JPH04130108A - Styrene copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain a styrene copolymer excellent in heat resistance, chemical resistance and electrical properties by specifying the structural units, intrinsic viscosity and structure. CONSTITUTION:A styrene copolymer comprising at least one structural unit of formula I (wherein R<1> is H, halogen or a substituent containing at least one C, Sn or Si atom; and (m) is 1-5) and a structural unit of formula II (wherein R<2> is H, halogen or 1-20C hydrocarbyl; R<3> and R<4> are each a substituent or element containing at least one C, N, S, Si, O or H atom or a metal ion; and (n) is 0-20), wherein the structural units of formula II are present in an amount of 0.01-99.9mol%, the intrinsic viscosity in 1,2,4-trichlorobenzene at 135 deg.C is 0.01-20dl/g, and the chain of the structural units of formula I is highly syndiotactic in its stereoregularity.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a styrenic copolymer and a method for producing the same, and more specifically, a styrenic copolymer derived from a structural unit derived from a styrenic monomer and an unsaturated hydrocarbon monomer containing a heteroatom. The present invention relates to a styrenic copolymer having a specific three-dimensional structure consisting of structural units such as the above, and an efficient method for producing the copolymer.

] [Prior art and problems to be solved by the invention] Styrenic polymers conventionally produced by radical polymerization, etc. are molded into various shapes by various molding methods, and are used in household appliances, office equipment, etc. .

Although it is widely used as household goods, packaging containers, toys, furniture, synthetic paper, and other industrial materials, it has a three-dimensional or atactic structure, which has the disadvantage of poor heat resistance and chemical resistance.

The group of the present inventors has succeeded in developing a styrenic polymer mainly having a syndiotactic structure in order to overcome the drawbacks of the styrenic polymer having an atactic structure. They also developed a styrene copolymer made by copolymerizing monomers with other components (Japanese Patent Application Laid-open No. 104818/1986, 62-18
No. 7708, No. 63-241009).

These polymers have excellent heat resistance, chemical resistance, and electrical properties, and are expected to have a wide variety of applications.

However, the above-mentioned styrenic (co)polymer is likely to cause problems during the molding process due to static electricity.

Problems remained unsolved, such as the tendency for dust to adhere to molded products, the generation of noise in electrical signals (VTR reels), and the high insulation resistance and tendency to charge, similar to general styrene-based polymers.

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 of mixing antistatic agents lacks long-lasting effects and has problems with compatibility with resins.
The method of surface treatment complicates the processing process.

Therefore, the present inventors continued their intensive research in order to develop a styrene-based copolymer with antistatic effect and high syndiotacticity.

[Means to solve the problem]

As a result, the above problems can be solved by using a copolymer having a syndiotactic structure and having a structural unit derived from a styrene monomer and a structural unit derived from an unsaturated hydrocarbon monomer containing a heteroatom. I found out. The present invention was completed based on this knowledge.

That is, the present invention provides the following: CI) [wherein R1 represents a hydrogen atom, a halogen atom, or a substituent containing at least one of carbon atom, tin atom, and silicon atom, and m represents 1 to 5 of Indicates an integer. However, when m is plural, each R1 may be the same or different. ] at least one structural unit CI) and -
[II] [In the formula, R2 represents a hydrogen atom, a halogen atom, or a hydrocarbon residue having 1 to 20 carbon atoms, and R1 and R4 each represent a carbon atom, a nitrogen atom, a sulfur atom, a silicon atom,
oxygen atom.

A substituent or element containing at least one of a hydrogen atom and a metal ion, and may be the same or different. n is an integer from 0 to 20. ] It has a structural unit (I[) represented by and contains 0.01 to 99.9 mol% of the structural unit (II), and was measured in 1,2,4-trichlorobenzene at 135 ° C. A styrenic copolymer having an intrinsic viscosity of 0.01 to 20 dl/g, and characterized in that the stereoregularity of the chain of the structural unit CI) is mainly a syndiotastic structure. It is.

Further, the present invention provides a compound represented by the general formula [I'] [wherein R1 and m are the same as above]. ] is polymerized in the presence of a catalyst consisting of a transition metal compound and aluminoxane, and then the polymerization reaction system is added to the general formula [■°] [wherein R2, R3, R4 and n are Same as. ]
The present invention provides a method for producing the above-mentioned styrenic copolymer, which comprises adding a monomer represented by the following and carrying out a copolymerization reaction.

The structural unit (repeat unit) represented by the general formula CI) is derived from the styrene monomer represented by the above general formula [I]. The styrenic copolymer of the present invention is
As described above, it consists of a repeating unit represented by the general formula CI) and a structural unit (repeat unit) represented by the general formula (II).

Specific examples of the styrene monomer represented by the general formula [I'] include styrene, p-methylstyrene, 0-methylstyrene, m-methylstyrene; 2,4-dimethylstyrene; 2,5-dimethylstyrene; , 4-dimethylstyrene; 3,5-dimethylstyrene; alkylstyrenes such as p-tert-butylstyrene, p-chlorostyrene.

m-chlorostyrene, 0-chlorostyrene, p-bromostyrene, m-bromostyrene, 0-bromostyrene,
Halogenated styrenes such as p-fluorostyrene, m-fluorostyrene, 0-fluorostyrene, O-methyl-p-fluorostyrene, 4-vinylbiphenyl, 3-fluorostyrene, etc.
vinylbiphenyl, vinylbiphenyls such as 2-vinylbiphenyl, and 1-(4-vinylphenyl)-naphthalene.

2-(4-vinylphenyl)-naphthalene, 1-(3-
Vinylphenylnaphthalenes such as vinylphenyl)-naphthalene, 2-(3-vinylphenyl)-naphthalene, 1-(2-vinylphenyl)-naphthalene, 2-(2-vinylphenyl)naphthalene, 1-(4-vinyl phenyl)-anthracene, 2-(4-vinylphenyl)-
Anthracene, 9-(4-vinylphenyl)-anthracene, 1-(3-vinylphenyl)-anthracene.

2-(3-vinylphenyl)-anthracene, 9-(3
Vinylphenylanthracenes such as -vinylphenyl)-anthracene, 1-(2-vinylphenyl)-anthracene, 2-(2-vinylphenyl)-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-(2-vinylphenyl)- Vinylphenylphenanthrenes such as phenanthrene, 4-(2-vinylphenyl)-phenanthrene, 9-(2-vinylphenyl)-phenanthrene, 1-(4-vinylphenyl)pyrene, 2-(4-vinylphenyl)-
Pirene.

■=(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-〇-terphenyl, 3-vinyl- p-terphenyl, 3-vinyl-m-terphenyl, 3-vinyl-〇-terphenyl, 2-pinyl-p-terphenyl, 2-vinyl-m-terphenyl, 2-vinyl-〇-terphenyl, etc. Vinylterphenyls, 4-(4-vinylphenyl)-p-
Vinylphenylterphenyls such as terphenyl, 4
-vinyl-4-methylbiphenyl, 4-vinyl-3゛-
Methylbiphenyl.

4-vinyl-2'-methylbiphenyl, 2-methyl-4
-Vinyl biphenyl, vinyl alkyl biphenyls such as 3-methyl-4-vinylbiphenyl, 4-vinyl-4
'-fluorobiphenyl, 4-vinyl-3'-fluorobiphenyl, 4-vinyl-2'-fluorobiphenyl,
4-vinyl 2-fluorobiphenyl, 4-vinyl-3-
Fluorobiphenyl, 4-vinyl-4'-chlorobiphenyl, 4-vinyl-3'-chlorobiphenyl.

4-vinyl-2'-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, halogenated vinylbiphenyls such as 4-vinyl-3-bromobiphenyl, 4-vinyl-
Trialkylsilylvinylbiphenyls such as 4'-trimethylsilylbiphenyl, 4-vinyl-4'-trimethylstannylbiphenyl, trialkylstanylvinylbiphenyls such as 4-vinyl-4'-tributylstannylbiphenyl, 4-vinyl Trialkylsilylmethylvinylbiphenyls such as -4'-trimethylsilylmethylbiphenyl, 4-vinyl-4'-trimethylstannylmethylbiphenyl.

Trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4'-tributylstannylmethylbiphenyl, p-chloroethylstyrene.

Halogen-substituted alkylstyrenes such as m-chloroethylstyrene and 0-chloroethylstyrene, p-trimethylsilylstyrene, m-)limethylsilylstyrene, 0-
Trimethylsilylstyrene.

p-triethylsilylstyrene, m-triethylsilylstyrene, 0-triethylsilylstyrene.

Alkylsilylstyrenes such as p-dimethyltert-butylsilylstyrene, p-dimethylphenylsilylstyrene, p-methyldiphenylsilylstyrene, p
- phenyl group-containing silylstyrenes such as triphenylsilylstyrene, p-dimethylchlorosilylstyrene,
p-methyldichlorosilylstyrene, p-trichlorosilylstyrene, p-dimethylbromosilylstyrene, p
Examples include halogen-containing silylstyrenes such as -dimethyliodosilylstyrene, silyl group-containing silylstyrenes such as p-(p-)limethylsilyl)dimethylsilylstyrene, and mixtures of two or more of these.

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 [■°]. Examples of the unsaturated hydrocarbon monomer containing a hetero atom represented by the general formula [■°] include acrylamide, N-monoalkyl derivatives, N,
N-dialkyl derivatives, N-hydroxyalkyl derivatives, N-haloalkyl derivatives, N-cyanoalkyl derivatives, formalin adducts, bisacrylamide derivatives, bismethacrylamide derivatives, N-aminoalkyl derivatives, N-sulfonalkyl derivatives, okinoalkyl derivatives , amino acid derivatives, ester derivatives.

Hydrazine derivatives, azo derivatives, diamine derivatives.

Examples include diamide derivatives, heterocyclic derivatives, and quinone derivatives. Specific examples include acrylamide, methacrylamide, N-methylacrylamide; N-ethylacrylamide, N-isopropylacrylamide;
-butylacrylamide; N-5ec-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-( 1,1,24-rimethylbrobyl) acrylamide; N-n-hebutylacrylamide; N-(1,
1-dimethylpentyl)acrylamide; N-(1-ethyl-1-methylbutyl)acrylamide; N-(1-
Ethyl-1゜2-dimethylpropyl)acrylamide,
N-(1,1-diethylpropyl)acrylamide; N
-n-octylacrylamide; N-(1,l.

3.3-Tetramethylbutyl)acrylamide: N-(
1,2,3,3-tetramethylbutyl)acrylamide; N-(1-ethyl-1,3-dimethylbutyl)acrylamide; N-(1,1-diethylbutyl)acrylamide; N-(1-ethyl-1 ~methylpentyl)acrylamide; N(l-propyl-1,3-dimethylbutyl)acrylamide; N-(1,I-diethylpentyl)
Acrylamide; N-(1-butyl-1,3-dimethylbutyl)acrylamide; N-dodecyl acrylamide; 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,O)hept-6-yl)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; N-n-butylmethacrylamide; N-tert-butylmethacrylamide; N-n-octylmethacrylamide; N-n
-Dodecylmethacrylamide; N-cyclohexylmethacrylamide; N-(7,7-dimethylpicyclo(3,
2,0)Hebdo-6-nyl)methacrylamide, N-allylmethacrylamide; N-(1,1-dimethylpropenyl)methacrylamide; N-benzylmethacrylamide; N-(1-(4-chlorophenyl))] Ethylmethacrylamide 2N-phenylmethacrylamide N-(2
-Methylphenyl)methacrylamide; N-(3-methylphenyl)methacrylamide; N-(4-methylphenyl)methacrylamide; N-(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-(2,3,64-licrophenyl)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-dicyclohexylacrylamide; Benzyl acrylamide; 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; -(1,l-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-(2,2,2-1lifluoroethyl) ) acrylamide; N-(3,3゜3-trifluoropropyl)acrylamide: N-(3,3-difluorobutyl)acrylamide; N,N-bis(2,2,2-)lifluoroethyl)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; 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-butoxymethyl)acrylamide, N,N'-methylenebisacrylamide; 1
, 2-bisacrylamidoethane; 1,3-bisacrylamidopropane; 1゜4-bisacrylamidobutane; l, 5-bisacrylamidopentane: 1,6-pisacrylamidohexane; 1,7-pisacrylamidohebutane; 1, 8-bisacrylamidooctane; 1゜9-bisacrylamidononane, 1.10-bisacrylamidodecane, 1.12-bisacrylamidododecane, 1,1.1-trimethylamine-2-(N-phenyl-N-acryloyl)propane Imide; 1,1-dimethyl-1-(2-hydroxy)propylamine-N-phenyl-N-methacryloylglycine imide; N-(2
-dimethylaminoethyl)acrylamide; N-(2-
diethylaminoethyl)acrylamide; N-(2-
Morpholinoethyl)acrylamide; N-(3-dimethylaminopropyl)acrylamide; N-(3-propylaminopropyl)acrylamide; -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)
Methylene acrylamide; 2-acrylamidopropanesulfonic acid; 2-acrylamido-n-butanesulfonic acid = 2-acturamide-n-hexane sulfonic acid: 2
-acrylamido-n-octanesulfonic acid; 2-acrylamido-n-dodecanesulfonic acid; 2-acrylamido-n-tetradecanesulfonic acid; 2-acrylamido-2-methylpropanesulfonic acid; 2-acrylamido-2-phenylpropanesulfonic acid ;2-acrylamido-2,4,4-1-limethylpentanesulfonic acid;
2-acrylamido-2-methylphenylethanesulfonic acid; 2-acrylamido-2-(chlorophenyl)propanesulfonic acid: 2-acrylamido-2-carboxymethylpropanesulfonic acid; 2-acrylamido-2
-(pyridyl)propanesulfonic acid; 2-acrylamido-1-methylpropanesulfonic acid; 3-acrylamido-3-methylbutanesulfonic acid; 2-methacrylamido-n-decanesulfonic acid: 2-methacrylamido-n
-Tetradecanesulfonic acid: sodium 4-methacrylamidobenzenesulfonate, or two or more of these components.

In the styrenic copolymer of the present invention, the repeating unit C
I) may be composed of two or more types of components, and the same applies to repeating unit (II). Binary, ternary and quaternary copolymers are thus possible. Further, the content of the above-mentioned repeating unit (II) is usually 0.0 to 99.9% by weight, preferably 0.0% by weight of the entire copolymer.
It is in the range of 1 to 80% by weight, more preferably 0.1 to 60% by weight. The content ratio of this repeating unit (II) is 0.
If the amount is less than 0.01% by weight, the improvement effects aimed at by the present invention, such as improvement in antistatic properties, will not be sufficiently achieved.

Moreover, if it exceeds 99.9% by weight, the heat resistance, which is a characteristic of styrenic polymers having a syndiotactic structure, will not be exhibited. The molecular weight of this copolymer is such that the intrinsic viscosity measured in a 1.2.4-trichlorobenzene solution (temperature 135°C) is generally 0.01 to 20 dl/g, preferably 0.1 to 15 dl/g. belongs to. Intrinsic viscosity is 0.0
1d! If it is less than /g, the mechanical properties are poor and it cannot be put to practical use.

Moreover, 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 to the extent that it does not significantly impair the properties of the resulting copolymer or the syndiotactic structure in the chain of repeating units CI). Examples of such compounds include dienes and vinylsiloxanes.

Examples include unsaturated carboxylic acid esters and acrylonitrile.

The styrenic copolymer of the present invention has a highly syndiotactic structure in which the repeating unit [I], that is, a chain of styrenic repeating units, has a highly syndiotactic structure.

Here, a highly syndiotactic structure in a styrenic polymer is a syndiotactic structure with a highly stereochemical structure, that is, a phenyl group or a substituted side chain with respect to the main chain formed from carbon-carbon bonds. It has a three-dimensional structure in which phenyl groups are alternately located in opposite directions, and its toughness is determined by nuclear magnetic resonance method using carbon isotopes ("C
-NMR method). Toughness measured by the 12C-NMR method is determined by the proportion of consecutive constituent units, e.g.
In the present invention, the styrenic copolymer having a highly syndiotactic structure is usually a racemic diat in the chain of styrenic repeating units. This indicates a syndiotacticity of 75% or more, preferably 85% or more for racemic pentads, or 30% or more, preferably 50% or more for racemic pentads. However, the degree of syndiotacticity varies slightly depending on the type of substituent and the content of repeating unit (II).

The copolymer of the present invention as described above has repeating units CI),
Fractionation by copolymerization of monomers corresponding to (II) and using the obtained copolymer as a raw material.

By applying blending or organic synthetic techniques, embodiments with desired stereoregularity and reactive substituents can be produced.

Among them, according to the production method of the present invention described above, a styrenic copolymer of high quality and high layer efficiency can be obtained.

The raw material monomers used in the production method of the present invention include the styrenic monomer represented by the general formula [I'] and the general formula [
■It is an unsaturated hydrocarbon monomer containing a heteroatom represented by ゛]. The styrene monomer and the unsaturated hydrocarbon monomer containing a hetero atom are polymerized to form repeating units [I].

(II) is constituted. Therefore, as specific examples of the styrenic monomer and the unsaturated hydrocarbon monomer containing a heteroatom, the above-mentioned repeating units CI), (II
) can be given as specific examples.

In the method of the present invention, these styrenic monomers (A
) A transition metal compound and (B) polymerization in the presence of a catalyst containing aluminoxane as a main component, and then copolymerizing the obtained styrenic polymer or oligomer with an unsaturated hydrocarbon monomer containing a hetero atom to obtain a copolymer. This is a method of manufacturing.

Here, there are various types of transition metal compounds that are component (A) of the catalyst, but preferably they are represented by the general formula % () [wherein R5 to R'' are each a hydrogen atom.

Halogen atom, alkyl group having 1 to 2 carbon atoms, 1 carbon number
~20 alkoxy group, aryl group having 6 to 2 carbon atoms,
Arylalkyl group having 7 to 2 carbon atoms, 6 to 2 carbon atoms
represents an aryloxy group, an acyloxy group having 1 to 2 carbon atoms, an acetylacetonyl group, a cyclopentagenyl group, a substituted cyclopentagenyl group, or an indenyl group.

Further, a, b, and c each represent an integer greater than or equal to 0 that satisfies 0≦a+b10≦4, and d.

e each represents an integer greater than or equal to 0 that satisfies 0≦d+e≦3, f represents an integer that satisfies 0≦f≦2, and g and h each represent an integer greater than or equal to 0 that satisfies 0≦g+h≦3. . Furthermore,
Ml.

M2 represents titanium, zirconium, hafnium or vanadium, and M' and M' represent vanadium. ] At least one compound selected from the transition metal compounds represented by: Among these transition metal compounds,
It is preferable to use a material in which Ml in the general formula (III) is titanium or zirconium.

Here, among those represented by R"-R" in the above formula,
Specifically, halogen atoms include chlorine atoms, bromine atoms,
There is an iodine atom or a fluorine atom. In addition, the substituted cyclopentadienyl group includes, for example, a cyclopentadienyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, specifically, a methylcyclopentadienyl group; a 1,2-dimethylcyclo Pentagenyl group: 1,3-dimethylcyclopentadienyl group; 1,3.4-)limethylcyclobentadienyl group; pentamethylcyclopentadienyl group, etc. In addition, R5 to R'' in the above formula are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, an amyl group). , isoamyl group, octyl group, 2-ethylhexyl group), alkoxy groups having 1 to 20 carbon atoms (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, octyloxy group, 2-
ethylhexyloxy group, etc.), an aryl group having 6 to 20 carbon atoms (specifically, a phenyl group, a naphthyl group, etc.), an arylalkyl group having 7 to 2 o carbon atoms (specifically, a benzyl group, a phenethyl group, 9-anthrylmethyl group, etc.), or an acyloxy group having 1 to 20 carbon atoms (specifically, an acetyloxy group, a stearoyloxy group, etc.).

These R'-R'' may be the same or different as long as the above conditions are met.

Such the general formula CI), (IV), (
Among the transition metal compounds represented by V) or (VI), specific examples of titanium compounds include tetramethoxytitanium,
Tetraethoxytitanium, tetra-n-butoxytitanium,
Tetraisopropoxytitanium, titanium tetrachloride, titanium trichloride, cyclopentadienyltrimethyltitanium, cyclopentadienyltriethyltitanium, cyclopentadienyltripropyltitanium, cyclopentadienyltributyltitanium.

Methylcyclopentadienyltrimethyltitanium.

1.2-dimethylcyclopentagenyltrimethyltitanium, pentamethylcyclopentagenyltrimethyltitanium, pentamethylcyclopentagenyltriethyltitanium, pentamethylcyclopentagenyltriethyltitanium, pentamethylcyclopentagenyltributyltitanium, cyclopenta Genyl methyl titanium dichloride, cyclopentajenyl ethyl titanium dichloride, pentamethyl cyclopentajenyl methyl titanium dichloride, pentamethyl cyclopentajenyl ethyl titanium dichloride, cyclopentajenyl dimethyl titanium monochloride, cyclopentajenyl diethyl titanium monochloride chloride,
Cyclopentadienyl titanium trimethoxide, cyclopentadienyl titanium triethoxide, cyclopentajenyl titanium triethoxide, cyclopentajenyl titanium triphenoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopenta Genyl titanium triethoxide, pentamethylcyclopentadienyl titanium triethoxide, pentamethylcyclopentagenyl titanium tributoxide, pentamethylcyclopentagenyl titanium triphenoxide, cyclopentadienyl titanium trichloride, pentamethylcyclopenta Genyl titanium trichloride, cyclopentajenyl methoxy titanium dichloride, cyclopentajenyl dimethoxy titanium chloride, pentamethyl cyclopentajenyl methoxy titanium dichloride, cyclopentajenyl tribenzyl titanium, pentamethyl cyclopentajenyl methyl jetoxy titanium, Indenyl titanium trichloride.

Examples include indenyl titanium trimethoxide, indenyl titanium triethoxide, indenyl trimethyl titanium, and indenyl tribenzyl titanium.

Among these titanium compounds, when it is necessary to increase the molecular weight of a part of the styrenic monomer, titanium compounds having a substituted π-electron system ligand such as an alkoxide or a substituted cyclopentagenyl group are preferred.

Further, when lowering the molecular weight, a titanium compound having a π-electron system ligand such as a cyclopentadienyl group or a halogen ligand is preferable.

In addition, the above - Shipura (I[), (IV), (V)
Among the transition metal compounds represented by (W), specific examples of zirconium compounds include cyclopentadienylzirconium trimethoxide, pentamethylcyclopentadienylzirconium trimethoxide, cyclopentadienyltribenzylzirconium, and pentamethyl. Examples include cyclopentadienyltribenzylzirconium, bisindenylzirconium dichloride, zirconium dibenzyldichloride, zirconiumtetrabenzyl, tributoxyzirconium chloride, triisopropoxyzirconium chloride, and the like.

Similarly, a specific example of a hafnium compound is cyclopentadienyl hafnium trimethoxide.

Pentamethylcyclopentagenylhafnium trimethoxide, cyclopentagenyltribenzylhafnium, pentamethylcyclopentagenyltribenzylhafnium, bisindenylhafnium dichloride, hafnium dibenzyl dichloride, hafnium tetrabenzyl, tributoxyhafnium chloride, triiso Examples include propoxyhafnium chloride.

Furthermore, specific examples of vanadium compounds include vanadium trichloride, vanadyl trichloride, and vanadium triacetylacetonate.

Examples include vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, and the like.

On the other hand, the other component of the catalyst (B) aluminoxane is
For example, it is the same type as that described in JP-A-62-187708, and the details are as follows.

That is, it is obtained by bringing various organic aluminums into contact with a condensing agent.

Here, the organoaluminum compound usually has the general formula A f R''s [wherein R'7 represents an alkyl group having 1 to 20 carbon atoms].

] Organic aluminum represented by these, specifically trimethylaluminum and triethylaluminum.

Examples include trialkylaluminum such as triisobutylaluminum, and trimethylaluminum is most preferred.

On the other hand, the condensing agent typically includes water,
In addition, any substance with which trialkylaluminum undergoes a condensation reaction, such as copper sulfate pentahydrate.

Examples include various types of water adsorbed on inorganic and organic substances.

As the aluminoxane which is the component (B) of the catalyst used in the present invention, there is a contact product of trialkylaluminum and water represented by the above general formula A f R17z, but specifically, the general formula [wherein R " is an alkyl group having 1 to 8 carbon atoms, q indicates the degree of polymerization and is a number from 2 to 52.] or the general formula % [wherein R" and q are the above-mentioned is the same as ] There are cyclic alkylaluminoxanes having a repeating unit represented by the following. Among such alkylaluminoxanes, R
Particularly preferred is methylaluminoxane where " is a methyl group.

Generally, the product of contact between an organoaluminum compound such as trialkylaluminum and water is a mixture of unreacted trialkylaluminum, various condensation products, as well as the above-mentioned linear alkylaluminoxane and cyclic alkylaluminoxane, and furthermore, a mixture of unreacted trialkylaluminum and various condensation products. are molecules that are complexly associated, and these produce various products depending on the contact conditions between trialkylaluminum and water.

There is no particular limitation on the method of contacting the organoaluminum compound with water at this time, and the reaction 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 brought into contact with water, ■ a method in which an organoaluminum compound is initially added during polymerization and water is added later, and ■ a method in which metal salts, etc. There is a method of reacting contained crystal water or water adsorbed on inorganic or organic substances with an organoaluminum compound. Note that the above 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 phosphorous esters.

In the present invention, the aluminoxane (e.g. alkylaluminoxane) used as component (B) of the catalyst is prepared after the above-mentioned catalytic reaction, when a water-containing compound is used, the solid residue is separated by filtration, and the filtrate is heated under normal pressure or reduced pressure for 30 minutes. ~200°
at a temperature of 20° C., preferably between 40 and 150° C.
Preferably, the mixture is heat-treated while distilling off the solvent for a period of minutes to 8 hours, preferably 30 minutes to 5 hours. In this heat treatment, the temperature may be set as appropriate depending on various circumstances, but it is usually carried out within the above range. Generally, if the temperature is less than 30°C, no effect will be exhibited, and if it exceeds 200°C, thermal decomposition of the alkylaluminoxane itself will occur, both of which are not preferred.

Depending on the heat treatment conditions, the reaction product can be obtained in the form of a colorless solid or a solution. The product thus obtained can be used as a catalyst solution by dissolving or diluting it with a hydrocarbon solvent, if necessary.

A preferable example of an aluminoxane, particularly an alkylaluminoxane, used as the catalyst (B) component is a high magnetic field component in the methyl proton signal region based on the aluminum-methyl group<Ap-CH2) bond observed in proton nuclear magnetic resonance spectroscopy. or less than 50%. In other words, when the proton nuclear magnetic resonance ('H-NMR) spectrum of the above contact product is observed in toluene solvent at room temperature, AI! Methyl proto-methyl based on CH2
Signals are seen in the range of 1.0 to -0.5 ppm based on tetramethylsilane (TMS).

The TMS proton signal (Oppm) is Aji'
Since it is in the methyl proton observation region based on CH2, the methyl proton signal based on 1-CH,
Methyl proton signal of toluene in S standard2.
Measured based on 35 ppm, high magnetic field component (i.e. -〇,
1 to -0.5 ppm) and other magnetic field components (i.e. 1.0
-0.1 ppm), the high-field component accounts for 50% or less of the total, preferably 45 to 5%, which can be suitably used as component (B) of the catalyst.

The catalyst used here has the above-mentioned components (A) and (B) as its main components, but in addition to the above, another catalyst component (C) can be added if desired, thereby increasing the catalyst component. By adding (C), the catalyst activity can be significantly improved.

This catalyst component (C) is, for example, -shipped% formula% [wherein R'' is a hydrogen atom, a halogen atom, or a carbon number of 1 to
8 shows the alkyl group. ] Trialkylaluminum or other existing metal compounds represented by the formula % can be added within the range not impairing the stereoregularity. ~2o hydrocarbon group, a substituted aromatic hydrocarbon group having 7 to 3 carbon atoms, or a substituted aromatic hydrocarbon group having 6 to 40 carbon atoms having a substituent containing a heteroatom such as oxygen, nitrogen, sulfur, etc. , P is a hydrocarbon group having 1 to 2 carbon atoms.

-o-, -s-, -5-s- R22 is 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 an integer of 0 to 5.

An organic compound represented by can be added.

Specific examples of the organic compound represented by the above general formula (■) include 2,2'-dihydroxy-3,3'-di-
Examples include t-butyl-5,5'-dimethyldiphenyl sulfide; 2,2'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethyldiphenyl ether.

When using an organic compound represented by the general formula (■), a reaction product with a transition metal compound is preferably used.

The reaction conditions at this time are such that the amount of the organic compound is 0.1 to 10 mol per mol of the metal atom in the transition metal compound, and the reaction may be carried out in the presence or absence of a solvent. As the solvent, a hydrocarbon solvent such as toluene or hexane, or a polar solvent such as THF (tetrahydrofuran) can be used.

When using these catalysts, (A) in the catalyst
The ratio of the component to the component (B) is based on the type of each component, the raw material styrenic monomer represented by the general formula [1'], and the unsaturated hydrocarbon containing a heteroatom represented by the general formula [■']. Although it cannot be determined uniquely depending on the type and other conditions, usually aluminum in component (B) and (A
1 to 10'', preferably 10
~10'.

The method of the present invention involves polymerizing the styrenic monomer represented by the general formula [I] in the presence of a catalyst containing the above-mentioned components (A) and (B) as main components, thereby producing a styrenic polymer (oligomer). (including) (polymerization step), and the styrenic polymer obtained in this polymerization step is
It consists of a two-step process (copolymerization process) of copolymerizing with an unsaturated hydrocarbon monomer containing a heteroatom represented by ゛] to produce the desired copolymer. This polymerization and copolymerization can be carried out by various methods such as bulk polymerization, solution polymerization, or suspension polymerization.

Examples of 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. Among 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 depending on various situations, but are usually as follows. That is, the molar ratio of styrenic monomer/aluminum in component (B) is 1 to 106, preferably 102 to 104.

In addition, the polymerization temperature is 0 to 120°C, preferably 10 to 7
The temperature was 0°C, and the polymerization time was 5 seconds to 5 hours.

Next, the conditions for the copolymerization step of the present invention are not limited as in the case of the above polymerization step, and are usually as follows. The amount of the unsaturated hydrocarbon monomer containing a heteroatom to be supplied can be arbitrarily determined depending on the composition of the desired styrenic copolymer. In addition, the copolymerization temperature is -78 to 120
°C1 Preferably -10 to 80 °C, polymerization time is 5
seconds to 24 hours.

The styrenic copolymer obtained by the method of the present invention is
Syndiotacticity of styrenic repeating unit chains
is high. In addition, after polymerization, if necessary, deashing with a washing solution containing hydrochloric acid, etc., followed by washing and drying under reduced pressure, and then washing with a solvent such as methyl ethyl ketone to remove soluble components, can significantly reduce syndiotacticity. A large and highly pure styrenic copolymer is obtained.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) (B) Preparation of methylaluminoxane In a glass container with an internal volume of 500 mm and replaced with argon, 20% of toluene was added
0rn1. Copper sulfate pentahydrate (CuSO45Ht○) 17.
7 g (71 mmol) and trimethylaluminum 2
4rnl (250 mmol) was added and reacted at 40°C for 8 hours. Thereafter, solid components were removed, and toluene was further distilled off under reduced pressure from the resulting solution to obtain 6.7 g of a contact product (methylaluminoxane). The molecular weight of this product was determined to be 610 by freezing point depression method. Also, the aforementioned 'H-
When observing the high magnetic field component by NMR measurement, that is, the proton nuclear magnetic resonance spectrum in toluene solution at room temperature,
(AI! CHI) The methyl proton signal based on the bond is 1.0 to -0.5 based on tetramethylsilane.
Found in the ppm range. This Al-C
The methyl proton signal based on the Hx bond was measured with respect to the methyl proton signal of toluene at 2,35 ppm in the tetramethylsilane standard, and the high field component (i.e. -0,1 to -0,5 ppm) and the other magnetic field component ( That is, 1
．． When divided into 0 to -0.1 ppm), the high-field component accounted for 43% of the total.

(2) Production of copolymer Dry i o Omf! under an argon atmosphere. 20 rnl of toluene and 2 mmol of methylaluminoxane obtained in the above (1) as a catalyst component were added to a reaction vessel at room temperature, and after adding 10-g of paramel styrene, the mixture was heated at 50°C for 3
It was left standing for 0 minutes.

1. In this container. 2. 3. 4. 5-Pentamethylcyclopentadienyl titanium trimethoxide (CI
)"Ti(OMs)x) was added in an amount of 5 micromoles to initiate polymerization.

After reacting for 8 minutes, a toluene solution of acrylamide (2 mol/I, equivalent to 10 mmol) was added and polymerization was carried out for 1 hour.Then, the reaction product was poured into a methanol-hydrochloric acid mixture to stop the reaction. After deashing, it was further washed with methanol and dried.

In order to further remove the amorphous polymer, Soxhlet extraction was performed with methyl ethyl ketone for 8 hours, and the insoluble portion was dried to obtain 0.4 g of polymer. The intrinsic viscosity of this polymer (
η) was 1.5 di/g.

“When C-NMR was measured, it was 134.7 ppm14
A sharp peak was observed at 2.8 ppm. This indicates that the paramethylstyrene chain has a syndiotactic structure. In addition, the infrared absorption spectrum (IR
), carbonyl absorption was observed near 1730an-', and the acrylamide unit content determined by 'H-NMR was found to be 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 were changed to those shown in Table 1. The results are shown in Table 1.

Example 5 (1) Synthesis of titanium catalyst component Polymer Preprints, Japan
Vol, 36. 6.1415 (1987), a complex (A) represented by the following formula was synthesized and made into a toluene solution (10 mmol/11).

Production of 1-Pr/isopropyl group (2) copolymer In Example 1 (2), the complex (A) obtained in (1) above was used as the catalyst component, and N was used instead of acrylamide. A copolymer was produced in the same manner as in Example 1(2) except that N-dimethylacrylamide was used. The results are shown in Table 2.

Examples 6 and 7 A copolymer was produced in the same manner as in Example 5(2) except that tetraethoxytitanium and titanium tetrachloride were used as titanium catalyst components, respectively. The results are shown in Table 2.

Example 8 (1) Preparation of copolymer 8 mmol of methylaluminoxane obtained in Example 1 (1) and 10 mmol of paramethylstyrene were added to a 200 rIL reaction vessel at room temperature as a catalytic acid content of 100-2 toluene.
ml was added and the temperature was raised to 70'C.

20 micromoles of pentamethylcyclopentadienyl titanium trimethoxide (CpTi(OM,)3) was added to this container and reacted for 45 minutes with stirring.

Then in a dry ice/methanol bath = 78°
Cool to 40°C and add N,N-dimethylacrylamide 40
mmol was added dropwise.

It took 1 hour to raise the temperature to 25°C, and copolymerization was continued for another 2 hours. When this reaction mixture was poured into a large amount of methanol to stop the reaction and deash, it was separated into a methanol-insoluble part and a methanol suspension.

The methanol-insoluble portion was separated by filtration and further recovered by washing with methanol. The yield after drying was 1.1 g.

The methanol suspension was recovered by repeating centrifugation and methanol washing. The yield of this product after drying was 2.0 g.

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

■Measurement by thin layer chromatography The methanol-insoluble part of the above (1), the methanol suspension, the syndiotactic polyparamethylstyrene produced in the above (1) without adding dimethylacrylamide, and the polymerization initiator azobisisobutylene. Each polydimethylacrylamide obtained by radical polymerization using lonitrile was dissolved in chloroform. A spot of polymer solution was created on a thin layer of silica gel on each glass substrate.
Dry. Next, these were added to hexane/chloroporm for 5 minutes.
It was developed with a mixed solvent of 5/45 (volume ratio).

When the front end of the solvent reached 8a[l, development was stopped and drying was performed. Furthermore, the color was developed using iodine vapor, and the R value was determined. The results are shown in Table 4.

In addition, from the development of a single spot, it was found that the methanol-insoluble part and the methanol suspension did not contain a syndiotactic homopolymer, but were copolymers.

In addition, volume resistivity was measured using a sheet cast from chloroform. The results are shown in Table 4.

Comparative Example 1 The above Example 1 (
After adding 2 mmol of methylaluminoxane obtained in 1) and further adding 10% of paramel styrene, the mixture was heated at 50°C for 3
It was left standing for 0 minutes.

Into this container was added 1,2,3,4,5-pentamethylcyclopentadienyl titanium trimethoxide (Cp”T i
5 micromoles of (OM2)3) was added and polymerization was carried out for 5 minutes. Thereafter, the reaction product was poured into a methanol-hydrochloric acid mixture to stop the reaction and deash, followed by further washing with methanol and drying. In order to further remove the amorphous polymer, Soxhlet extraction was performed with methyl ethyl ketone for 8 hours, and the insoluble portion was dried to obtain 0.1 g of polymer.

When I3C-NMR was measured, it was found to be 134.7 ppm1.
A sharp peak was observed at 42.4 ppm. This means that
This shows that the paramethylstyrene chain has a syndiotactic structure. The results are shown in Table 1.

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

In addition, from the development in a single spot, it was found that the methanol-insoluble part and the methanol suspension did not contain a homopolymer with a syntactic structure, but were copolymers.

The analytical equipment and conditions used in the above analysis are shown below.

[Melting point]

A Seiko Electronics DSC-200 differential scanning calorimeter was used. The measurement conditions were: 300″C for 5 minutes, 30°C
After cooling at 7 °C/min (first cooling) to 3
The melting point was measured during second heating, which was held at 0°C for 5 minutes and raised to 300°C at a rate of 20°C/min.

[Limiting viscosity]

An automatic viscosity measuring device manufactured by Rigosha was used.

The measurements were carried out in 1.2.4-)dichlorobenzene at 135°C.

[Volume resistance]

The following procedure was performed using a 16055A shield box manufactured by Yokogawa Hewlett-Packard and a 617 electrometer manufactured by KEITHLEY.

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

〔Effect of the invention〕

As described above, the styrenic copolymer of the present invention has a highly syndiotactic structure and exhibits antistatic ability.

Therefore, the styrenic copolymer of the present invention has good processability into molded products, and can of course be used as a molding material as it is, or can be blended with other molding materials to effectively prevent static electricity in the materials.

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

Patent applicant: Idemitsu Kosan Co., Ltd. “-m-bottom Agent Patent Attorney Tamotsu Otani

Claims (2)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I] [In the formula, R^1 is either a hydrogen atom, a halogen atom, or a carbon atom, a tin atom, or a silicon atom It represents one or more substituents, and m represents an integer of 1 to 5. However, m
When there is a plurality of R^1's, each R^1 may be the same or different. ] At least one structural unit represented by [I] and general formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] [In the formula, R^2 is a hydrogen atom, a halogen atom, or a carbon atom. Indicates a number of 1 to 20 hydrocarbon residues, R^3 and R^4
are substituents or elements each 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, and may be the same or different. n is an integer from 0 to 20. ] It has a structural unit [II] represented by, and contains 0.01 to 99.9 mol% of the structural unit [II], and it was measured in 1,2,4-trichlorobenzene at 135 ° C. A styrenic copolymer having an intrinsic viscosity of 0.01 to 20 dl/g and having a highly syndiotactic structure in which the stereoregularity of the chain of the structural unit [I] is high. (2) General formula [I ′] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [I ′] [In the formula, R^" and m are the same as above.] The styrenic monomer represented by Polymerization occurs in the presence of a catalyst consisting of a metal compound and aluminoxane, and then the polymerization reaction system has the general formula [II'] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II'] [In the formula, R^2 , R^3, R^4 and n are the same as above.] The method for producing a styrenic copolymer according to claim 1, characterized in that a copolymerization reaction is carried out by adding a monomer represented by the following.