JP2904898B2 - Styrene copolymer and method for producing the same - Google Patents

Description

The present invention relates to a styrenic copolymer and a method for producing the same, and more particularly to a styrenic copolymer derived from a styrene-based monomer and an unsaturated hydrocarbon monomer containing a hetero atom. The present invention relates to a styrenic copolymer having a specific three-dimensional structure composed of structural units having the same structure and an efficient production method thereof.

[Problems to be solved by conventional technology and invention]

Conventionally, styrene-based polymers 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, furniture, synthetic paper, and the like. Although it is widely used as an industrial material, it has a drawback that its three-dimensional structure has an atactic structure and is inferior in heat resistance and chemical resistance.

The group of the present inventors has succeeded in developing a styrene-based polymer mainly having a syndiotactic structure so far, as a solution to the disadvantage of the styrene-based polymer having an atactic structure. Styrene-based copolymers obtained by copolymerizing monomers and other components have also been developed (JP-A-62-104818, JP-A-62-187708, and JP-A-63-241009).

These polymers are excellent in heat resistance, chemical resistance and electrical properties, and are expected to be applied in various fields.

However, the styrenic (co) polymers described above are liable to cause troubles in the molding process due to static electricity, easily adhere dust to molded products, or generate noise in electrical signals (VT
As in general styrene-based polymers such as reels for R), problems such as high insulation resistance and easy electrification remain unsolved.

In order to improve this, it is usual to mix an antistatic agent or to perform a surface treatment on the surface of the molding material. However, the method in which an antistatic agent is mixed lacks the continuity of the effect, and has a problem in compatibility with the resin. On the other hand, the method in which the surface treatment is performed complicates a processing step.

Then, the present inventors continued intensive research in order to develop a styrene-based copolymer having a high syndiotacticity having an antistatic effect.

[Means for solving the problem]

As a result, using a copolymer having a structural unit derived from a styrene-based monomer and a structural unit derived from an unsaturated hydrocarbon monomer containing a hetero atom and using a copolymer having a syndiotactic structure can solve the above problem. I found it. The present invention has been completed based on such findings.

That is, the present invention relates to a compound represented by the general formula [I]: [In the formula, R ¹ represents a hydrogen atom, a halogen atom, or a substituent containing at least one of a carbon atom, a tin atom and a silicon atom, and m represents an integer of 1 to 5. However, when m is plural, each R ¹ may be the same or different. At least one structural unit [I] and a general formula [II] [Wherein R ² is a hydrogen atom, a halogen atom or a carbon atom 1
Represents 20 to 20 hydrocarbon residues, and R ³ and R ⁴ are each a carbon atom, a nitrogen atom, a sulfur atom, a silicon atom, an oxygen atom,
A substituent or element containing at least one of a hydrogen atom and a metal ion, which may be the same or different. n is an integer of 0 or more and 20 or less. And the structural unit [II] contains 0.01 to 99.9 mol% at 135 ° C.
The intrinsic viscosity measured in 1,2,4-trichlorobenzene is 0.01 to 20 dl / g, and the stereoregularity of the chain of the structural unit [I] is mainly a zindiotactic structure. To provide a styrenic copolymer.

The present invention also relates to a compound of the general formula [I '] Wherein R ¹ and m are the same as above. Is polymerized in the presence of a catalyst comprising a transition metal compound and an aluminoxane, and then the polymerization reaction system of the general formula [II '] Wherein R ² , R ³ , R ⁴ and n are the same as above. ] It is intended to provide a method for producing the styrenic copolymer, characterized by adding a monomer represented by the following formula to carry out a copolymerization reaction.

Here, the structural unit (repeating unit) represented by the general formula [I] is derived from the styrene monomer represented by the general formula [I ']. The styrenic copolymer of the present invention comprises a repeating unit represented by the general formula [I] and a structural unit (repeating unit) represented by the general formula [II] as described above.
Consists of

Specific examples of the styrene monomer represented by the general formula [I '] include styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene; 2,4-dimethylstyrene;
2,5-dimethylstyrene; 3,4-dimethylstyrene; 3,5-
Dimethyl styrene; alkyl styrene such as p-tert-butyl styrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m
-Fluorostyrene, o-fluorostyrene, o-methyl-
halogenated styrene such as p-fluorostyrene, 4-
Vinyl biphenyls such as vinyl biphenyl, 3-vinyl biphenyl and 2-vinyl biphenyl, 1- (4-vinyl phenyl) -naphthalene, 2- (4-vinyl phenyl) -naphthalene, 1- (3-vinyl phenyl) -naphthalene , 2−
Vinylphenylnaphthalenes such as (3-vinylphenyl) -naphthalene, 1- (2-vinylphenyl) -naphthalene, 2- (2-vinylphenyl) 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)-
Vinylphenylanthracenes such as anthracene, 9- (2-vinylphenyl) -anthracene, 1- (4-vinylphenyl) -phenanthrene, 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- (3-vinylphenyl) -phenanthrene, 4- (3-vinylphenyl)
-Phenanthrene, 9- (3-vinylphenyl) -phenanthrene, 1- (2-vinylphenyl) -phenanthrene, 2- (2-vinylphenyl) -phenanthrene, 3-
Vinylphenylphenanthrenes such as (2-vinylphenyl) -phenanthrene, 4- (2-vinylphenyl) -phenanthrene, 9- (2-vinylphenyl) -phenanthrene, 1- (4-vinylphenyl) -pyrene, 2-
(4-vinylphenyl) -pyrene, 1- (3-vinylphenyl) -pyrene, 2- (3-vinylphenyl) -pyrene, 1
Vinylphenylpyrenes such as-(2-vinylphenyl) -pyrene and 2- (2-vinylphenyl) -pyrene;
Vinyl-p-terphenyl, 4-vinyl-m-terphenyl, 4-vinyl-o-terphenyl, 3-vinyl-p-terphenyl, 3-vinyl-m-terphenyl, 3-vinyl-o
Vinyl terphenyls such as -terphenyl, 2-vinyl-p-terphenyl, 2-vinyl-m-terphenyl, 2-vinyl-o-terphenyl, and 4- (4-vinylphenyl) -p-terphenyl Vinylphenyl terphenyls, 4-vinyl-4'-methylbiphenyl, 4-vinyl-3'-methylbiphenyl, 4-vinyl-2'-methylbiphenyl, 2-methyl-4-vinylbiphenyl, 3-methyl Vinylalkyl biphenyls such as -4-vinyl biphenyl, 4-vinyl-4'-fluorobiphenyl, 4-vinyl-3'-fluorobiphenyl, 4-vinyl-2'-fluorobiphenyl, 4-vinyl-2-fluorobiphenyl , 4-vinyl-3-fluorobiphenyl, 4-vinyl-
4'-chlorobiphenyl, 4-vinyl-3'-chlorobiphenyl, 4-vinyl-2'-chlorobiphenyl, 4-vinyl-2-chlorobiphenyl, 4-vinyl-3-chlorobiphenyl, 4-vinyl-4 ' -Bromobiphenyl, 4-vinyl-
3'-bromobiphenyl, 4-vinyl-2'-bromobiphenyl, 4-vinyl-2-bromobiphenyl, 4-vinyl-
Halogenated vinyl biphenyls such as 3-bromobiphenyl, trialkylsilylvinyl biphenyls such as 4-vinyl-4'-trimethylsilylbiphenyl, 4-vinyl-4'-trimethylstannylbiphenyl, 4-vinyl-4'-tributyl Trialkylstannylvinylbiphenyls such as stannylbiphenyl, 4-vinyl-
Trialkylsilylmethylvinylbiphenyls such as 4'-trimethylsilylmethylbiphenyl, 4-vinyl-
Trialkylstannylmethylvinylbiphenyls such as 4'-trimethylstannylmethylbiphenyl and 4-vinyl-4'-tributylstannylmethylbiphenyl;
p-chloroethylstyrene, m-chloroethylstyrene, o
Halogen-substituted alkylstyrenes such as -chloroethylstyrene, p-trimethylsilylstyrene, m-trimethylsilylstyrene, o-trimethylsilylstyrene, p-triethylsilylstyrene, m-triethylsilylstyrene, o
-Alkylsilylstyrenes such as -triethylsilylstyrene, p-dimethyltert-butylsilylstyrene, phenyl group-containing silylstyrenes such as p-dimethylphenylsilylstyrene, p-methyldiphenylsilylstyrene and p-triphenylsilylstyrene; Halogen-containing silylstyrenes such as -dimethylchlorosilylstyrene, p-methyldichlorosilylstyrene, p-trichlorosilylstyrene, p-dimethylbromosilylstyrene, p-dimethyliodosilylstyrene, and p- (p-trimethylsilyl) dimethylsilylstyrene And the like, or a mixture of two or more thereof.

On the other hand, the repeating unit represented by the general formula [II] is derived from an unsaturated hydrocarbon monomer containing a hetero atom represented by the general formula [II ']. Examples of the unsaturated hydrocarbon monomer containing a hetero atom represented by the general formula (II ′) include acrylamide, N-monoalkyl derivatives, N, N-dialkyl derivatives, N-hydroxyalkyl derivatives, N-haloalkyl derivatives, N-cyano Alkyl derivatives, formalin adducts, bisacrylamide derivatives, bismethacrylamide derivatives, N-aminoalkyl derivatives, N-sulfonalkyl derivatives, quinoalkyl derivatives, amino acid derivatives,
Examples include ester derivatives, hydrazine derivatives, azo derivatives, diamine derivatives, diamide derivatives, heterocyclic derivatives, quinone derivatives and the like. Specific examples include acrylamide, methacrylamide, N-methylacrylamide; N-ethylacrylamide, N-isopropylacrylamide;
N-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) acrylamide; 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-dodecylacrylamide; 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-dimethylpicyclo [3,2,0]
Hept-6-nyl) acrylamide; N-allylacrylamide; N- (1,1-dimethylpropyl) acrylamide;
N-benzylacrylamide; N-phenylacrylamide; N- (2-methylphenyl) acrylamide; N- (4
-Methylphenyl) acrylamide; N- (1-naphthyl) acrylamide; N- (2-naphthyl) acrylamide; N-methylmethacrylamide; N-ethylmethacrylamide; Nn-butylmethacrylamide; N-tert-butylmethacryl Amide; N-n-octyl methacrylamide; N
-N-dodecyl methacrylamide; N-cyclohexyl methacrylamide; N- (7,7-dimethylpicyclo [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) methacrylamide; N- (3-methylphenyl) methacrylamide; N- (4-methylphenyl) methacrylamide;
(2,3-dimethylphenyl) methacrylamide; N- (2
-Phenylphenyl) methacrylamide; N- (2-hydroxyphenyl) methacrylamide; N- (2-methoxyphenyl) methacrylamide; 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-dibenzylacrylamide; N, N-bis (2-ethylhexyl) acrylamide; N-methyl-N-phenylacrylamide; N-acryloylpyrrolidine; N-acryloylpiperidine; N-acryloylmorpholine; N-acryloylthiamorpholine; N, N-dimethylmethacrylamide; N, N-diethylmethacrylamide; N, N-diphenylmethacrylamide; N-methyl-N-phenylmethacrylamide; N-methacryloylpiperidine; 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- Chill 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-trifluoro Ethyl) acrylamide;
N- (3,3,3-trifluoropropyl) acrylamide; N
-(3,3-difluorobutyl) acrylamide; N, N-bis (2,2,2-trifluoroethyl) acrylamide; ethyl-2-acrylamide acetate; acryloyldicyandiamide; methacryloyldicyandiamide; 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; N, N-bis (2-cyanoethyl) acrylamide; N- (4-cyano-2,2,6,6-
Tetramethyl-4-pipericyl) 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-butoxymethyl) acrylamide; N, N'-methylenebisacrylamide;1,2-bisacrylamidoethane;1,3-bisacrylamidopropane;1,4-bisacrylamidobutane;1,5-bisacrylamidopentane;1,6-bisacrylamidohexane;1,7-bisacrylamidoheptane;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-methacryloyl Glycinimide; N- (2-dimethylaminoethyl) acrylamide; N- (2-diethylaminoethyl) acrylamide; N
-(2-morpholinoethyl) acrylamide; N- (3-
Dimethylaminopropyl) acrylamide; N- (3-propylaminopropyl) acrylamide; N- [3-bis (2-hydroxyethyl) aminopropyl] acrylamide; N- (1,1-dimethyl-2-dimethylaminoethyl) acrylamide N- (2,2-dimethyl-3-dimethylaminopropyl) 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-acrylamide-2,4,4-trimethylpentanesulfonic acid; 2-acrylamide-2-methylphenylethanesulfonic acid; 2-acrylamide-2- (chlorophenyl) propanesulfonic acid; 2-acrylamide -2-carboxymethylpropanesulfonic acid; 2-acrylamide-
2- (pyridyl) propanesulfonic acid; 2-acrylamide-1-methylpropanesulfonic acid; 3-acrylamide-3-methylbutanesulfonic acid; 2-methacrylamide-
n-decanesulfonic acid: 2-methacrylamide-n-tetradecanesulfonic acid: sodium 4-methacrylamidobenzenebenzenesulfonate, and the like, or two or more of these components.

In the styrenic copolymer of the present invention, the repeating unit [I] may be composed of two or more components,
This is the same for the repeating unit [II]. Therefore, binary, ternary and quaternary copolymers are possible. The content of the repeating unit [II] is usually in the range of 0.01 to 99.9% by weight, preferably 0.01 to 80% by weight, and more preferably 0.1 to 60% by weight of the whole copolymer. If the content of the repeating unit [II] is less than 0.01% by weight, the desired improvement effects of the present invention, such as improvement in antistatic properties, cannot be sufficiently achieved.

On the other hand, when the content exceeds 99.9% by weight, the heat resistance characteristic of the styrene polymer having a syndiotactic structure is not exhibited. The molecular weight of this copolymer is generally such that the intrinsic viscosity measured in a 1,2,4-trichlorobenzene solution (temperature 135 ° C.) is 0.0
It is 1-20 dl / g, preferably 0.1-15 dl / g. If the intrinsic viscosity is less than 0.01 dl / g, the mechanical properties are low and cannot be put to practical use. On the other hand, if the intrinsic viscosity exceeds 20 dl / g, it is not suitable for ordinary melt molding.

In the present invention, a third component may be added within a range that does not significantly impair the properties of the obtained copolymer or the syndiotactic structure in the chain of the repeating unit [I]. Such compounds include, for example, dienes,
Examples include vinylsiloxanes, unsaturated carboxylic esters, acrylonitrile, and the like.

The styrenic copolymer of the present invention has a highly repeating syndiotactic structure of the repeating unit [I], that is, the styrene repeating unit. Here, the advanced syndiotactic structure in the styrene-based polymer refers to a highly syndiotactic structure having a stereochemical structure having a high stereochemical structure, that is, a phenyl group or a substituted side chain with respect to a main chain formed from carbon-carbon bonds. The phenyl group has a steric structure in which the phenyl groups are alternately located in opposite directions, and its tacticity is quantified by nuclear magnetic resonance ( ¹³ C-NMR) using isotope carbon. Tacticity measured by ¹³ C-NMR method is
The abundance ratio of a plurality of continuous structural units, for example, a diad for two, a triad for three, and a pentad for five, can be represented by a high syndiotactic structure referred to in the present invention. A styrene-based copolymer having at least 75%, preferably at least 85%, or at least 30%, preferably at least 50%, of racemic dyads in a chain of styrene-based repeating units. The one having tisity is shown. However, the degree of syndiotacticity slightly varies depending on the type of the substituent and the content of the repeating unit [II].

The copolymer of the present invention as described above has a repeating unit [I],
An embodiment having desired stereoregularity and reactive substituents by monomer copolymerization corresponding to [II], and by applying separation, blending or organic synthetic techniques using the obtained copolymer as a raw material. Things can be manufactured.

Among them, according to the production method of the present invention described above, a styrene-based copolymer with higher efficiency and higher quality can be obtained.

The raw material monomers used in the production method of the present invention are a styrene monomer represented by the general formula [I '] and an unsaturated hydrocarbon monomer containing a hetero atom represented by the general formula [II']. The styrene monomer and the unsaturated hydrocarbon monomer containing a hetero atom are polymerized to form repeating units [I] and [II], respectively. Accordingly, specific examples of the styrene monomer and the unsaturated hydrocarbon monomer containing a hetero atom include those corresponding to the specific examples of the above-mentioned repeating units [I] and [II].

The method of the present invention, these styrenic monomers,
Polymerization is carried out in the presence of a catalyst comprising (A) a transition metal compound and (B) an aluminoxane as a main component, and then the obtained styrene-based polymer or oligomer is copolymerized with an unsaturated hydrocarbon monomer containing a hetero atom to form a copolymer. This is a method for producing a polymer.

Here, there are various transition metal compounds as the component (A) of the catalyst. [Wherein, R ^{5 to} R ¹⁶ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms. An arylalkyl group, an aryloxy group having 6 to 20 carbon atoms,
It represents an acyloxy group having 1 to 20 carbon atoms, acetylacetonyl group, cyclopentadienyl group, substituted cyclopentadienyl group or indenyl group. A, b, and c each represent an integer of 0 or more satisfying 0 ≦ a + b + c ≦ 4, d and e each represent an integer of 0 or more satisfying 0 ≦ d + e ≦ 3, and f represents 0 ≦ f ≦ 2. And g and h each represent an integer of 0 or more that satisfies 0 ≦ g + h ≦ 3. Further, M ¹ and M ² represent titanium, zirconium, hafnium or vanadium, and M ³ and M ⁴ represent vanadium. ] At least one compound selected from the transition metal compounds represented by Among these transition metal compounds,
Preferably, M ¹ in the general formula (III) is titanium or zirconium.

Here, among those represented by R ^{5 to} R ¹⁶ in the above formula,
As the halogen atom, specifically, a chlorine atom, a bromine atom,
There is an iodine atom or a fluorine atom. The substituted cyclopentadienyl group is, for example, a cyclopentadienyl group substituted by one or more alkyl groups having 1 to 6 carbon atoms, specifically, a methylcyclopentadienyl group; Pentadienyl group; 1,3-dimethylcyclopentadienyl group; 1,3,4-trimethylcyclopentadienyl group; pentamethylcyclopentadienyl group and the like. R ^{5 to} R ¹⁶ in the above formula are each independently a hydrogen atom,
To 20 alkyl groups (specifically, a methyl group, an ethyl group,
Propyl group, n-butyl group, isobutyl group, amyl group, isoamyl group, octyl group, 2-ethylhexyl group), alkoxy group having 1 to 20 carbon atoms (specifically, methoxy group, ethoxy group, propoxy group, butoxy group) Group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, etc.), aryl group having 6 to 20 carbon atoms (specifically, phenyl group, naphthyl group, etc.), arylalkyl group having 7 to 20 carbon atoms ( Specifically, it may be a benzyl group, a phenethyl group, a 9-anthrylmethyl group, etc.) or an acyloxy group having 1 to 20 carbon atoms (specifically, an acetyloxy group, a stearoyloxy group, etc.). These R ^{5 to} R ¹⁶ may be the same or different as long as the above conditions are satisfied.

Specific examples of the titanium compound among the transition metal compounds represented by the general formulas [III], [IV], [V], and [VI] include tetramethoxytitanium, tetraethoxytitanium, and tetra-n- Butoxytitanium, tetraisopropoxytitanium, titanium tetrachloride, titanium trichloride, cyclopentadienyltrimethyltitanium, cyclopentadienyltriethyltitanium, cyclopentadienyltripropyltitanium, cyclopentadienyltributyltitanium, methylcyclopentadienyl Trimethyl titanium, 1,2
Dimethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltripropyltitanium,
Pentamethylcyclopentadienyltributyltitanium,
Cyclopentadienylmethyltitanium dichloride, cyclopentadienylethyltitanium dichloride, pentamethylcyclopentadienylmethyltitanium dichloride, pentamethylcyclopentadienylethyltitanium dichloride,
Cyclopentadienyl dimethyl titanium monochloride, cyclopentadienyl diethyl titanium monochloride, cyclopentadienyl titanium trimethoxide, cyclopentadienyl titanium triethoxide, cyclopentadienyl titanium tripropoxide, cyclopentadienyl titanium Triphenoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium triethoxide, pentamethylcyclopentadienyl titanium tripropoxide, pentamethylcyclopentadienyl titanium tributoxide, pentamethylcyclopenta Dienyl titanium triphenoxide, cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl methoxy tita Dichloride, cyclopentadienyldimethoxytitanium chloride, pentamethylcyclopentadienylmethoxytitanium dichloride, cyclopentadienyltribenzyltitanium, pentamethylcyclopentadienylmethyldiethoxytitanium, indenyltitaniumtrichloride, indenyltitaniumtrimethoxy , Indenyltitanium triethoxide, indenyltrimethyltitanium, indenyltribenzyltitanium and the like.

When it is necessary to increase the molecular weight of the styrene-based monomer portion among these titanium compounds, a titanium compound having a substituted π-electron ligand such as an alkoxide or a substituted cyclopentadienyl group is preferable. When the molecular weight is reduced, a titanium compound having a π-electron ligand such as a cyclopentadienyl group or a halogen ligand is preferable.

In addition, the general formula [III], [IV], [V] or [V
Specific examples of the zirconium compound among the transition metal compounds represented by I] include cyclopentadienyl zirconium trimethoxide, pentamethylcyclopentadienyl zirconium trimethoxide, cyclopentadienyl tribenzyl zirconium, and pentamethylcyclopentadienyl zirconium. Examples include pentadienyl tribenzyl zirconium, bisindenyl zirconium dichloride, zirconium dibenzyl dichloride, zirconium tetrabenzyl, tributoxy zirconium chloride, and triisopropoxy zirconium chloride.

Similarly, specific examples of the hafnium compound include cyclopentadienyl hafnium trimethoxide, pentamethylcyclopentadienyl hafnium trimethoxide, cyclopentadienyl tribenzyl hafnium, pentamethylcyclopentadienyl tribenzyl hafnium, bis Indenyl hafnium dichloride, hafnium dibenzyl dichloride, hafnium tetrabenzyl, tributoxy hafnium chloride, triisopropoxy hafnium chloride and the like can be mentioned.

Similarly, specific examples of the vanadium compound include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, and vanadyl triacetylacetonate. Can be

On the other hand, the aluminoxane (B) as another component of the catalyst is, for example, of the same kind as that described in JP-A-62-187708, and is described in detail below.

That is, it is obtained by contacting various kinds of organic aluminum with a condensing agent.

Here, as the organic aluminum compound, usually, in the general formula AlR ¹⁷ ₃ [wherein, R ¹⁷ represents an alkyl group having 1 to 20 carbon atoms. ], Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, among which trimethylaluminum is most preferred.

On the other hand, as the condensing agent, water is typically mentioned, and in addition to this, any other agent capable of condensing trialkylaluminum, such as copper sulfate pentahydrate, water adsorbed on inorganic or organic substances, etc. Is mentioned.

Aluminoxanes as the component (B) of the catalyst used in the present invention, the general formula AlR ¹⁷ has contact product of trialkylaluminum and water, represented by _3, but specifically, the general formula [In the formula, R ¹⁸ is an alkyl group having 1 to 8 carbon atoms, q indicates a degree of polymerization, and is a number of 2 to 52. A chain alkylaluminoxane represented by the general formula Wherein R ¹⁸ and q are the same as above. And a cyclic alkylaluminoxane having a repeating unit represented by the formula: Among such alkylaluminoxanes, R
¹⁸ is particularly preferably methylaluminoxane which is a methyl group.

In general, a contact product of an organoaluminum compound such as a trialkylaluminum and water is mixed with an unreacted trialkylaluminum, various condensation products together with the above-mentioned chain alkylaluminoxane or cyclic alkylaluminoxane, Are complexly associated molecules, and these are various products depending on the contact conditions between the trialkylaluminum and water.

The method of contacting the organoaluminum compound with water at this time is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization, and then water is added later, and furthermore, a method in which a metal salt or the like is contained There is a method of reacting water of crystallization, water adsorbed on inorganic or organic substances with an organoaluminum compound. The water may contain up to about 20% of ammonia, amines such as ethylamine, sulfur compounds such as hydrogen sulfide, and phosphorus compounds such as phosphite.

In the present invention, the aluminoxane (for example, alkylaluminoxane) used as the component (B) of the catalyst, when a hydrated compound is used after the above-mentioned contact reaction, the solid residue is separated by filtration, and the filtrate is treated under normal pressure or reduced pressure. At a temperature of ~ 200 ° C, preferably at a temperature of 40 ~ 150 ° C, for 20 minutes to 8 hours,
Preferably, the mixture is heat-treated while distilling off the solvent for a period of 30 minutes to 5 hours. In this heat treatment, the temperature may be appropriately determined depending on various conditions, but is usually in the above range. In general, at a temperature lower than 30 ° C., no effect is exhibited, and at a temperature higher than 200 ° C., thermal decomposition of the alkylaluminoxane itself occurs, and both are not preferred.

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

Suitable examples of such catalysts (B) aluminoxane used as component, in particular alkyl aluminoxane, aluminum is observed by proton nuclear magnetic resonance spectrum - methyl (Al-CH ₃₎ high magnetic field in the methyl proton signal region based on binding The component is less than 50%. That is, when the above contact product is observed for its proton nuclear magnetic resonance ( ¹ H-NMR) spectrum in a toluene solvent at room temperature, the methyl proton signal based on Al—CH ₃ is 1.0% based on tetramethylsilane (TMS). It is found in the range of -0.5 ppm. TMS proton signal (0 ppm) is Al-C
Because of the methyl protons observation area based on the H _3, the Al
Methyl proton signal based on -CH _3, high magnetic field component is measured based on the methyl proton signal 2.35ppm toluene in TMS standard (i.e., -1.0 to-0.5 ppm) and other magnetic field component (i.e., 1.0 to-0.1 ppm)
Those having a high magnetic field component of 50% or less, preferably 45 to 5% of the whole can be suitably used as the component (B) of the catalyst.

The catalyst used here is mainly composed of the above-mentioned components (A) and (B). In addition to the above, another catalyst component (C) can be further added as required, whereby the catalyst component can be added. By adding (C), the catalytic activity can be significantly improved.

The catalyst component (C), for example the general formula AlR ¹⁹ ₃ wherein, R ¹⁹ is a hydrogen atom, 1 to halogen atoms or carbon atoms
8 represents an alkyl group. Etc. can be added trialkyl aluminum or other organometallic compounds represented by], also in the scope of not impairing the stereoregularity of the general formula ^{W-R 20 - (P)} r -R 21 -W '... ( VII) [wherein, R ²⁰ and R ^{21 each} have a hydrocarbon group having 1 to 20 carbon atoms, a substituted aromatic hydrocarbon group having 7 to 30 carbon atoms, or a substituent containing a hetero atom such as oxygen, nitrogen, or sulfur. P represents a substituted aromatic hydrocarbon group having 6 to 40 carbon atoms, and P represents a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SS-, R ²² is a hydrocarbon group having 1 to 6 carbon atoms. W and W 'represent a hydroxyl group, an aldehyde group and a carboxyl group, and r is 0-5.
Indicates an integer. ] The organic compound represented by these can be added.

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

When the organic compound represented by the general formula (VII) is used, a reaction product with a transition metal compound is preferably used. The reaction conditions at this time are such that the organic compound is used in an amount of 0.1 to 10 mol per 1 mol of the metal atom in the transition metal compound, and the reaction may be performed in the presence or absence of a solvent.
Examples of the solvent include hydrocarbon solvents such as toluene and hexane, and T
A polar solvent such as HF (tetrahydrofuran) can be used.

In using these catalysts, the ratio of the component (A) to the component (B) in the catalyst depends on the type of each component, the styrene monomer represented by the general formula [I '] as a raw material, and the general formula [ Although it depends on the type of unsaturated hydrocarbon containing a hetero atom represented by II ′] and other conditions and cannot be unambiguously determined, usually, there is a difference between aluminum in the component (B) and the transition metal in the component (A). The ratio, ie, aluminum / transition metal (molar ratio) is 1 to 10 ⁶ , preferably 1
0 of ^4.

In the method of the present invention, a styrene-based monomer represented by the general formula [I '] is polymerized in the presence of a catalyst containing the above-mentioned components (A) and (B) as main components, and a styrene-based polymer (oligomer) is obtained. ) (Polymerization step);
A step of producing a target copolymer by copolymerizing the styrene polymer obtained in this polymerization step with an unsaturated hydrocarbon monomer containing a hetero atom represented by the above general formula [II '] (copolymerization step) )). This polymerization and copolymerization, such as bulk polymerization, solution polymerization or suspension polymerization,
This can be done in various ways.

Solvents that can be used in the above polymerization or copolymerization 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, aromatic hydrocarbons are preferred. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected, but is preferably 1 or less.

The conditions for the polymerization step of the present invention are not particularly limited, and may be appropriately selected according to various situations, and are usually as follows. That is, the styrene monomer / aluminum (molar ratio) in the component (B) is 1 to 10 ⁶ , preferably 1 to 10 ⁶ .
0 ² to 10 ⁴ . Further, the polymerization temperature is 0 to 120 ° C, preferably 10 to 70 ° C, and the polymerization time is 5 seconds to 5 hours.

Next, the conditions of the copolymerization step of the present invention are not limited as in the case of the above polymerization step, but are usually as follows. The supply amount of the unsaturated hydrocarbon monomer containing a hetero atom can be arbitrarily determined according to the intended composition of the styrene copolymer. The copolymerization temperature is -78 to 120.
° C, preferably -10 to 80 ° C, and the polymerization time is 5 seconds to 24 hours.
Time.

The styrenic copolymer obtained by the method of the present invention has high syndiotacticity of a styrenic repeating unit chain. After polymerization, if necessary, deashing treatment with a washing solution containing hydrochloric acid or the like, washing, drying under reduced pressure, and washing with a solvent such as methyl ethyl ketone to remove soluble components can provide extremely high syndiotacticity. A high-purity styrene-based copolymer is obtained.

〔Example〕

 Next, the present invention will be described in more detail with reference to examples.

Glass container of Example 1 (1) (B) methylaluminoxane prepared purged with argon internal volume 500 ml, toluene 200 ml, copper sulfate pentahydrate _{(CuSO 4 · 5H 2 O)} 17.7g (71 mmol) and trimethyl aluminum 24 ml (250 mmol) was added and reacted at 40 ° C. for 8 hours. Thereafter, toluene was further distilled off under reduced pressure from the solution obtained by removing the solid component to obtain 6.7 g of a contact product (methylaluminoxane).
The molecular weight measured by the freezing point depression method was 610. When the proton nuclear magnetic resonance spectrum is observed in a toluene solution at room temperature at a high magnetic field component by ¹ H-NMR measurement, the methyl proton signal based on the (Al—CH ₃ ) bond is 1.0 to 1.0 based on tetramethylsilane. −
It is found in the range of 0.5 ppm. Since the protons of tetramethylsilane signal (0 ppm) is in the observation area based on the methyl proton based on Al-CH ₃ bonds, the Al-CH methyl proton signal 2.35 of toluene methyl proton signal at tetramethylsilane reference based on ₃ binding When measured on the basis of ppm and divided into high magnetic field components (i.e., -0.1 to -0.5 ppm) and other magnetic field components (i.e., 1.0 to -0.1 ppm),
The high magnetic field component was 43% of the whole.

(2) Production of copolymer Under an argon atmosphere, in a dry 100 ml reaction vessel, at room temperature, 20 ml of toluene, 2 mmol of methylaluminoxane obtained in the above (1) as a catalyst component were added, and 10 ml of paramel styrene was further added. After that, it was left still at 50 ° C. for 30 minutes.

In this container, 1,2,3,4,5-pentamethylcyclopentadienyl titanium trimethoxide (Cp ^* Ti (OM ₃ ) ₃ )
Micromoles were added to initiate polymerization.

After the reaction was carried out for 8 minutes, 10 mmol of a toluene solution of acrylamide (2 mol / l) was added, and polymerization was carried out for 1 hour. Thereafter, the reaction product was added to a methanol-hydrochloric acid mixture, the reaction was stopped, and decalcification was performed. Then, the resultant was further washed with methanol and dried. Further, in order to remove non-quality polymers, Soxhlet extraction was performed for 8 hours with methyl ethyl ketone, and the insoluble portion was dried to obtain 0.4 g of a polymer. The intrinsic viscosity (η) of this polymer was 1.5 dl / g.

^{When 13} C-NMR was measured, sharp peaks were observed at 134.7 ppm and 142.8 ppm. This indicates that the paramethylstyrene chain has a syndiotactic structure. Further, in the infrared absorption spectrum (IR), absorption of carbonyl was observed at around 1730 cm ⁻¹ , and it was found that the acrylamide unit content determined by ¹ H-NMR was 3.3 mol%. The results are shown in Table 1.

Examples 2 to 4 Copolymers were produced in the same manner as in Example 1, except that the conditions shown in Table 1 were changed. The results are shown in Table 1.

Example 5 (1) Synthesis of titanium catalyst component Polymer Preprints, Japan Vol. 36, No. 6, 1415 (1987)
According to the method described, a complex [A] represented by the following formula was synthesized to obtain a toluene solution (10 mmol / 1).

(2) Production of copolymer In Example 1 (2), the catalyst component was used in the complex [A] obtained in the above (1), and N, N-dimethylaryl was used instead of acrylamide. A copolymer was produced in the same manner as in Example 1 (2) except that amide was used. Table 2 shows the results.

Examples 6, 7 Copolymers were produced in the same manner as in Example 5 (2), except that tetraethoxytitanium and titanium tetrachloride were used as titanium catalyst components, respectively. Table 2 shows the results.

Example 8 (1) Production of copolymer In a 200 ml reaction vessel, 100 ml of toluene, 8 mmol of methylaluminoxane obtained in Example 1 (1) as a catalyst component and 10 ml of paramethylstyrene were added at room temperature at 70 ° C.
Temperature.

20 μmol of pentamethylcyclopentadienyltitanium trimethoxide [CpTi (OM _e ) ₃ ] was added to this vessel, and the mixture was reacted for 45 minutes with stirring.

Thereafter, the mixture was cooled to -78 ° C in a dry ice / methanol bath, and N, N-dimethylacrylamide (40 mmol) was added dropwise.

It took 1 hour, the temperature was raised to 25 ° C., and the copolymerization was further performed for 2 hours. This reaction mixture was poured into a large amount of methanol, and the reaction was stopped and demineralized. As a result, a methanol insoluble portion and a methanol suspension were separated. The methanol-insoluble portion was separated by filtration and recovered by washing with methanol. The yield after drying was 1.1 g.

The methanol suspension was recovered by repeated centrifugation and methanol washing. The yield after drying was 2.0 g.

(2) Analysis of copolymer The methanol-insoluble part and the methanol suspension obtained in the above (1) were measured for N, N'-dimethylacrylamide unit content, melting point, intrinsic viscosity and ¹³ C-NMR. Table 3 shows the results.

Measurement by thin layer chromatography: The methanol-insoluble part of the above (1), methanol suspension,
Furthermore, polydimethylacrylamide obtained by radical polymerization using the syndiotactic polyparamethylstyrene prepared in (1) above without adding dimethylacrylamide and the polymerization initiator azobisisobutyronitrile was dissolved in chloroform. These were each formed into a spot of a polymer solution on a thin layer of silica gel on a glass substrate and dried. Next, these were developed in hexane / chloroform with a mixed solvent of 55/45 (volume ratio). When the tip of the solvent reached 8 cm, the development was stopped and the solvent was dried. Further, the color was developed using iodine vapor, and the _Rf value was determined. Table 4 shows the results.

It should be noted that, when developed in a single spot, it was found that the methanol-insoluble portion and the methanol suspension did not contain a syndiotactic homopolymer, but were a copolymer.

The volume resistance was measured using a sheet cast from chloroform. Table 4 shows the results.

Comparative Example 1 In a dry 100 ml reaction vessel under an argon atmosphere, at room temperature, 20 ml of toluene, the above Example 1 (1) as a catalyst component
2 mmol of the methylaluminoxane obtained in the above was added, and 10 ml of paramellar styrene was further added, followed by standing at 50 ° C. for 30 minutes.

In this container, 1,2,3,4,5-pentamethylcyclopentadienyl titanium trimethoxide (Cp ^* Ti (OM ₃ ) ₃ )
Micromol was added and polymerization was carried out for 5 minutes. Thereafter, the reaction product was added to a methanol-hydrochloric acid mixture, the reaction was stopped, and decalcification was performed. Then, the resultant was further washed with methanol and dried. Further, in order to remove non-quality polymers, Soxhlet extraction was performed with methyl ethyl ketone for 8 hours, and the insoluble portion was dried to obtain 0.1 g of a polymer.

^{When 13} C-NMR was measured, sharp peaks were observed at 134.7 ppm and 142.4 ppm. This indicates that the paramethylstyrene chain has a syndiotactic structure. The results are shown in Table 1.

Comparative Example 2 The same operation as in Comparative Example 1 was performed, except that styrene was used instead of paramethylstyrene in Comparative Example 1. The results are shown in Table 1.

The development into a single spot revealed that the methanol-insoluble portion and the methanol suspension did not include a homotactic polymer having a cyclic structure, but were a copolymer.

 The analytical instruments and conditions used for the above analysis are shown below.

(Melting point)

A DSC-200 differential scanning calorimeter manufactured by Seiko Denshi was used.
The measurement conditions were as follows: hold at 300 ° C for 5 minutes, cool to 30 ° C at 7 ° C / min (fast cooling), hold at 30 ° C for 5 minutes, and raise the temperature to 300 ° C at 20 ° C / min. The melting point was measured at the time of pitting.

(Intrinsic viscosity)

 An automatic viscosity measuring device manufactured by Rigosha was used.

The measurement was performed in 1,2,4-trichlorobenzene at 135 ° C.

(Volume resistance)

Using a Yokogawa Hewlett-Packard 16055A shield box and KEITHLEY 617 electrometer, the procedure was as follows.

That is, a sample of the above polymer (200 μ × 0.6 mm × 20 m
m) was mounted on a shield box, and the current value was measured at a voltage of 100 V using an electrometer. From the obtained current value and the shape of the sample, the volume resistance was calculated.

[Effects of the Invention] As described above, the styrenic copolymer of the present invention has a highly syndiotactic structure and an antistatic ability.

Therefore, the styrenic copolymer of the present invention has good processability of a molded product and can be used as it is as a molding material, and it can be effectively used as an antistatic agent by blending it with another molding material.

Therefore, the styrenic copolymer of the present invention is expected to be effectively used in various industrial fields where antistatic of resins such as engineering plastics is required.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08F 212/00-212/36 C08F 220/54-220/60

Claims (2)

(57) [Claims] 1. A compound of the formula [I] [In the formula, R ¹ represents a hydrogen atom, a halogen atom, or a substituent containing at least one of a carbon atom, a tin atom and a silicon atom, and m represents an integer of 1 to 5. However, when m is plural, each R ¹ may be the same or different. At least one structural unit [I] and a general formula [II] [Wherein R ² is a hydrogen atom, a halogen atom or a carbon atom 1
Represents up to 20 hydrocarbon residues, and R ³ and R ⁴ are each a substituent or an element containing at least one of a carbon atom, a nitrogen atom, a sulfur atom, a silicon atom, an oxygen atom, a hydrogen atom and a metal ion. , May be the same or different. n is an integer of 0 or more and 20 or less. And the structural unit [II] contains 0.01 to 99.9 mol% at 135 ° C.
The intrinsic viscosity measured in 1,2,4-trichlorobenzene is 0.01 to 20 dl / g, and the structural unit [I] has a highly stereoregular syndiotactic structure. Styrene copolymer. 2. A compound of the general formula [I '] Wherein R ¹ and m are the same as above. Is polymerized in the presence of a catalyst comprising a transition metal compound and an aluminoxane, and then the polymerization reaction system of the general formula [II '] Wherein R ² , R ³ , R ⁴ and n are the same as above. The method for producing a styrenic copolymer according to claim 1, wherein the copolymerization reaction is carried out by adding a monomer represented by the following formula: