ and M ⁶ , s is an integer of 2 to 8, u is an integer of 1 to 7 in ionic valence of L ¹ -H, L ² , and v is 1 or more. Integer, i = u × v /
(St). ]

[0049] Specific examples of the Lewis base represented by the above L ^1, dimethyl ether, diethyl ether, tetrahydrofuran and the like, thioethers such as tetrahydrothiophene, esters such as ethyl benzoate, nitriles such as acetonitrile and benzonitrile ,
Amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, 2,2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; ethylene and butadiene as chain unsaturated hydrocarbons; -Pentene, isoprene, pentadiene, 1-hexene and derivatives thereof, and cyclic unsaturated hydrocarbons such as benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Can be

Specific examples of M ⁵ and M ⁶ include B, Al,
Specific examples of M ⁷ such as Si, P, As, and Sb include Li,
Specific examples of M ⁸ such as Na, Ag, and Cu are Fe, C
o, Ni and the like. Specific examples of X ^{1 to} X ^s include, for example, a dimethylamino group, a diethylamino group as a dialkylamino group, a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group, and a phenoxy group, 2,6-dimethyl as an aryloxy group. Phenoxy group, naphthyloxy group, alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, n-octyl group, 2-ethylhexyl group, carbon number 6 A phenyl group as an aryl group, an alkylaryl group or an arylalkyl group, p-
Tolyl group, benzyl group, pentafluorophenyl group,
3,5-di (trifluoromethyl) phenyl group, 4-tert-butylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 1,2-dimethyl Examples of the phenyl group and halogen include F, Cl, and Br, l, and 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 for R ²¹ and R ²² include:
Examples include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

Among the compounds of the formulas [12] and [13], the following compounds can be particularly preferably used. For example, as the compound of the formula [12], triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) tetraphenylborate
Ammonium, tri (n-butyl) ammonium tetra (o, p-dimethylphenyl) borate, trimethylammonium tetraphenylborate, tri (n-butyl) ammonium tetra (p-trifluoromethyl) borate, triphenylphosphonium tetraphenylborate, Tri (methylphenyl) phosphonium tetraphenylborate, tri (dimethylphenyl) phosphonium tetraphenylborate, i-propylammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate, triethylammonium tetra (pentafluorophenyl) borate, tetra ( Pentafluorophenyl)
Tri (n-butyl) ammonium borate, triethylammonium hexafluoroarsenate, dimethylanilinium tetra (pentafluorophenyl) borate, diethylanilinium tetra (pentafluorophenyl) borate, di-n-butylanily tetra (pentafluorophenyl) borate And diphenylammonium tetra (pentafluorophenyl) borate and p-bromo-N, N-dimethylanilinium tetra (pentafluorophenyl) borate.

On the other hand, as compounds of the formula [13], ferrocenium tetraphenylborate, ferrocenium tetra (pentafluorophenyl) borate, decamethylferrocenium tetra (pentafluorophenyl) borate, and acetylferrocerate tetra (pentafluorophenyl) borate Nium,
Formylferrocenium tetra (pentafluorophenyl) borate, cyanopherosenium tetra (pentafluorophenyl) borate, silver tetraphenylborate, silver tetra (pentafluorophenyl) borate, trityl tetraphenylborate, tetra (pentafluorophenyl) borate Trityl, silver hexafluoroarsenate, silver hexafluoroantimonate, silver tetrafluoroborate and the like.

The catalyst used in the method of the present invention comprises the above-mentioned components (A) and (B) as main components, and (A)
In addition to the components having the components (B) and (D) as the main components, there are components having the components (A) and (C) as the main components. component,
There are some which have the component (C) and the component (D) as main components.
In this case, the addition ratio of the component (A) and the component (C) is not particularly limited, but the molar ratio of the component (A) to the component (C) is
1: 0.01 to 1: 100, particularly preferably 1: 1 to 1:10. Further, the components (A) and (C) may be brought into contact with each other in advance, and the contact product may be separated and washed before use, or may be brought into contact in a polymerization system. The amount of the component (D) is usually 0 to 100 mol per 1 mol of the component (A). When the component (D) is used, the polymerization activity can be improved. However, if the amount is too large, the effect corresponding to the added amount is not exhibited. The component (D) may be used in contact with the component (A), the component (C) or the contact product of the component (A) with the component (C). This contact may be carried out in advance, or may be added sequentially into the polymerization system and brought into contact.

Incidentally, the polymerization temperature, polymerization time,
The polymerization method and the like may be appropriately selected, but generally the polymerization temperature is 0 to 120 ° C, preferably 10 to 80 ° C, and the polymerization time may be selected in the range of 1 second to 10 hours. As the polymerization method, any of bulk, solution and suspension polymerization can be used. In the solution polymerization, usable solvents include aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. Of these, aliphatic hydrocarbons and aromatic hydrocarbons are preferred. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. The amount of the component (C) used is such that the raw material monomer / coordination complex compound (molar ratio) is 1-1.
0 ^9, it is preferable that the particular 100 to 10 ^7.

In the method of the present invention, a styrenic copolymer is produced in the above-mentioned step 1, and then an ethylenically unsaturated monomer (monomer) is graft-polymerized to this (step 2).
I do. Here, the structure of the styrene copolymer obtained in Step 1 is not particularly limited. However, as described above, as the hydrocarbon group-containing styrene monomer having an unsaturated bond, a monomer containing a styrene skeleton and an α-olefin skeleton in the same molecule is used, and the catalyst of the production method of the present invention is used. In the case of producing a polymer, even if the copolymerization ratio of this monomer is relatively high, the crosslinking reaction can be suppressed and a linear copolymer can be obtained efficiently. As a result of examining the cause, it has been clarified that the copolymer is not a styrene skeleton of the monomer but an α-olefin skeleton and a double bond of the styrene skeleton remains. A copolymer having such a structure has not been hitherto known. The ethylenically unsaturated monomer that can be used here is represented by the following general formula [3]

[0056]

Embedded image

[Wherein Q ¹ , Q ² , Q ³ and Q ⁴ are each a hydrogen atom, a halogen atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom. It represents a substituent containing any one or more kinds, and these Q ^{1 to} Q ⁴ may be the same or different. As long as it is represented by this formula, various monomers can be used as long as they are copolymerizable with the repeating unit of the styrene-based copolymer. Preferred are (1) acrylic acid, methacrylic acid, derivatives thereof, (2) acrylamide, methacrylamide,
Their derivatives, (3) vinyl acetate, their derivatives, (4) cinnamic acid, crotonic acid, their derivatives, (5) acrylonitrile, methacrylonitrile, their derivatives, (6) maleic acid, fumaric acid, anhydride Maleic acid, their derivatives, (7) maleimide, its derivatives, (8) itaconic acid, itaconic anhydride, their derivatives, (9) acrolein,
(10) Vinyl ketones, (11) dienes, (12) styrene, derivatives thereof, (13) α-olefins and (14) cyclic olefins.

Here, the derivatives of (meth) acrylic acid in the compound of (1) include allyl acrylate; isopropyl acrylate; ethyl acrylate;
Epoxypropyl; 2-chloroethyl acrylate; acrylic chloride; cyclododecyl acrylate; dibromopropyl acrylate; 6,8-dimethyl acrylate-1
-Oxy-5-chromanylmethyl;
2,2-tetrachloroethyl; tetrahydrofurfuryl acrylate; hydroxyethyl acrylate; hydroxypropyl acrylate; η ^6- (2-phenylethyl acrylate) tricarbonylchromium; butyl acrylate; 2-propynyl acrylate; Benzyl; 2- (1-aziridinyl) ethyl methacrylate; p-acetylphenyl methacrylate; 2-acetoxylethyl methacrylate; 1- (9-anthryl) ethyl methacrylate;
Ethyl methacrylate; 2,3-epithiopropyl methacrylate; 2,3-epoxypropyl methacrylate; octadecyl methacrylate; octafluoropentyl methacrylate; p-chlorophenyl methacrylate; chloromethyl methacrylate; 2- (diethylamino methacrylate) )
Ethyl; cyclohexyl methacrylate; 2,6-di-tert-butylphenyl methacrylate; p-dimethylaminobenzyl methacrylate; 2- (N,
N-dimethylcarbamoyloxyethyl); 2,6-dimethylphenyl methacrylate; 1,2,2-methacrylic acid
2,2-tetrachloroethyl; trifluoroethyl methacrylate; 2,2,4-trimethyl-3-methacrylate
On-1-pentyl; p-nitrophenol methacrylate; 2-pyridyl methacrylate; phenyl methacrylate; ferroceneethyl methacrylate; te methacrylate
rt-butyl; methacrylic acid fluoride; benzyl methacrylate; p-methylphenyl methacrylate; 3,4-methylenedioxybenzyl methacrylate; methacrylic acid 2
-Mercaptobenzthiazole; methacrylic acid (-)-
3-menthyl and the like.

Derivatives of (meth) acrylamide which is the compound of the above (2) include N-methylacrylamide;
N-ethylacrylamide; N-isopropylacrylamide; Nn-butylacrylamide; N-sec-
Butylacrylamide; N-isobutylacrylamide; N-tert-butylacrylamide; N- (1,
1-dimethylpropyl) acrylamide; N-cyclohexylacrylamide; N- (1,1-dimethylbutyl) acrylamide; N- (1-ethyl-1-methylpropyl) acrylamide; N- (1,1,2-trimethylpropyl) Acrylamide; Nn-heptylacrylamide; N- (1,1-dimethylpentyl) acrylamide; N- (1-ethyl-1-methylbutyl) acrylamide; N- (1-ethyl-1,2-dimethylpropyl) acrylamide; N- (1,1-diethylpropyl) acrylamide; Nn-octylacrylamide; N- (1,1,3,3-tetramethylbutyl) acrylamide; N- (1,2,3,3-tetramethylbutyl ) Acrylamide; N- (1-ethyl-1,3-dimethylbutyl) acrylia De; N-(1,1-diethyl-butyl) acrylamide; N-(1-ethyl-1-methylpentyl) acrylamide; N-(1-propyl -
1,3-dimethylbutyl) acrylamide; N- (1,
1-diethylpentyl) acrylamide; N- (1-butyl-1,3-dimethylbutyl) acrylamide; N-
N- (1-methylundecyl) acrylamide; N- (1,1-dibutylpentyl) acrylamide; N- (1-methyltridecyl) acrylamide; N- (1-methylpentadecyl) acrylamide; N- (1-methylheptadecyl) acrylamide; N- (1-adamantyl) acrylamide; N-
(7,7-dimethylbicyclo [3,2,0] hept-6
-Nyl) acrylamide; N-allylacrylamide;
N- (1,1-dimethylpropynyl) acrylamide;
N-benzylacrylamide; N-phenylacrylamide; N- (2-methylphenyl) acrylamide; N
-(4-methylphenyl) acrylamide; N- (1-
N- (2-naphthyl) acrylamide; N-methylmethacrylamide; N-ethylmethacrylamide; Nn-butylmethacrylamide;
N-tert-butyl methacrylamide; Nn-octyl methacrylamide; Nn-dodecyl methacrylamide; N-cyclohexyl methacrylamide;
(7,7-dimethylbicyclo [3,2,0] hept-6
-Nyl) methacrylamide; N-allyl methacrylamide; N- (1,1-dimethylpropenyl) methacrylamide; N-benzyl methacrylamide; N- [1- (4
-Chlorophenyl)] ethyl methacrylamide; N-phenylmethacrylamide; N- (2-methylphenyl)
N- (3-methylphenyl) methacrylamide; N- (4-methylphenyl) methacrylamide; N, N-bis (2-cyanoethyl) acrylamide; N- (4-cyano-2,2,6 6-tetramethyl-4-piperidyl) acrylamide; N- (2-cyanoethyl) methacrylamide; N- (1,1-dimethyl-
2- (cyanoethyl) acrylamide; N- (hydroxymethyl) acrylamide; N- (methoxymethyl) acrylamide; N- (ethoxymethyl) acrylamide;
N- (n-propoxymethyl) acrylamide; N-
(Isopropoxymethyl) acrylamide; N- (n-
N, N'-methylenebisacrylamide;1,2-bisacrylamidoethane;1,3-bisacrylamidopropane;1,4-bisacrylamidobutane;1,5-bisacrylamidopentane; 1,6- Bisacrylamidohexane; 1,
1,8-bisacrylamidooctane; 1,9-bisacrylamidononane; 1,10-bisacrylamidodecane; 1,12-
Bisacrylamidododecane; 1,1,1-trimethylamine-2- (N-phenyl-N-acryloyl) propanimide; 1,1-dimethyl-1- (2-hydroxy) propylamine-N-phenyl-N-methacryloylglycine Imide; N- (2-dimethylaminoethyl)
Acrylamide; N- (2-diethylaminoethyl) acrylamide; N- (2-monophorinoethyl) acrylamide; N- (3-dimethylaminopropyl) acrylamide; N- (3-diethylaminopropyl) acrylamide; N- (3-propylaminopropyl ) Acrylamide; N- [3-bis (2-hydroxyethyl) aminopropyl] acrylamide; N- (1,1-dimethyl-2-dimethylaminoethyl) acrylamide;
(2,2-dimethyl-3-dimethylaminopropyl) acrylamide; N- (2,2-dimethyl-3-diethylaminopropyl) acrylamide; N- (2,2-dimethyl-3-dibutylaminopropyl) acrylamide;
N- (1,1-dimethyl-3-dimethylaminopropyl) acrylamide; N-acryloylglycinamide; N- (2,4-dinitrophenylhydrazono) methyleneacrylamide; 2-acrylamidepropanesulfonic acid; 2-acrylamide-n -Butanesulfonic acid;
2-acrylamide-n-hexanesulfonic acid; 2-acrylamide-n-octanesulfonic acid; 2-acrylamide-n-dodecanesulfonic acid; 2-acrylamide-n-tetradecanesulfonic acid; 2-acrylamide-
2-methylpropanesulfonic acid; 2-acrylamide-
2-phenylpropanesulfonic acid; 2-acrylamido-2,4,4-trimethylpentanesulfonic acid; 2-acrylamido-2-methylphenylethanesulfonic acid;
2-acrylamide-2- (4-chlorophenyl) propanesulfonic acid; 2-acrylamide-2-carboxymethylpropanesulfonic acid; 2-acrylamide-2-
(2-pyridyl) propanesulfonic acid; 2-acrylamide-1-methylpropanesulfonic acid; 3-acrylamide-3-methylbutanesulfonic acid; 2-methacrylamide-n-decanesulfonic acid; 2-methacrylamide-
n-tetradecanesulfonic acid; 4-methacrylamide sodium benzenesulfonate; N- (2,3-dimethylphenyl) methacrylamide; N- (2-phenylphenyl) methacrylamide; N- (2-hydroxyphenyl) methacrylamide; N- (2-methoxyphenyl)
N- (4-methoxyphenyl) methacrylamide; N- (3-ethoxyphenyl) methacrylamide; N- (4-ethoxyphenyl) methacrylamide; N- (2-chlorophenyl) methacrylamide;
N- (3-chlorophenyl) methacrylamide; N-
(4-chlorophenyl) methacrylamide; N- (4-
Bromophenyl) methacrylamide; N- (2,5-dichlorophenyl) methacrylamide; N- (2,3,6
-Trichlorophenyl) methacrylamide; N- (4-
Nitrophenyl) methacrylamide; N, N-dimethylacrylamide; N, N-diethylacrylamide;
N, N-dibutylacrylamide; N, N-diisobutylacrylamide; N, N-dicyclohexylacrylamide; N, N-bis (4-methylpentyl) acrylamide; N, N-diphenylacrylamide; N, N-
Bis (5-methylhexyl) acrylamide; N, N-
N, N-bis (2-ethylhexyl) acrylamide; N-methyl-N-phenylacrylamide; N-acryloylpyrrolidine; N-acryloylpiveridine; N-acryloylmorpholine;
N-acryloylthiamorpholine; N, N-dimethylmethacrylamide; N, N-diethylmethacrylamide;
N, N-diphenylmethacrylamide; N-methyl-N
-Phenylmethacrylamide; N-methacryloylpiveridine; N- (2-hydroxyethyl) acrylamide; N- (2-hydroxypropyl) acrylamide;
N- (1,1-dimethyl-2-hydroxyethyl) acrylamide; N- (1-ethyl-2-hydroxyethyl) acrylamide; N- (1,1-dimethyl-3-hydroxybutyl) acrylamide; N- (2 -Chloroethyl) acrylamide; N- (1-methyl-2-chloroethyl) acrylamide; N- (2,2,2-trichloro-1-hydroxyethyl) acrylamide; N-
(2,2,2-trichloro-1-methoxyethyl) acrylamide; N- (1,2,2,2-tetrachloroethyl) acrylamide; N- (2,2,3-trichloro-
2-hydroxypropyl) acrylamide; N- (2-
Chlorocyclohexyl) acrylamide; N- (2,2
-Difluoroethyl) acrylamide; N- (2,2,
2-trifluoroethyl) acrylamide; N- (3,
3,3-trifluoropropyl) acrylamide; N-
(3,3-difluorobutyl) acrylamide; N, N
-Bis (2,2-difluoroethyl) acrylamide;
N, N-bis (2,2,2-trifluoroethyl) acrylamide; ethyl-2-acrylamide acetate;
Acryloyl dicyandiamide; methacryloyl dicyandiamide; N- (1-naphthyl) methacrylamide;
N- (2-naphthyl) methacrylamide; N-formylacrylamide; N-acetylacrylamide; N-
(2-oxopropyl) acrylamide; N- (1-methyl-2-oxopropyl) acrylamide; N- (1
-Isobutyl-2-oxopropyl) acrylamide;
N- (1-benzyl-2-oxopropyl) acrylamide; N- (1,1-dimethyl-3-oxobutyl) acrylamide and the like.

Further, vinyl acetate which is the compound of (3),
Examples of the derivatives include vinyl acetate, vinyl thioacetate, and α- (1-cyclohexenyl) vinyl acetate.

Derivatives of the compounds (4), cinnamic acid and crotonic acid, include ethyl cinnamate, phenyl cinnamate, tert-butyl cinnamate, crotonaldehyde, methyl crotonate, α-cyanocrotonic acid Ethyl and methyl α-methoxycrotonate.

Among the compounds of (5), the derivatives of (meth) acrylonitrile include vinylidene cyanide, α-methoxyacrylonitrile, α-phenylacrylonitrile, α-acetoxyacrylonitrile and the like.

Among the compounds of (6), the maleic acid, fumaric acid and maleic anhydride derivatives include maleic acid, fumaric acid esters and substituted maleic acid, fumaric acid and maleic anhydride. Diethyl fumarate, diphenyl fumarate, fumalonitrile, methyl fumaric acid, diethyl methyl fumarate, methyl maleic anhydride, dimethyl maleic anhydride, phenyl maleic anhydride, diphenyl maleic anhydride, chloromaleic anhydride, dichloromaleic anhydride, fluoromaleic anhydride Acid, difluoromaleic anhydride, bromomaleic anhydride, dibromomaleic anhydride, methylmaleic acid, dimethylmaleic acid, phenylmaleic acid, chloromaleic acid, dichloromaleic acid, fluoromaleic acid, difluoromaleic acid, bromomaleic Acid, dimethyl maleate, diethyl maleate, diethyl methyl maleate,
Dipropyl maleate, diisopropyl maleate, dibutyl maleate, diisobutyl maleate, dipentyl maleate, diisopentyl maleate, dihexyl maleate, diheptyl maleate, dioctyl maleate, bis (2-ethylhexyl) maleate, dinonyl maleate, maleate Dihexadecyl acid, dipropargyl maleate, bis [2- (2-chloroethoxy) ethyl] maleate, dipendyl maleate, methylallyl maleate, methyl-2-butenyl maleate, methyl-3-butenyl maleate, allyl maleate -3-
Methylthiopropyl, allyl-3-ethylthiopropyl maleate, allyl-3-acetylthiopropyl maleate, allyl-3-phenylthiopropyl maleate,
Methyl maleate-p-chlorophenyl, butyl maleate-p-chlorophenyl, benzyl maleate-p-
Chlorophenyl, diphenyl maleate, di-m-cresyl maleate, di-p-cresyl maleate, n-heptyl maleate, nonyl maleate, decyl maleate, dodecyl maleate, octadecyl maleate,
And fluoroalkyl maleate.

Among the compounds of (7), maleimide derivatives include N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N-cyclohexylmaleimide, and N- (2,6-dimethyl) Maleimide, N- (2,6-diethyl) maleimide, N-
(Α-naphthyl) maleimide and the like.

Among the compounds (8), derivatives of itaconic acid and itaconic anhydride include diethyl itaconate, di-n-octyl itaconate, cis-glutaconic acid, cis-
Diethyl glutaconate, trans-glutaconic acid, t
trans-diethyl glutaconate and the like.

The acroleins of the compound (9) include
Acrolein, methacrolein, α-chloroacrolein, β-cyanoacrolein and the like.

Examples of the vinyl ketones of the compound (10) include methyl vinyl ketone, phenyl vinyl ketone, ethyl vinyl ketone, n-propyl vinyl ketone, cyclohexyl vinyl ketone, isobutyl vinyl ketone and the like.

The dienes of the compound (11) include 1,3
-Butadiene; isoprene; 1-ethoxy-1,3-butadiene; chloroprene; 1-methoxy-1,3-cyclohexadiene; 1-acetoxy-1,3-butadiene; 2-acetoxy-3-methyl-1,3- Butadiene; 1-chloro-1,3-butadiene; 1- (4-pyridyl) -1,3-butadiene; muconic acid; diethyl muconate;

As the styrene of the compound (12) or a derivative thereof, for example, a styrene monomer I represented by the above general formula [1] can be used.
p-dimethylaminostyrene; butyl styrenesulfonate; p-nitrostyrene; p-hydroxystyrene; p
2,3-epoxypropyl vinylbenzoate; p-vinylbenzoic acid chloride; phenyl p-vinylbenzoate; p
-Methyl vinyl benzoate; 3-methoxyphenyl p-vinylbenzoate; p-isopropenylphenol; p-cyanostyrene; an oxygen atom such as p-acetoxystyrene;
A styrene derivative containing a hetero atom such as a nitrogen atom or α-methylstyrene may be used.

The α-olefins of the compound (13) include ethylene; propylene; 1-butene; 1-octene; 4-methylpentene-1; 3-methylbutene-1 and the like.

The cyclic olefins of the compound (14) include cyclobutene; cyclopentene; monocyclic olefins such as cyclohexene; 3-methylcyclopentene;
Substituted monocyclic olefins such as -methylcyclohexene,
Norbornene; 1,2-dihydrodicyclopentadiene; 1,4,5,8-dimethano-1,2,3,4,4
polycyclic olefins such as a, 5,8,8a-octhydronaphthalene, 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; 5,5-trimethylnorbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5-ethylidenenorbornene; 5-vinylnorbornene; 2-methyl-1,4,5,8-dimethano-1,
2,3,4,4a, 5,8,8a-octhydronaphthalene; 2-ethyl-1,4,5,8-dimetano-1,
2,3,4,4a, 5,8,8a-octhydronaphthalene; 2,3-dimethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octhydronaphthalene; 5-chloronorbornene; 5,5-dichloronorbornene; 5-fluoronorbornene; 5,5,6
And substituted polycyclic olefins such as -trifluoro-6-trifluoromethylnorbornene; 5-chloromethylnorbornene; 5-methoxynorbornene; and 5-dimethylaminonorbornene. The selection of these monomers is appropriately determined depending on the purpose of use of the obtained graft copolymer. For example, for the purpose of improving adhesion and the like, those having a polar group such as an unsaturated carboxylic acid or a derivative thereof are preferable. . In order to improve the heat resistance, maleimide or a derivative thereof, or a cyclic olefin such as norbornene, and an ethylenically unsaturated monomer having a high glass transition temperature of the polymer are preferable.

In the method of the present invention, when performing the graft polymerization in step 2, unreacted styrene monomers I and II and a catalyst were removed from the styrene copolymer obtained in step 1 as necessary. Thereafter, the above-mentioned ethylenically unsaturated monomer is added to carry out a reaction. Here, the graft polymerization usually proceeds with a polymerization initiator, light irradiation, or the like. In the graft polymerization, an ethylenically unsaturated monomer may be added after the styrene-based copolymer has been activated by a polymerization initiator, light irradiation, or the like. Along with or after the addition of the saturated monomer, a polymerization initiator may be added, or light or the like may be irradiated.

As the polymerization initiator, there are various ones which have been conventionally used, and examples thereof include an anionic polymerization initiator, a cationic polymerization initiator and a radical polymerization initiator. Further, polymerization can be initiated by heat, light (ultraviolet light, visible light, infrared light), electron beam, radiation, or the like. Further, α such as ethylene and propylene
-When grafting olefins, styrenes and cyclic olefins, it is possible to increase the rate of grafting and the amount of grafting by using a catalyst mainly composed of a transition metal and an organic metal.

Examples of the anionic polymerization initiator include, for example, alkali metals (Cs, Rb, K, Na, Li), alkali metal alkyls (n-butyl Li, octyl K, dibenzyl Ba), alkali metal aromatic compound complexes ( Na
-Naphthalene), alkali metal amide (KNH ₂ , Li
N (C ₂ H ₅ ) ₂ ).

Next, as the cationic polymerization initiator, for example,
For example, protonic acid, carbanium ion salt, halogen, etc.
There is. Examples of the protonic acid include hydrogen halide (H
Cl, HI, etc.), oxo acids (sulfuric acid, methanesulfonic acid)
), Superacids and their derivatives (HClO_Four, CF_Three
SO_ThreeH, ClSO_ThreeH, CH_ThreeCOCLO_FourSuch),
Metal oxide (silica alumina, CrO_Three, MoO_ThreeWhat
And other solid acids (polystyrenesulfonic acid,
Nafion-H, sulfuric acid-aluminum sulfate complex, etc.)
There is. In addition, as the carbanium ion salt,
Phenylmethyl salt (Pb_ThreeC⁺Base^-), Tropiriu
Salt (C₇H₇ ⁺Base^-) (Where Base
^-Is SbCl₆ ^-, SnCl_Five ^-, PF₆ ^-, ClO
_Four ^-And so on. ). As halogen, I_Two, I
Br and the like. In addition, metal halides (AlC
l_Three, SnCl_Four, SnBr_Four, TiCl_Four, FeCl
_Three, BF_Three, BCl_ThreeEtc.) and organometallic compounds (RAl
Cl_Two, R_TwoAlCl, R_ThreeAl, R _TwoZn) (here
And R represents an alkyl group such as a methyl group or an ethyl group.
You. ).

As the radical polymerization initiator, peroxide,
Examples include azo compounds and other compounds. As the peroxide, for example, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chloroperoxide Benzoyl,
2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1
-Hydroperoxide, pertriphenylacetic acid-tert
-Butyl, tert-butyl hydroperoxide, tert-butyl formate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl per-4-methoxyacetate, perN- (3
Tert-butyl carbamate; Specific examples of the azo compound include 2,2′-azobispropane; 2,2′-dichloro-2,2′-azobispropane; 1,1′-azo (methylethyl) diacetate; 2,2 ′ -Azobis (2-amidinopropane) hydrochloride; 2,2'-azobis (2-amidinopropane) nitrate; 2,2'-azobisisobutane;2,2'-azobisisobutylamide;2,2'-azoBisisobutyronitrile;2,2'-azobisisobutyronitrile / Sn
Cl ₄ (1 / 21.5), methyl 2,2′-azobis-2-methylpropionate; 2,2′-dichloro-2,2 ′
Azobisbutane; 2,2′-azobis-2-methylbutyronitrile; dimethyl 2,2′-azobisisobutyrate;
Dimethyl 2,2'-azobisisobutyrate / SnCl ₄ (1
/19.53); 1,1'-azobis (1-methylbutyronitrile-3-sodium sulfonate); 2- (4-methylphenylazo) -2-methylmalonodinitrile;
4,4'-azobis-4-cyanovaleric acid; 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile; 2- (4-bromophenylazo) -2-allylmalonodinitrile; 2,2 'Azobis-2-methylvaleronitrile; dimethyl 4,4′-azobis-4-cyanovalerate; 2,2′-azobis-2,4-dimethylvaleronitrile; 1,1′-azobiscyclohexanenitrile; 2, 2′-azobis-2-propylbutyronitrile; 1,1′-azobis-1-chlorophenylethane;
1,1′-azobis-1-cyclohexanecarbonitrile; 1,1′-azobis-cycloheptanenitrile;
1,1′-azobis-1-phenylethane; 1,1′-
Azobiscumene; ethyl 4-nitrophenylazobenzylcyanoacetate; phenylazodiphenylmethane; phenylazotriphenylmethane; 4-nitrophenylazotriphenylmethane; 1,1'-azobis-1,2-diphenylethane; poly (bisphenol A- 4,4'-
Azobis-4-cyanopentanoate); poly (tetraethylene glycol-2,2'-azobisisobutyrate) and the like. Still other compounds include 1,4
-Bis (pentamethylene) -2-tetrazene; 1,4-
Dimethoxycarbonyl-1,4-diphenyl-2-tetrazene; benzenesulfonyl azide;

When α-olefins such as ethylene and propylene, styrenes and cyclic olefins are grafted with a catalyst containing a transition metal and an organic metal as main components, the transition metal compound is represented by the aforementioned general formula [4] ], [5],
In addition to [6] and [7], chromium compounds, nickel compounds, and niobium compounds can be used. Further, as the organometallic compound, the aforementioned general formula [8],

The aluminoxane [9] and the organoaluminum compound of the general formula [10] can be used.

In the method of the present invention, the graft polymerization step (step 2) uses the above-mentioned raw materials and initiators,
The polymerization reaction proceeds by appropriately selecting the conditions.
The reaction conditions of the styrene-based copolymer obtained in Step 1 and the initiator include a reaction temperature of −100 to 200 ° C.
Preferably, the temperature is in the range of -80 to 120 ° C and the reaction time is 1
What is necessary is just to select suitably in the range of seconds to 10 hours. After the initiator such as alkyl lithium is reacted with the styrene-based copolymer obtained in the step 1, the unreacted remaining initiator is washed to increase the grafting efficiency. When the graft chain is formed as a copolymer chain with an unreacted styrenic monomer, after the synthesis of the graft precursor (step 1), the graft reaction is carried out by adding the ethylenically unsaturated monomer together with the graft initiator as it is. Just do it. Here, when the catalyst used in the step 1 can be used also in the graft polymerization step in the step 2, specifically, as the ethylenically unsaturated monomer, α such as ethylene or propylene is used.
The use of dienes such as olefins, butadiene and isoprene makes it possible to produce graft copolymers with very high efficiency. Styrene monomer used in step 1
The ratio of II to initiator is usually the latter / former = 1 × 10 ⁻⁷
To 10 (molar ratio). The conditions for the graft polymerization are not particularly limited, and are appropriately determined according to various situations. Usually, the styrenic monomer II used in step 1
The ratio of the ethylenically unsaturated monomer to be grafted with the former / the latter is 0.01 to 500 (molar ratio), preferably 0.1 to 500.
300 (molar ratio). The polymerization temperature is -100 ° C.
To 200 ° C, preferably -80 ° C to 120 ° C, and the polymerization time is appropriately selected in the range of 5 seconds to 24 hours.

The polymerization method in the above step 2 can be any of bulk, solution and suspension polymerization. In the solution polymerization, usable solvents include aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. Polymerization solvents containing heteroatoms such as oxygen, nitrogen and sulfur can also be used. Here, the solvent used may be the same as or different from that used in Step 1 above. Further, a washing step can be performed to remove the remaining unreacted monomer and catalyst and increase the grafting efficiency.

The three-dimensional structure of the graft copolymer obtained by the method of the present invention is preferably such that the main chain structure is a syndiotactic structure (specifically, a styrene monomer I
And a repeating unit derived from styrene-based monomer II), and particularly preferably a styrene-based copolymer having a high syndiotactic structure. Various molecular weights of the main chain can be obtained depending on polymerization conditions and the like.
PC [1,2,4-trichlorobenzene, 135 ° C., converted to polystyrene] has a weight average molecular weight of 1,000
0 to 3,000,000, preferably 5,000 to 2,500,000
00.

The advanced syndiotactic structure is
Syndiotactic structure having a high stereochemical structure, that is, a stereostructure in which phenyl groups and substituted phenyl groups which are side chains with respect to the main chain formed from carbon-carbon bonds are alternately located in opposite directions. The tacticity is quantified by nuclear magnetic resonance ( ^13C -NMR) using isotope carbon. Tacticity measured by the ¹³ C-NMR method is the proportion of a plurality of continuous structural units,
For example, a styrene-based copolymer having a high syndiotactic structure as referred to in the present invention is a styrene-based copolymer having a high syndiotactic structure. In a chain of repeating units, usually at least 75% racemic dyad, preferably at least 85%, or 30% racemic pentad
As described above, those having a syndiotacticity of preferably 50% or more are shown.

The steric structure of the graft chain of the above graft copolymer is not particularly limited, and an atactic, isotactic or syndiotactic structure can be obtained depending on the type of the polymerization initiator and the like.

The thus obtained graft copolymer of the present invention has various molecular weights, but preferably has a graft component content of 0.005 in the graft copolymer.
It has a reduced viscosity of 0.01 to 20 dl / g at a concentration of 0.05 g / dl measured at 135 ° C. in 1,2,4-trichlorobenzene. If the reduced viscosity is too small, the physical properties of the polymer will not be sufficiently exhibited, and if it is too large, the moldability will be poor. This graft copolymer is particularly derived from a styrene monomer derived from a styrene monomer (styrene monomer I or the like) constituting the main chain and a hydrocarbon group-containing styrene monomer having an unsaturated bond (styrene monomer II). The styrene unit has a syndiotactic structure (preferably a co-syndiotactic structure), to which an ethylenically unsaturated monomer (preferably a monomer having a polar group) is grafted. Here, the content of the graft monomer in the graft copolymer depends on the type of the monomer used,
Since it is not always uniform depending on the ratio of the graft starting points, it is usually 0.005 to 90% by weight, preferably 0.01 to 90% by weight.
70% by weight. Further, various additives can be added to the styrene-based graft copolymer or the composition thereof of the present invention. For example, heat stabilizers, weather stabilizers, antistatic agents, slip agents, antiblocking agents, antifogging agents, lubricants, foaming agents, dyes, pigments, natural oils, synthetic oils, waxes, etc. can be blended. The compounding amount is an appropriate amount.
For example, as a stabilizer to be blended as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane; β- (3,5-di- t-butyl-4-hydroxyphenyl) propionic acid alkyl ester; 2,2'-oxamidobis [ethyl-3 (3,5-di-t-butyl-
4-hydroxyphenyl)] phenolic antioxidants such as propionate, zinc stearate; calcium stearate; fatty acid metal salts such as calcium 12-hydroxystearate; glycerin monostearate; glycerin monolaurate; glycerin distearate;
Examples include polyhydric alcohol fatty acid esters such as pentaerythritol monostearate; pentaerythritol distearate; and pentaerythritol tristearate. These may be blended alone or in combination. For example, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane and zinc stearate and Examples thereof include a combination with glycerin monostearate.

[0084]

Next, the present invention will be described in more detail with reference to examples. The present invention is not limited by the following examples.

Example 1 (1) Preparation of methylaluminoxane In a glass container having an inner volume of 500 ml and being purged with argon,
Toluene 200 ml, copper sulfate pentahydrate (CuSO ₄ · 5H
₂ O) placed 17.7 g (71 mmol) and trimethyl aluminum 24 ml (250 mmol), 8 at 40 ° C.
Allowed to react for hours. Thereafter, toluene was further distilled off under reduced pressure from the solution obtained by removing the solid components, and the catalyst product 6.
7 g were obtained. Its molecular weight measured by freezing point depression method was 610. Also, Japanese Patent Application Laid-Open No. 62-32539
High magnetic field components by ¹ H-NMR measurement based on No. ¹
That is, observing the proton nuclear magnetic resonance spectrum at room temperature the toluene solution (Al-CH ₃₎ methyl proton signal based on the binding seen in the range of 1.0 to-0.5 ppm in tetramethylsilane standard. The proton signal of tetramethylsilane (0 ppm) is Al-
Because of the observation area based on the methyl proton based on the CH ₃ bond, it is measured based on the methyl proton signal 2.35ppm toluene methyl proton signal based on the Al-CH ₃ bonds in tetramethylsilane standard, high magnetic field component (That is, -0.1 to -0.5 ppm)
And the other magnetic field components (i.e., 1.0 to -0.1 ppm), the high magnetic field components accounted for 43% of the whole.

(2) Production of p-methylstyrene-divinylbenzene copolymer A reaction vessel equipped with a stirrer having an inner volume of 0.5 liter was purged with nitrogen, heated to 70 ° C., and then thoroughly dried with 50 ml of toluene. And 50 ml of p-methylstyrene and a divinylbenzene-containing monomer (divinylbenzene (m-, p-
66.1% by weight, ethylstyrene (m-, p-
Mixture of 33.9% by weight) and 3.0 ml of
1.5 mM of methylaluminoxane obtained in (1) and 1.5 mM of triisobutylaluminum (TIBA) were added, and the mixture was stirred for 30 minutes. Then, pentamethylcyclopentadienyltitanium trimethoxide was added to 0.003.
mM was added and the reaction was performed for 2 hours. Thereafter, 1/10 was withdrawn with stirring to make the whole uniform, and methanol was injected to terminate the reaction. Next, a mixed solution of hydrochloric acid and methanol was added to decompose the catalyst component. Furthermore, when the obtained styrene-based copolymer was washed with methyl ethyl ketone (containing 2% by weight of pt-butylcatechol) at 50 ° C. for 2 hours, 99% was insoluble. The styrene copolymer insoluble in methyl ethyl ketone was dissolved in chloroform, and a chloroform solution of the styrene copolymer was obtained from the soluble matter. The weight average molecular weight of the styrene copolymer soluble in chloroform was 658,000, and the number average molecular weight was 180,000. Further, it is proved from the results of an infrared absorption spectrum (IR) and a nuclear magnetic resonance spectrum (NMR) that the styrene-based copolymer is a thermoreactive styrene-based copolymer having a syndiotactic structure.

(A) Measurement by IR In the IR spectrum of the styrene copolymer, the peak of the double bond remaining at the polymerization site of divinylbenzene was confirmed at 1630 cm ^-1 .

(B) Measurement by NMR As a result of measuring the ¹³ C-NMR spectrum of the styrenic copolymer, the aromatic ring C ₁ carbon signal was found to be 14.5.
1 ppm, 144.9 ppm, and 142.3 ppm were observed. From this signal, it was confirmed that the steric structure of the styrene copolymer was a syndiotactic structure.

(3) Grafting reaction of methyl methacrylate (MMA) The above-mentioned p-methylstyrene-divinylbenzene copolymer was washed three times with 200 ml of toluene to remove unreacted monomers and unreacted catalyst. . Next, toluene was added to bring the total volume to 300 ml. Thereafter, 4 mM of n-butyllithium (n-BuLi) was added and reacted at room temperature for 8 hours. After the completion of the reaction, washing was performed three times with 200 ml of toluene to remove unreacted n-BuLi. Then, toluene was added to bring the total volume to 300 ml. Thereafter, the reaction system is quenched at −78 ° C. (dry ice + methanol). Next, 20 ml of MMA was added dropwise and reacted for 8 hours. After completion of the reaction, methanol was injected to stop the reaction. The yield of the obtained MMA-grafted styrene-based copolymer was 4.2 g. Of IR spectrum of the styrene copolymer, the 1730 cm ^-1 of MMA (C
= O) A peak was confirmed. Furthermore, disappearance of the peak of the double bond of divinylbenzene at 1630 cm ^-1 was confirmed. The reduced viscosity of this copolymer at a concentration of 0.05 g / dl measured at 135 ° C. in a 1,2,4-trichlorobenzene solution was 1.98 dl / g. In addition, 1, 2, 4
At 135 ° C. in trichlorobenzene
^{When 13} C-NMR was measured, the aromatic signal derived from syndiotactic polystyrene was found to be 145.4 ppm.
Was observed. This indicates that the styrene chain has a syndiotactic structure. Also ¹³ CN
Tacticity is 95 in racemic diads by MR
%Met. Further, the ratio of p-methylstyrene to MMA determined by NMR was 1: 2.75 (weight ratio).

Example 2 Production of Styrene Copolymer Example 1 was repeated except that styrene was used in place of p-methylstyrene during polymerization.
MMA grafted styrene-divinylbenzene copolymer was obtained in the same manner as in (2) and (3). The yield of the obtained styrenic copolymer was 5.8 g. Of the IR spectrum of the above styrene copolymer, 1730 cm ^-1
A (C = O) peak of MMA was confirmed. The reduced viscosity of this copolymer at a concentration of 0.05 g / dl measured at 135 ° C. in a 1,2,4-trichlorobenzene solution was 1.98.
dl / g. Tacticity was 95% by racemic diad according to ¹³ C-NMR. Further N
The ratio of styrene to MMA determined by MR was 1: 2.82 (weight ratio).

Example 3 An acrylonitrile-grafted styrene-divinylbenzene copolymer was obtained in the same manner as in Example 2, except that acrylonitrile was used instead of MMA at the time of grafting. The yield of the obtained styrenic copolymer was 25.2 g. In the IR spectrum of the styrene copolymer, a peak of acrylonitrile was confirmed at 2240 cm ^-1 . The reduced viscosity of this copolymer at a concentration of 0.05 g / dl measured in a 1,2,4-trichlorobenzene solution at 135 ° C. was 1.94 dl / g. Also ¹³ CN
Tacticity is 95 in racemic diads by MR
%Met. Further, the ratio of styrene to acrylonitrile determined by NMR was 1: 5.8 (weight ratio).

Example 4 At the time of grafting, isoprene was used instead of MMA.
A styrene-divinylbenzene copolymer grafted with isoprene was obtained in the same manner as in Example 2 except that the reaction was carried out at ℃. The yield of the obtained styrenic copolymer was 12.3.
g. 840 cm ^-1 of the IR spectrum of the styrene copolymer, 1380 cm ^-1, 2960 cm
^-1 each, the peak of isoprene was confirmed. 135 of this copolymer in 1,2,4-trichlorobenzene solution
The reduced viscosity at a concentration of 0.05 g / dl measured at 0 ° C. is 1.
It was 87 dl / g. Tacticity was 95% by racemic diad according to ¹³ C-NMR. Further, the ratio of styrene to isoprene determined by NMR was 1: 7.
20 (weight ratio).

Example 5 At the time of grafting, butadiene was used instead of MMA.
A styrene-divinylbenzene copolymer grafted with butadiene was obtained in the same manner as in Example 2 except that the reaction was carried out at ℃. The yield of the obtained styrenic copolymer is 8.4 g.
Met. A butadiene peak was confirmed at 960 cm ^-1 in the IR spectrum of the styrene copolymer. The reduced viscosity of this copolymer at a concentration of 0.05 g / dl measured at 135 ° C. in a 1,2,4-trichlorobenzene solution was 1.89 dl / g. Tacticity was 95% by racemic diad according to ¹³ C-NMR. Further, the ratio of styrene to butadiene determined by NMR was 1: 4.60 (weight ratio).

Example 6 Production of Styrene Copolymer In the polymerization, the same procedure as in Example 2 was carried out except that tetraethoxytitanium (TET) was used instead of pentamethylcyclopentadienyltitanium trimethoxide as a catalyst. Thus, a styrene-divinylbenzene copolymer grafted with MMA was obtained. The yield of the obtained styrenic copolymer was 3.5 g. Of the IR spectrum of the above styrene copolymer, 1730 cm
^{At -1} , the (C = O) peak of MMA was confirmed. 135 ° C. in a 1,2,4-trichlorobenzene solution of this copolymer
The reduced viscosity at a concentration of 0.05 g / dl measured in the above was 2.0.
It was 0 dl / g. Tacticity was 95% by racemic diad according to ¹³ C-NMR. Further, the ratio of styrene to MMA determined by NMR was 1: 2.18.
(Weight ratio).

Example 7 An MMA-grafted styrene-divinylbenzene copolymer was obtained in the same manner as in Example 2 except that the polymerization solvent was changed from toluene to hexane. The yield of the obtained styrenic copolymer was 5.6 g. Of IR spectrum of the styrene copolymer, MMA to 1730 cm ^-1
(C = O) peak was confirmed. 1 of this copolymer
The reduced viscosity at a concentration of 0.05 g / dl measured in a 2,4-trichlorobenzene solution at 135 ° C. is 2.01 dl / g.
Met. Tacticity was 95% by racemic diad according to ¹³ C-NMR. Further, the ratio of styrene to MMA determined by NMR was 1: 4.09 (weight ratio).

Example 8 An MMA-grafted styrene-divinylbenzene copolymer was obtained in the same manner as in Example 2 except that the polymerization solvent was changed from toluene to heptane. The yield of the obtained styrenic copolymer was 8.1 g. Of IR spectrum of the styrene copolymer, MMA to 1730 cm ^-1
(C = O) peak was confirmed. 1 of this copolymer
The reduced viscosity at a concentration of 0.05 g / dl measured in a 2,4-trichlorobenzene solution at 135 ° C. is 2.05 dl / g.
Met. Tacticity was 95% by racemic diad according to ¹³ C-NMR. Further, the ratio of styrene to MMA determined by NMR was 1: 6.36 (weight ratio).

Example 9 MMA-grafted styrene-divinylbenzene copolymer was obtained in the same manner as in Example 2 except that azobisisobutyronitrile (AIBN) was used instead of n-BuLi as a catalyst during grafting. A coalescence was obtained. The yield of the obtained styrenic copolymer was 3.1 g. In the IR spectrum of the styrene-based copolymer, a peak (C = O) of MMA was confirmed at 1730 cm ^-1 . The reduced viscosity of this copolymer at a concentration of 0.05 g / dl measured at 135 ° C. in a 1,2,4-trichlorobenzene solution was 2.07 d.
1 / g. Tacticity was 95% by racemic diad according to ¹³ C-NMR. Further NM
The ratio of styrene to MMA determined from R was 1: 1.82 (weight ratio).

Example 10 In an argon atmosphere, 70 ml of toluene, 60 ml of styrene and 2 ml of p-divinylstyrene were added to a 200 ml reaction vessel at room temperature, 10 mmol of methylaluminoxane prepared in Example 1 (1) was added, and the temperature was raised to 50 ° C. Warmed. Further, 0.1 mmol of tetraethoxytitanium was added and a copolymerization reaction was carried out for 1 hour. Thereafter, a reaction product equivalent to 5 ml was fractionated from this copolymerization reaction system under an argon atmosphere,
The mixture was transferred to a pressure-resistant glass reaction vessel, and the copolymer powder was washed three times with 100 ml of hexane by a decantation method. Finally, 200 ml of hexane was charged. To this was added 2 mmol of diethylaluminum monochloride and ethylene was continuously introduced at 70 ° C. for 3 hours at 2.4 kg / cm ² G. The pressure was released, and the obtained copolymer was poured into methanol, washed and air-dried to obtain 2.85 g of the copolymer. The following analysis was performed to prove that the obtained copolymer was a graft copolymer of ethylene having a syndiotactic polystyrene as a main chain. First, when the IR and ¹³ C-NMR of the graft precursor were measured, the absorption of the vinyl group of the divinylbenzene residue was observed at 1630 cm ⁻¹ , and the IR of the graft precursor was 1605 cm ^{−1 of the} styrene residue unit.
And the absorbance ratio (D ₁₆₃₀ / D ₁₆₀₅ ) was 0.26. In addition, according to the measurement of ¹³ C-NMR, a sharp peak based on an aromatic ring quaternary carbon was recognized at 145.2 ppm, and it was found that the styrene chain had a syndiotactic structure.
Further, IR measurement of the copolymer after grafting revealed that absorption at 720 cm ^-1 and 730 cm ^-1 derived from a methylene chain was observed, and the absorption intensity of the vinyl group derived from the divinylbenzene residue was reduced. ₁₆₃₀ / D ₁₆₀₅ was found to be produced graft copolymer since decreased 0.16. To determine the copolymer composition, by changing the mixing ratio of the high-density polyethylene and syndiotactic polystyrene were measured IR, a calibration curve was prepared from the absorbance ratio of 720 cm ^-1 and 1605 cm ^-1. The weight ratio of styrene to ethylene thus determined was 1: 1.03. In addition, a 1,2,4-trichlorobenzene solution of
The reduced viscosity at a concentration of 0.05 g / dl measured at 35 ° C. was 1.66 dl / g.

Example 11 (1) Tri-n-tetra (pentafluorophenyl) borate
Preparation of butylammonium pentafluorophenyllithium prepared from bromopentafluorobenzene (152 mmol) and butyllithium (152 mmol) is reacted with 45 mmol of boron trichloride in hexane to give tri (pentafluorophenyl) boron in white. Obtained as a solid. Lithium tetra (pentafluorophenyl) boron was isolated as a white solid by reacting 41 mmol of this tri (pentafluorophenyl) boron with 41 mmol of lithium pentafluorophenyl. Next, by reacting 16 mmol of lithium tetra (pentafluorophenyl) boron and 16 mmol of tri-n-butylamine hydrochloride in water, tetra- (pentafluorophenyl) boron tri-n-butylammonium was obtained as a white solid. 8 mmol could be obtained.

(2) Production of Styrene-Divinylbenzene-Ethylene Copolymer Under an argon atmosphere, a dry 100 ml stainless steel reaction vessel was charged with 20 ml of styrene and 1.2 ml of divinylbenzene (the compound described in Example 1). Ingredients,
0.03 mmol of triisobutylaluminum (TIBA) was added and kept at 70 ° C. for 30 minutes. Further, 0.5 μmol of tetra (pentafluorophenyl) boron tri-n-butylammonium and 0.5 μmol of pentamethylcyclopentadienyltrimethyltitanium prepared in the above (1) were added, and the copolymerization was started with stirring. . After performing the reaction for 2 hours, 30 ml of dry toluene was added to make a slurry state, and a small amount was partially sampled to obtain a slurry.
R, ¹³ C-NMR was measured. 1630cm for IR
^-1 absorption of vinyl group divinylbenzene residues observed absorbance ratio of the 1605 cm ^-1 in styrene residues units (D ₁₆₃₀ / D ₁₆₀₅₎ was 0.31. Also, ¹³ C-N
MR measurement revealed a sharp peak at 145.2 ppm based on the aromatic ring quaternary carbon, indicating that the styrene chain had a syndiotactic structure. Further, in order to continue the graft reaction, ethylene was continuously introduced into the reaction system at 70 ° C. at 9 kg / cm ² G for 10 hours. After that, depressurize, put the copolymer in methanol,
After washing, it was air-dried to obtain 4.86 g of a copolymer. The copolymer was subjected to IR measurement and found to be 720 cm ⁻¹ , 73
At 0 cm ^-1 , absorption due to the methylene chain was observed, and the absorption intensity of the vinyl group derived from the divinylbenzene residue was reduced. D ₁₆₃₀ / D ₁₆₀₅ was reduced to 0.18. Turned out to be. In order to determine the copolymer composition, IR was measured while changing the mixing ratio of high-density polyethylene and syndiotactic polystyrene.
A calibration curve was prepared from the absorbance ratio of 20 cm ^-1 and 1605 cm ^-1. The weight ratio of styrene to ethylene thus determined was 1: 0.07. Moreover, 1,2,2 of this copolymer
Concentration measured at 135 ° C. in 4-trichlorobenzene solution
The reduced viscosity at 0.05 g / dl was 1.34 dl / g.

Example 12 After a reaction vessel equipped with a stirrer having an internal volume of 0.5 liter was replaced with nitrogen, the reaction vessel was heated to 70 ° C., and thoroughly dried toluene 5
0 ml, 50 ml of styrene, and divinylbenzene-containing monomer (divinylbenzene (meta-para mixture) 66.1
Wt%, ethyl styrene (meta-para mixture) 33.9
0.1% by weight) and 1.5 mmol of the methylaluminoxane obtained in Example 1 (2) and 1.5 mmol of triisobutylaluminum (TIBA).
Stirring was performed for 0 minutes. Next, 0.003 mmol of pentamethylcyclopentadienyltitanium trimethoxide was added and the reaction was carried out for 2 hours. After completion of the reaction, a large amount of hexane was added, and the copolymer was washed by a decantation method. Thereafter, the total volume was adjusted to 100 ml, and 3.0 mmol of a hexane solution of normal butyl lithium was added at 50 ° C., and the mixture was reacted for 2 hours. After the reaction, unreacted n-butyllithium was washed and removed in the same manner by a decantation method. The obtained copolymer was cooled to −78 ° C., the total volume was made 100 ml with hexane, 30 ml of glycidyl methacrylate was added, and graft copolymerization was performed for 12 hours. After the completion of the reaction, the mixture was poured into a large amount of methanol, washed and dried to obtain 17.8 g of a graft copolymer. When the obtained graft copolymer was subjected to Soxhlet extraction using methyl ethyl ketone as an extraction solvent, 93% was an insoluble portion. The reduced viscosity of the insoluble portion at a concentration of 0.05 g / dl measured at 135 ° C. in a 1,2,4-trichlorobenzene solution was 1.47 dl / g. Further, using a differential scanning calorimeter (DSC-200, manufactured by Seiko Denshi Co., Ltd.), 5.7 mg of a sample of the above copolymer was added to 50 to 31.
After the temperature was raised to 0 ° C at a rate of 20 ° C / min, the temperature was raised to 310 to 30 ° C.
The temperature was lowered at a rate of 0 ° C./min. Furthermore, 30-315 again
An endothermic pattern was observed when the temperature was raised to 20 ° C at a rate of 20 ° C / min. As a result, the graft copolymer was 263 ° C.
To have a melting temperature. Also, ¹³ C-NM
As measured by R, the syndiotacticity was more than 95% for racemic pentad. ^{According to 1} H-NMR measurement, the composition of the graft copolymer was 55 styrene units.
% Glycidyl methacrylate was found to be 45% by weight.

Example 13 A graft copolymer was synthesized in the same manner as in Example 12, except that the amount of glycidyl methacrylate was changed to 2 ml. After completion of the reaction, the mixture was poured into a large amount of methanol, washed and dried to obtain 6.73 g of a graft copolymer. When the obtained graft copolymer was subjected to Soxhlet extraction using methyl ethyl ketone as an extraction solvent, 97% was an insoluble portion. The reduced viscosity of the insoluble portion at a concentration of 0.05 g / dl measured at 135 ° C. in a 1,2,4-trichlorobenzene solution was 1.53 dl / g. Using a differential scanning calorimeter (DSC-200, manufactured by Seiko Denshi Co., Ltd.), 5.7 mg of a sample of the above copolymer was taken at 50 to 310 ° C.
Temperature at a rate of 20 ° C / min.
/ Min. Further, an endothermic pattern when the temperature was raised again to 30 to 315 ° C. at a rate of 20 ° C./min was observed. As a result, it was confirmed that the above graft copolymer had a melting temperature of 263 ° C. According to the measurement of ¹³ C-NMR, the syndiotacticity was 95% or more for racemic pentad. By measurement of ¹ H-NMR,
The composition of the graft copolymer was found to be 92% by weight of styrene units and 8% by weight of glycidyl methacrylate.

Example 14 Maleic anhydride 2 instead of glycidyl methacrylate
g and 2.1 g of styrene, using 50 mg of benzoyl peroxide as a radical polymerization initiator instead of normal butyryllithium, and graft-polymerizing at 70 ° C. for 4 hours. Was synthesized. After the reaction, put into a large amount of methanol,
After washing and drying, 6.0 g of the graft copolymer was obtained. When the obtained graft copolymer was subjected to Soxhlet extraction using methyl ethyl ketone as an extraction solvent, 98% was insoluble. The reduced viscosity of the insoluble portion at a concentration of 0.05 g / dl measured at 135 ° C. in a 1,2,4-trichlorobenzene solution was 1.37 dl / g. Further, using a differential scanning calorimeter (DSC-200, manufactured by Seiko Denshi Co., Ltd.), 5.7 mg of the above polymer sample was weighed from 50 to 310.
After the temperature was raised to 20 ° C / min at a rate of 20 ° C / min,
The temperature was lowered at a rate of ° C./min. 30-315 ° C again
An endothermic pattern was observed when the temperature was raised at a rate of 20 ° C./min. As a result, it was confirmed that the above graft copolymer had a melting temperature of 263 ° C. According to the measurement of ¹³ C-NMR, syndiotacticity was at least 93% in racemic pentad. ¹ H-NMR measurement revealed that the composition of the graft copolymer was 97% by weight of styrene units and 3% by weight of maleic anhydride.

Example 15 A reaction vessel equipped with a stirrer having an inner volume of 0.5 l was purged with nitrogen, heated to 70 ° C., and thoroughly dried with toluene 3
00ml, styrene 200ml and p- (3-butenyl)
Example 1 A mixture with 30 mmol of styrene was added.
12 mmol of the aluminoxane obtained in (2) and TIB
A12 mmol was added, and the mixture was stirred for 30 minutes. Then
15 μmol of pentamethylcyclopentadienyltitanium trimethoxide was added and reacted for 2 hours. After the completion of the reaction, the mixture was poured into a large amount of methanol, washed and dried to obtain 10.5 g of a copolymer. When the obtained copolymer was subjected to Soxhlet extraction using methyl ethyl ketone as an extraction solvent, 98% was insoluble. In addition, the insoluble part is 1, 2,
Concentration measured at 135 ° C. in 4-trichlorobenzene solution
The reduced viscosity at 0.05 g / dl was 2.0 dl / g. In addition, a differential scanning calorimeter (manufactured by Seiko Denshi Co., Ltd., D
SC-200), 5.7 m sample of the above copolymer
g at 50 to 310 ° C. at a rate of 20 ° C./min.
The temperature was lowered to 10 to 30 ° C at a rate of 20 ° C / min. further,
An endothermic pattern when the temperature was raised again to 30 to 315 ° C at a rate of 20 ° C / min was observed. As a result, the copolymer is
It was confirmed to have a melting temperature of 245 ° C. Also, ¹³
According to the C-NMR measurement, the syndiotacticity was at least 92% for racemic pentad. IR has 1
At 630 cm ^-1 , stretching vibration of a carbon-carbon double bond caused by the styrene unit was observed, and it was found that the copolymerization reaction with styrene proceeded mainly with the olefin unit of p- (3-butenyl) styrene. did. 5 g of this copolymer was dispersed in 100 ml of toluene under an argon atmosphere, and a graft copolymer was synthesized in the same manner as in Example 12 using 10 ml of glycidyl methacrylate. After the completion of the reaction, the reaction mixture was poured into a large amount of methanol, washed and dried, and the graft copolymer 6.5 was obtained.
g was obtained. When the obtained graft copolymer was subjected to Soxhlet extraction using methyl ethyl ketone as an extraction solvent, 96% was insoluble. In addition, this insoluble portion is
The reduced viscosity at a concentration of 0.05 g / dl measured at 135 ° C. in a 2,4-trichlorobenzene solution is 2.10 dl / g.
Met. Also, a differential scanning calorimeter (Seiko Electronics Co., Ltd.)
Sample of the above polymer using DSC-200)
After raising the temperature of 5.7 mg to 50 to 310 ° C at a rate of 20 ° C / min, the temperature was lowered to 310 to 30 ° C at a rate of 20 ° C / min. Further, an endothermic pattern when the temperature was raised again to 30 to 315 ° C. at a rate of 20 ° C./min was observed. As a result, it was confirmed that the graft copolymer had a melting temperature of 244 ° C. According to the measurement of ¹³ C-NMR, the syndiotacticity was 91% or more for racemic pentad.
¹ H-NMR measurement revealed that the composition of the graft copolymer was 80% by weight of styrene units and 20% by weight of glycidyl methacrylate. The IR has 16
The disappearance of the absorption line at 30 cm ^-1 confirmed that the product was a graft.

Example 16-1 (1) Production of Styrene-Divinylbenzene Copolymer (Graft Precursor) After replacing a reactor with an internal volume of 4.0 liters equipped with a stirrer with nitrogen, the reactor was heated to 70 ° C. Sufficiently dried toluene 2
50 ml, 1000 ml of styrene, and divinylbenzene-containing monomer (divinylbenzene (meta-para mixture)
66.1% by weight, ethyl styrene (meta-para mixture)
33.9% by weight) in 0.1 ml.
8.5 mmol of methylaluminoxane obtained in (1) and 8.5 mmol of triisobutylaluminum (TIBA) were added, and the mixture was stirred for 30 minutes. Then, pentamethylcyclopentadienyl titanium trimethoxide was added to 0.043
The reaction was carried out for 5 hours with the addition of mmol. After completion of the reaction, methanol was injected to stop the reaction, and the polymer was washed with methanol acetate to decompose the catalyst component. The obtained copolymer was washed with methyl ethyl ketone (containing 2% by weight of pt-butylcatechol) at 50 ° C. for 4 hours.
% Was insoluble. This insoluble matter was dissolved in chloroform, and a chloroform solution of a styrene copolymer was obtained from the soluble matter. The weight average molecular weight of the styrene copolymer soluble in chloroform is 724,000, and the number average molecular weight is 24.
It was 3,000. In addition, as a result of using a differential scanning calorimeter (DSC-II, manufactured by PerkinElmer), it was confirmed that the graft copolymer had a melting temperature at 268 ° C and a glass transition temperature at 98 ° C. ^{By 13} C-NMR measurement, an aromatic ring C ₁ carbon signal was observed at 145.2 ppm, confirming that it had a syndiotactic structure. In IR, absorption of a vinyl group of a divinylbenzene residue was observed at 1630 cm ^-1 .

(2) n-phenylmaleimide (nPM
I) Grafting reaction The styrene-divinylbenzene copolymer obtained in the above (1) was washed with toluene, further thoroughly washed with methanol, and dried under reduced pressure at 40 ° C. 140 g was charged into a reactor equipped with a stirrer, and was replaced with nitrogen. Next, 420 ml of sufficiently dried toluene was added, and the mixture was heated to 50 ° C. and the inside of the system was gently stirred. 1
After an hour, sufficiently dry THF is added to 200 ml of nPMI.
A solution in which 45.9 g was dissolved and THF which had been dried in the same manner.
A solution in which 2.13 g of azobisisobutyronitrile (AIBN) as a radical initiator was added to 30 ml,
After raising the temperature in the system to 70 ° C., the reaction was carried out for 5 hours. The reaction was stopped by charging methanol, and acetone (nPM
Washing was sufficiently performed using a good solvent of I) and N, N-dimethylformamide (a good solvent of poly-nPMI). After the completion of the reaction, the mixture was poured into a large amount of methanol, washed and dried to obtain 163 g of a graft copolymer. The obtained copolymer was insoluble in 90% of this washing treatment. The reduced viscosity of the insoluble portion at a concentration of 0.05 g / dl measured at 135 ° C. in a 1,2,4-trichlorobenzene solution was 1.30.
dl / g. Further, using a differential scanning calorimeter (DSC-200, manufactured by Seiko Denshi Co., Ltd.), 5.7 mg of the polymer sample was heated to 50 to 310 ° C. at a rate of 20 ° C./min, and then heated to 310 to 30 ° C. The temperature was lowered at a rate of 20 ° C./min. Further, an endothermic pattern when the temperature was raised again to 30 to 315 ° C. at a rate of 20 ° C./min was observed. As a result, it was confirmed that the graft copolymer had a melting temperature of 265 ° C. In addition, ¹³ C-NMR of the graft copolymer
As a result, an aromatic signal derived from the syndiotactic structure was observed at 145.4 ppm. Furthermore, according to the measurement of ¹³ C-NMR, syndiotacticity was 94% or more for racemic pentad. ¹ H-
According to NMR measurement, nPMI of the above graft copolymer was determined.
Was found to be 8% by weight. In the IR, the absorption peak at 1630 cm ^{-1 due} to the double bond of divinylbenzene disappeared, and the (C) of nPMI was newly added to 1710 cm ^-1.
= O) The appearance of a peak was confirmed.

Examples 16-2 to 16-14 The reaction was carried out in the same manner as in Example 16-1, except for the conditions shown in Table 1. In the graft reaction, when the monomer is α
-In the case of methylstyrene, the precursor is n-heptane 60
After cooling to −78 ° C., the mixture was stirred gently, and 5 ml of a methylene chloride solution (1 mol / l) of triethyloxonium boron tetrafluoride and sufficiently dried α-methylstyrene were added, and the mixture was inverted for 6 hours. Was. Further, in the grafting reaction, when the monomer is norbornene, the precursor is added to 420 ml of toluene, heated to 50 ° C., and then gently stirred to give 0.75 ml of a nickel acetylacetonate solution (0.02 mol / l). , 3 mmol of methylaluminoxane and a toluene solution of norbonene (6.7 mol / l) were added, and the mixture was inverted for 6 hours. In Examples 16-1, 16-10, and 16-14, the obtained styrene-based graft polymer was treated at a cylinder temperature of 3%.
A test piece was obtained by pelletizing using a twin-screw kneader at 00 ° C. and injection molding at 300 ° C., and further heat-treated at 230 ° C. for 10 minutes. The heat distortion temperature (HDT;
JIS-K7270) and flexural modulus (JIS-K7)
203). Table 1 shows the obtained results. Here, as a physical property standard, the syndiotactic polystyrene has a heat deformation temperature of 100.3 ° C. and a flexural modulus of 39,500.
kg / cm ² .

[0108]

[Table 1]

[0109]

[Table 2]

[0110]

[Table 3]

[0111]

[Table 4]

Example 17 10 g of the styrene-p- (3-butenyl) styrene copolymer having a syndiotactic structure produced in Example 15 was
In an argon atmosphere, the mixture was dispersed in 200 ml of toluene, and 30 ml of p-bromostyrene and 0.31 g of azobisisobutyronitrile (AIBN) were added.
The reaction was performed at a temperature of 5 ° C. for 5 hours. After completion of the reaction, the reaction was stopped by pouring into a large amount of methanol, followed by washing and drying to obtain 13.7 g of a copolymer. When the obtained copolymer was subjected to Soxhlet extraction using methyl ethyl ketone as an extraction solvent, 93% was an insoluble portion. When the insoluble portion was measured in the same manner as in Example 15, the reduced viscosity was 1.90 dl / g.
Met. In addition, it was confirmed that the copolymer had a melting temperature of 246 ° C. Furthermore, the content of p-bromostyrene in the above graft copolymer was 20.1% by weight, and the absorption line at 1630 cm ^-1 disappeared in IR, confirming that the graft copolymer was obtained.

The styrenic copolymer of the present invention is one in which the syndiotactic polystyrene retains the heat resistance, chemical resistance, etc., and the compatibility, adhesion, coating properties and wettability are remarkably improved. is there. Therefore, the styrenic copolymer of the present invention can be easily compounded with other resins, glass fiber, talc, metal, etc., and can be applied to composite materials of syndiotactic styrenic resin. Is what you do. Further, the styrene copolymer of the present invention is effectively used as various resin modifiers, compatibilizers, multilayer materials and the like.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 212/08 C08F 4/645 C08F 212/00 C08F 212/34 C08F 257/02

Claims (8)

(57) [Claims] 1. A catalyst comprising a styrene-based monomer and a hydrocarbon-group-containing styrene-based monomer having an unsaturated bond as a main component, which comprises a contact product of (A) a transition metal compound and (B) an organoaluminum compound with a condensing agent. A method for producing a styrene-based graft copolymer, comprising copolymerizing in the presence of styrene and then graft-polymerizing an ethylenically unsaturated monomer to the obtained styrene-based copolymer. 2. A styrene-based monomer and a styrene-based monomer having a hydrocarbon group having an unsaturated bond are reacted with (A) a transition metal compound and (C) a compound capable of forming an ionic complex by reacting with the transition metal compound. A method for producing a styrene-based graft copolymer, comprising copolymerizing in the presence of a catalyst as a component, and then graft-polymerizing an ethylenically unsaturated monomer to the obtained styrene-based copolymer. 3. The method for producing a styrene-based graft copolymer according to claim 1, wherein the styrene-based copolymer has a syndiotactic structure. 4. A styrenic monomer represented by the general formula [1]: [Wherein, R ¹ represents a hydrogen atom, a halogen atom or a carbon atom,
A substituent containing at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom; However, when m is plural, each R ¹ may be the same or different. A styrene-based monomer I represented by the formula
General formula [2] [Wherein, R ² represents a hydrocarbon group having an unsaturated bond,
n shows the integer of 1 or 2. R ¹ and m are the same as above. Styrene-based monomer II represented by
The ethylenically unsaturated monomer is represented by the general formula [3] [Wherein Q ¹ , Q ² , Q ³ and Q ⁴ are each one of a hydrogen atom, a halogen atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom. A substituent containing at least one kind is shown, and these Q ^{1 to} Q ⁴ may be the same or different. ]
The method for producing a styrenic graft copolymer according to any one of claims 1 to 3, which is represented by: 5. An ethylenically unsaturated monomer comprising: (1) acrylic acid, methacrylic acid, a derivative thereof, (2) acrylamide, methacrylamide, a derivative thereof, (3) vinyl acetate, a derivative thereof, (4) Cinnamic acid, crotonic acid, their derivatives, (5) acrylonitrile, methacrylonitrile, their derivatives, (6) maleic acid, fumaric acid,
Maleic anhydride, their derivatives, (7) maleimide, its derivatives, (8) itaconic acid, itaconic anhydride, their derivatives, (9) acroleins, (10) vinyl ketones, (1
The method for producing a styrene-based graft copolymer according to any one of claims 1 to 4, which is 1) a diene, (12) styrene, a derivative thereof, (13) an α-olefin, or (14) a cyclic olefin. 6. A synth comprising a styrene monomer and a styrene monomer containing a hydrocarbon group having an unsaturated bond.
A styrene-based graft copolymer obtained by graft-polymerizing an ethylenically unsaturated monomer onto a copolymer having a geotactic structure . 7. The ethylenically unsaturated monomer is styrene graft copolymer of claim 6 wherein the polar group-containing monomer. 8. A graft component having a content of 0.005 to 99% by weight and a content of 1: 1 in 1,2,4-trichlorobenzene.
The styrene-based graft copolymer according to claim 6 , wherein the reduced viscosity at a concentration of 0.05 g / dl measured at 35 ° C is 0.01 to 20 dl / g.