JPH0597927A - Production of styrenic polymer and copolymer - Google Patents

Abstract

PURPOSE:To obtain the subject syndiotactic (co)polymer excellent in color hue, heat-resistance and mechanical strength and useful for molding, etc., in high efficiency by (co)polymerizing a styrenic monomer having aryl substituent, etc., in the presence of a specific catalyst. CONSTITUTION:The objective (co)polymer can be produced by (co)polymerizing a styrenic monomer having aryl substituent (e.g. 4-vinylbiphenyl) or a styrenic monomer mixture containing the above styrenic monomer having aryl substituent and other styrenic monomer (e.g. styrene) in the presence of a catalyst composed mainly of (A) a transition metal compound (e.g. cyclopentadienyl compound of Ti, Zr, Hf, etc.) and (B) a compound capable of forming an ionic complex by reacting with the transition metal compound (e.g. tetraphenylboric acid triethylammonium salt).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a styrenic polymer and a copolymer, and more particularly, to efficiently produce an aryl styrene polymer and a copolymer having a syndiotactic structure by using a specific catalyst. Well about the manufacturing method.

[0002]

BACKGROUND OF THE INVENTION Styrenic polymers conventionally manufactured by radical polymerization or the like are molded into various shapes by various molding methods, and are used for household electric appliances, office equipment, household products, packaging containers, toys, It is widely used as furniture, synthetic paper, and other industrial materials, but its three-dimensional structure has an atactic structure, which has the drawback of poor heat resistance and chemical resistance.

The inventors of the present invention have succeeded in developing a styrene-based polymer having a syndiotactic structure to solve the drawbacks of such a styrene-based polymer having an atactic structure, and have further improved heat resistance. An aryl styrene-based polymer having excellent properties was also developed (JP-A-62-
No. 104818, No. 62-187708, Japanese Patent Application Nos. 1-246187 and 2-257484).

However, this Japanese Patent Application No. 1-261818
In the production method disclosed in the specification No. 7 and the specification No. 2-257484, there are various problems such that the catalyst used is expensive, the polymerization activity is not sufficient, and a deashing step is required. It was That is, in general, a transition metal / aluminoxane-based catalyst production method uses a large amount of aluminoxane with respect to a transition metal, so that a large amount of catalyst residues remain in the produced polymer and a deashing step is indispensable.

By the way, olefin polymerization using a cationic transition metal complex has been reported for a long time. For example
(1) Natta et al. Reported that ethylene was polymerized using titanocene dichloride / triethylaluminum as a catalyst (J. Polymer Sci., 26 , 120 (1964)). Also, Br
Eslow et al. reported the polymerization of ethylene with a titanocene dichloride / dimethylaluminum chloride catalyst (J. Am. Chem. Soc., 79 , 5072 (1957)). In addition, Dy
achkovskii et al. suggest that the titanocene dichloride / dimethylaluminum chloride-catalyzed ethylene polymerization activity is a titanocene monomethyl cation (J. Polymer Sci., 16 , 2333 (1967)). However, the ethylene activity in these methods is extremely low.

(2) Jordan et al. Synthesize and isolate [biscyclopentadienylzirconium methyl (tetrahydrofuran)] [tetraphenyl boric acid] by reacting zirconocene dimethyl with silver tetraphenyl borate, and use it to produce ethylene. (J. Am.
Chem. Soc., 108, 7410 (1986)). They have also synthesized and isolated [biscyclopentadienylzirconium benzyl (tetrahydrofuran)] [tetraphenylborate] by reacting zirconocene dibenzyl with ferrocenium tetraphenylborate (J. Am. Chem. Soc., 109, 4
111 (1987)). However, although it was confirmed that ethylene was slightly polymerized also in these catalysts, the polymerization activity was extremely low.

(3) Turner, et al. A polymerization method is proposed (Japanese Patent Publication No. 1-502036). However, the application of such a catalyst system is limited to homopolymerization and copolymerization of α-olefins, and is not currently applied to styrene-based monomers.

[0008]

Therefore, the present inventors have found that
In view of the above-mentioned current situation, the inventors have earnestly studied to develop a method for efficiently producing an arylstyrene polymer or copolymer having excellent heat resistance. As a result, they have found that the object can be achieved by using a specific complex-forming compound instead of aluminoxane as one component of the catalyst. The present invention has been completed based on such findings.

[0009]

That is, the present invention provides a styrene monomer having an aryl substituent or a styrene monomer containing the styrene monomer having the aryl substituent and another styrene monomer (A).
Styrene having a syndiotactic structure characterized by being polymerized or copolymerized in the presence of a catalyst containing a transition metal compound and (B) a compound that reacts with the transition metal compound to form an ionic complex as a main component. A method for producing a styrene-based polymer or a styrene-based copolymer is provided.

In the method of the present invention, one or more styrene-based monomers (aryl styrene-based monomers) having an aryl substituent as a raw material monomer, or styrene containing the aryl styrene-based monomer and another styrene-based monomer. A system monomer is used. here,
There are various kinds of aryl styrene-based monomers, and the preferable one is the general formula (I).

[0011]

[Chemical 3]

[Wherein R ¹ is any ^one of a hydrogen atom, a halogen atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom.
A substituent containing at least one species is shown, and m is an integer of 1 to 5.
However, among m R ¹ , at least ^one of them is an aryl group having a hydrogen atom, an aryl group having a halogen atom, or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom. One of
An aryl group having a substituent containing at least one species. ] The aryl styrene type monomer represented by these can be mentioned.

In the general formula (I) showing this aryl styrene-based monomer, R ¹ represents various substituents as described above, and the halogen atom can be chlorine, fluorine, bromine or iodine. .. Specific examples of the substitution including a carbon atom include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and a tertiary butyl group, or an alkyl group having a carbon number of 1 to 20 such as a chloroethyl group and a bromoethyl group. There are halogen-substituted alkyl groups.
Further, specific examples of the substituent containing a carbon atom and an oxygen atom include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group, or a carbon number 1 to 1 such as a methoxycarbonyl group and an ethoxycarbonyl group. 10
The alkoxycarbonyl group of is mentioned. Specific examples of the substituent containing a carbon atom and a silicon atom include an alkylsilyl group having 1 to 20 carbon atoms such as a trimethylsilyl group, and specific examples of the substituent containing a carbon atom and a tin atom include trimethylstannyl. Group, tri-n-butylstannyl group, triphenylstannyl group, etc., having 1 to 20 carbon atoms
And the alkylstannyl group or the arylstannyl group.

Specific examples of the substituent containing a carbon atom and a nitrogen atom include an alkylamino group having 1 to 20 carbon atoms such as a dimethylamino group and a cyano group. Furthermore, specific examples of the substituent containing a sulfur atom include a sulfonyl group, a sulfonic acid alkyl ester group, an alkylthio group,
Examples thereof include an arylthio group and a mercapto group, and specific examples of the substituent containing a selenium atom include an alkylseleno group, an arylseleno group, an alkylselenoxyl group, and an arylselenoxyl group. Specific examples of the substituent containing a phosphorus atom include a phosphoric acid ester group, a phosphorous acid ester group, a dialkylphosphino group, a diarylphosphino group, an alkylphosphinyl group, and an arylphosphinyl group. Furthermore, examples of the group containing no carbon atom include a nitro group and a diazo group.

[0015] In the above R ¹ , at least one of m existing ones is an aryl group having a hydrogen atom,
It represents an aryl group having a halogen atom or an aryl group having a substituent containing at least one of carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom, silicon atom and tin atom. If m is present, at least one substituent of R ¹ is a hydrogen atom, a halogen atom, or a substituent containing a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom or a tin atom. Must be an aryl group with any position. The substituent of this aryl group is the same as that described above. Further, as the aryl group,
Benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, chrysene ring, biphenyl ring, terphenyl ring, fluorene ring, pentalene ring, indene ring, azulene ring, heptalen ring, biphenylene ring, as
-Indacene ring, s-indacene ring, acenaphthylene ring, phenalene ring, fluoranthene ring, acephenanthrene ring, aceanthrylene ring, triphenylene ring, naphthacene ring, preaden ring, picene ring, perylene ring, pentaphene ring, pentacene ring, rubicene A substituent containing a ring, a colocene ring, a pyranthrene ring or an ovalen ring is shown.

Specific examples of the aryl styrene-based monomer represented by the general formula (I) include vinylphenyls such as 4-vinylbiphenyl, 3-vinylbiphenyl and 2-vinylbiphenyl; 1- (4- Vinylphenyl) naphthalene, 2- (4-vinylphenyl) naphthalene, 1- (3-vinylphenyl) naphthalene, 2- (3
Vinylphenylnaphthalenes such as -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
Such as-(3-vinylphenyl) anthracene, 9- (3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, 2- (2-vinylphenyl) anthracene, 9- (2-vinylphenyl) anthracene. Vinylphenylanthracenes; 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-
Vinylphenylphenanthrenes such as (2-vinylphenyl) phenanthrene, 3- (2-vinylphenyl) phenanthrene, 4- (2-vinylphenyl) phenanthrene, 9- (2-vinylphenyl) phenanthrene;
Vinylphenylpyrenes such as 1- (4-vinylphenyl) pyrene, 2- (4-vinylphenyl) pyrene, 1- (3-vinylphenyl) pyrene; 4-vinyl-4′-bromobiphenyl, 4-vinyl- Halogenated vinyl biphenyls such as 3'-bromobiphenyl, 4-vinyl-2'-bromobiphenyl, 4-vinyl-2-bromobiphenyl, 4-vinyl-3-bromobiphenyl; 4-vinyl-4'-methoxybiphenyl , 4-vinyl-3'-methoxybiphenyl, 4-vinyl-2'-methoxybiphenyl, 4-vinyl-2-methoxybiphenyl, 4-vinyl-3-methoxybiphenyl, 4-vinyl-4'-ethoxybiphenyl, 4 -Vinyl-3'-ethoxybiphenyl, 4-vinyl-2'-ethoxybiphenyl, 4-vinyl-2-ethoxybiphenyl, 4 Alkoxy vinyl phenyls such as vinyl-3-ethoxy-biphenyl; 4-
Alkoxycarbonylvinylbiphenyls such as vinyl-4′-methoxycarbonylbiphenyl and 4-vinyl-4′-ethoxycarbonylbiphenyl; 4-vinyl-
Alkoxyalkyl vinyl biphenyls such as 4′-methoxymethyl biphenyl; trialkylsilyl vinyl biphenyls such as 4-vinyl-4′-trimethylsilyl biphenyl; 4-vinyl-4′-trimethylstannyl biphenyl, 4-vinyl-4 ′ -Trialkylstannylvinylbiphenyls such as tributylstannylbiphenyl; trialkylsilylmethylvinylbiphenyls such as 4-vinyl-4'-trimethylsilylmethylbiphenyl; 2- (3-vinylphenyl) pyrene, 1- (2- Vinylphenylpyrenes such as vinylphenyl) pyrene and 2- (2-vinylphenyl) pyrene; 4-vinyl-p-
Terphenyl, 4-vinyl-m-terphenyl, 4-vinyl-o-terphenyl, 3-vinyl-p-terphenyl, 3-vinyl-m-terphenyl, 3-vinyl-o-
Vinyl terphenyls such as terphenyl, 2-vinyl-p-terphenyl, 2-vinyl-m-terphenyl, 2-vinyl-o-terphenyl; 4- (4-vinylphenyl) -p-terphenyl, etc. Vinylphenyl terphenyls; 4-vinyl-4′-methylbiphenyl, 4-
Vinyl-3'-methylbiphenyl, 4-vinyl-2'-
Methylbiphenyl, 2-methyl-4-vinylphenyl,
Vinylalkyl biphenyls such as 3-methyl-4-vinylphenyl; 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 '
Halogenated vinylbiphenyls such as -chlorobiphenyl, 4-vinyl-2'-chlorobiphenyl, 4-vinyl-2-chlorobiphenyl, 4-vinyl-3-chlorobiphenyl; 4-vinyl-4'-trimethylstannylmethyl Examples thereof include trialkylstannylmethylvinylbiphenyls such as biphenyl and 4-vinyl-4′-tributylstannylmethylbiphenyl. Among these, vinyl biphenyls, vinyl phenylene anthracenes and vinyl terphenyls are preferable. Further, regarding vinyl biphenyls, 4-vinyl biphenyls in which an aryl group is substituted at the 4-position (p-position) of styrene is most suitable. In the method of the present invention, when the above-mentioned aryl styrene-based monomer is used as a raw material monomer, one or more of these are used and polymerization or copolymerization is carried out. At this time, the copolymerization is carried out by copolymerizing two or more of the above arylstyrene monomers (that is, 4-vinylbiphenyl (p-phenylstyrene) and 3-vinylbiphenyl (m), for example.
-Phenylstyrene) and other arylstyrene-based monomers are copolymerized with each other.

In the method of the present invention, the arylstyrene monomer and the styrene monomer containing the other styrene monomer are used as the raw material monomer, and the arylstyrene monomer is copolymerized with the other styrene monomer. It can be performed. Here, as the other styrenic monomer that can be used, various ones other than the aryl styrenic monomer can be mentioned, but the general formula (II) is preferable.

[0018]

[Chemical 4]

[Wherein R ² is any one of a hydrogen atom, a halogen atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom.
A substituent containing at least one species is shown, and n is an integer of 1 to 5.
However, when n is plural, each R ² may be the same or different. ] The styrene-type monomer represented by these can be mentioned. In the styrene-based monomer represented by the general formula (II), R ² represents various kinds of substituents, but R ² has the same variety as the substituent of R ¹ described above except that an aryl group or a substituted aryl group is not essential. There are many things.

Specific examples of the styrenic monomer of the general formula (II) include styrene, p-methylstyrene; o-
Methyl styrene; m-methyl styrene; 2,4-dimethyls m-chlorostyrene; o-chlorostyrene; p-bromostyrene; m-bromostyrene; p-fluorostyrene; m-fluorostyrene; o-fluorostyrene;
Mention may be made of halogenated styrenes such as o-methyl-p-fluorostyrene.

In the method of the present invention, the above-mentioned styrene-based monomer is polymerized or copolymerized. More specifically, the arylstyrene-based monomer represented by the general formula (I) is homopolymerized, or two or more general formulas are used. The arylstyrene-based monomers of (I) are copolymerized with each other, or the arylstyrene-based monomer of the general formula (I) and the styrene-based monomer of the general formula (II) are copolymerized. The catalyst used in the polymerization or copolymerization is (A) transition metal compound and (B)
The main component is a compound that reacts with the transition metal compound to form an ionic complex. Here, as the transition metal compound as the component (A), the periodic table IIIB, IVB, VB,
VIB, VIII, a metal compound of the lanthanoid group, preferably IVB, VIB, a metal compound of the lanthanoid group of the periodic table, particularly preferably a metal compound of group IVB of the periodic table, especially Ti, Z
It is a compound of r or Hf. Among the transition metal compounds as the component (A), as the transition metal compound of Group IVB of the periodic table, a cyclopentadienyl compound represented by the following general formula (III), (IV) or (V) Derivatives are preferred. ^{_{CpM 1 R 3 a R 4 b}} R 5 C ··· (III) Cp 2 M 1 R 3 d R 4 e ··· (IV) (Cp-A f -Cp) M 1 R 3 d R 4 e · .. (V) [In the formulas (III) to (V), M ¹ represents a Ti, Zr or Hf atom, and Cp represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, A tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is shown. R
³ , R ⁴ and R ⁵ are each a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, and 1 to 2 carbon atoms.
0 alkoxy group, 6-20 carbon aryl group, alkylaryl group or arylalkyl group, 1 carbon atom
~ 20 acyloxy group, allyl group, substituted allyl group, acetylacetonate group, substituted acetylacetonate group,
A substituent containing a silicon atom, or a ligand such as carbonyl, an oxygen molecule, a nitrogen molecule, a Lewis base, a chain unsaturated hydrocarbon, or a cyclic unsaturated hydrocarbon is shown, and A shows a bridge by a covalent bond. a, b and c are each an integer of 0 to 3,
d and e each represent an integer of 0 to 2, and f represents an integer of 0 to 5. Two or more of R ³ , R ⁴ and R ⁵ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. ]

Examples of the substituted cyclopentadienyl group in the above formulas (III) to (V) include methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethyl. Cyclopentadienyl group; tetramethylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group; 1,
2,3-trimethylcyclopentadienyl group; 1,2,
4-trimethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group and the like. Specific examples of R ^{3 to} R ⁵ include, for example, halogen atoms such as F, Cl, Br,
I: Methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, octyl group, 2-ethylhexyl group as an alkyl group having 1 to 20 carbon atoms;
20 alkoxy groups such as methoxy group, ethoxy group, broboxy group, butoxy group, phenoxy group, carbon number 6-20
Of the aryl group, alkylaryl group or arylalkyl group of phenyl group, tolyl group, xylyl group, benzyl group, heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms, trimethylsilyl group as a substituent containing a silicon atom, ( (Trimethylsilyl) methyl group, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran as Lewis bases, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine,
Tributylamine, N, N-dimethylaniline, 2,
Amines such as 2'-bipyridine and phenanthroline, phosphines such as triethylphosphine and triphenylphosphine, ethylene, butadiene, 1-pentene, isoprene, pentadiene and 1-as chain unsaturated hydrocarbons.
Examples include hexene and derivatives thereof, and cyclic unsaturated hydrocarbons such as benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the covalent crosslink of A include methylene crosslink, dimethylmethylene crosslink, ethylene crosslink, dimethylsilylene crosslink, dimethylgermylene crosslink, and dimethylstannylene crosslink.

Particularly preferred among the compounds of formulas (III) to (V) are at least two of R ^{3 to} R ^{5 in} the compound of formula (III), and also formulas (IV) and ( In the compound V), at least one of R ³ and R ⁴ has 1 to 20 carbon atoms.
And an aryl group having 6 to 20 carbon atoms.

Here, specific examples of the compound of the formula (III) include cyclopentadienyltrimethyl titanium, cyclopentadienyl triethyl titanium, cyclopentadienyl tripropyl titanium, cyclopentadienyl tributyl titanium and methylcyclo. Pentadienyl trimethyl titanium, methyl cyclopentadienyl tribenzyl titanium,
1,2-Dimethylcyclopentadienyltrimethyl titanium, tetramethylcyclopentadienyl trimethyl titanium, pentamethyl cyclopentadienyl trimethyl titanium, pentamethyl cyclopentadienyl triethyl titanium, pentamethyl cyclopentadienyl tripropyl titanium, penta Methyl cyclopentadienyl tributyl titanium, pentamethyl cyclopentadienyl triphenyl titanium, pentamethyl cyclopentadienyl tribenzyl titanium, cyclopentadienyl methyl titanium dichloride, cyclopentadienyl ethyl titanium dichloride, pentamethyl cyclopentadienyl Methyl titanium dichloride, pentamethyl cyclopentadienyl ethyl titanium dichloride, cyclopentadienyl dimethyl titanium monochloride, cyclope Tadienyl diethyl titanium monochloride, cyclopentadienyl titanium trimethoxide, cyclopentadienyl titanium triethoxide, cyclopentadienyl titanium tripropoxide, cyclopentadienyl titanium triphenoxide, pentamethylcyclopentadienyl titanium tri Methoxide, pentamethylcyclopentadienyl titanium triethoxide, pentamethyl cyclopentadienyl titanium tripropoxide, pentamethyl cyclopentadienyl titanium tributoxide, pentamethyl cyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium Trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl methoxy titanium dichloride, cyclopentadienyl dimethoxy titanium chloride , Pentamethylcyclopentadienylmethoxytitanium dichloride, cyclopentadienyltribenzyltitanium, cyclopentadienyldimethylmethoxytitanium, methylcyclopentadienyldimethylmethoxytitanium, pentamethylcyclopentadienylmethyldiethoxytitanium, trimethylsilylcyclopenta Examples thereof include dienyl trimethyl titanium, indenyl titanium trichloride, indenyl titanium trimethoxide, indenyl titanium triethoxide, indenyl trimethyl titanium and indenyl tribenzyl titanium.

Specific examples of the compound of the formula (IV) are bis (cyclopentadienyl) dimethyl titanium, bis (cyclopentadienyl) diphenyl titanium, bis (cyclopentadienyl) diethyl titanium and bis. (Cyclopentadienyl) dibenzyl titanium, bis (methylcyclopentadienyl) dimethyl titanium, bis (pentamethylcyclopentadienyl) dimethyl titanium, bis (methylcyclopentadienyl) dibenzyl titanium, bis (pentamethylcyclo) Examples thereof include pentadienyl) dibenzyl titanium, bis (pentamethylcyclopentadienyl) chloromethyl titanium, and bis (pentamethylcyclopentadienyl) hydridomethyl titanium.

Further, specific examples of the compound of the formula (V) include ethylenebis (indenyl) dimethyltitanium, ethylenebis (tetrahydroindenyl) dimethyltitanium,
Examples thereof include dimethylsilylene bis (cyclopentadienyl) dimethyl titanium. In addition to the above titanium compounds, tetramethoxy titanium, tetraethoxy titanium, tetra-n-butoxy titanium, tetraisopropoxy titanium, titanium tetrachloride, titanium trichloride, dimethoxy titanium dichloride, methoxy titanium trichloride, trimethoxy titanium chloride, etc. Can also be used.

In the method of the present invention, the catalyst (A) is used as a catalyst.
The component (B) is used together with the component. If the component (B) is a compound that reacts with the transition metal compound that is the component (A) to form an ionic complex as described above, the type thereof is particularly Although not limited, preferred ones are:
Cation and multiple groups are VB group, VIB group, VIIB group,
A coordination complex compound including an anion bound to an element selected from Group VIII, Group IB, Group IIB, Group IIIA, Group IVA, and Group VA can be given. The type of the coordination complex compound is not particularly limited, but the coordination complex compound represented by the following formula (VI) or (VII) can be preferably used. ([L ¹ -H] ^g +) _h ^{([M 2 X 1 X 2 ··· X} p ] _{^{(pq) -) i ··· (}} VI) or ([L ^{2] g} +) _h ([M ³ X ¹ X ² ... X ^p ] ^(pq)- ) _i ... (VII) [wherein L ² is M ⁴ , R ⁶ R ⁷ M ⁵ or R ⁸ ₃ C]. ] In the formulas (VI) and (VII), L ¹ is a Lewis base,
M ² and M ³ are VB group, VIB group and VIIB group of the periodic table, respectively.
An element selected from group VIII, group VIII, group IB, group IIB, group IIIA, group IVA or group VA, M ⁴ is group IB, group IIB, group VIII of the periodic table
A metal selected from Group VIII, M ⁵ is a metal selected from Group VIII of the periodic table, X ^{1 to} X ^p are a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, and a carbon number of 1, respectively.
To an alkyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organic metalloid group or a halogen atom, and R ⁶ and R ⁷ are a cyclopentadienyl group and a substituted group, respectively. Cyclopentadienyl group, indenyl group or fluorenyl group,
R ⁸ represents a hydrocarbon group. q is the valence of M ² and M ³ and is 1
To an integer of 7, p is an integer of 2 to 8, g is an integer of 1 to 7 as an ionic valence of L ¹ -H and L ² , h is an integer of 1 or more, i = h
Xg / (pq).

Specific examples of the Lewis base represented by L ¹ include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile. ,
Amine such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, 2,2'-bipyridine, phenanthroline, phosphine such as triethylphosphine and triphenylphosphine, ethylene, butadiene as a chain unsaturated hydrocarbon, 1 -Pentene, isoprene, pentadiene, 1-hexene and their derivatives, cyclic unsaturated hydrocarbons such as benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and their derivatives. Be done. M ² and M
Specific examples of ³ include B, Al, Si, P, As, and Sb.
As specific examples of M ⁴ , Li, Na, Ag, Cu, etc.,
Specific examples of M ⁵ include Fe, Co, Ni and the like. Specific examples of X ^{1 to} X ^p include, for example, a dialkylamino group such as a dimethylamino group and a diethylamino group,
Methoxy group, ethoxy group, n-butoxy group as alkoxy group, phenoxy group as aryloxy group, 2,6
-Dimethylphenoxy group, naphthyloxy group, carbon number 1
To 20 alkyl groups such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, n-octyl group, 2-ethylhexyl group, aryl group having 6 to 20 carbon atoms, alkylaryl group or As an arylalkyl group, a phenyl group, a p-tolyl group, a benzyl group, a pentafluorophenyl group, a 3,5-di (trifluoromethyl) phenyl group, a 4-tert-butylphenyl group, a 2,6-dimethylphenyl group, 3 , 5-dimethylphenyl group, 2,4-dimethylphenyl group, 1,2-dimethylphenyl group, as halogen, F, Cl, Br, I,
Examples of the organic metalloid group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron group. Specific examples of the substituted cyclopentadienyl group for R ⁶ and R ⁷ include a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.

Among the compounds of the formulas (VI) and (VII), the following can be used particularly preferably. For example, as the compound of formula (VI), triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (n-butyl) tetra (o, p-dimethylphenyl) borate Ammonium, trimethylammonium tetraphenylborate, tri (n-butyl) ammonium tetra (p-trifluoromethyl) borate, triphenylphosphonium tetraphenylborate, tri (methylphenyl) phosphonium tetraphenylborate, tri (dimethylphenyl) tetraphenylborate Phosphonium, i-propylammonium tetra (pentafluorophenyl) borate, dicyclohexylammonium tetraphenylborate, triethylammonium tetra (pentafluorophenyl) borate System, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, triethylammonium hexafluoroarsenate, dimethylanilinium tetra (pentafluorophenyl) borate, diethylanilinium tetra (pentafluorophenyl) borate, tetra (pentafluoro) Phenyl) borate di-n-butylanilinium, tetra (pentafluorophenyl) borate methyldiphenylalmonium, tetra (pentafluorophenyl) borate p-bromo-N, N-dimethylanilinium and the like.

On the other hand, as compounds of formula (VII), ferrocenium tetraphenylborate, ferrocenium tetra (pentafluorophenyl) borate, decamethylferrocenium tetra (pentafluorophenyl) borate, acetylferrotetra (pentafluorophenyl) borate Cenium, formylferrocenium tetra (pentafluorophenyl) borate, cyanoferrocenium tetra (pentafluorophenyl) borate, silver tetraphenylborate, silver tetra (pentafluorophenyl) borate, trityl tetraphenylborate, tetra (pentafluoro) Phenyl) trityl borate, silver hexafluoroarsenate, silver hexafluoroantimonate, silver tetrafluoroborate and the like.

In the method of the present invention, the above-mentioned components (A) and (B) are used as main components, but (C) is further added if necessary.
Organoaluminum compounds can also be used. (C)
Examples of the organoaluminum compound as a component include those represented by the general formulas (VIII), (IX) and (X). R ⁹ _k AlY _3-k (VIII) [R ⁹ is a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 12 alkyl groups, alkenyl groups, aryl groups, aralkyl groups, etc., Y is a hydrogen atom. Or represents a halogen atom. k
Is in the range of 1 ≦ k ≦ 3. ] Specifically, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, general formula (IX)

[0032]

[Chemical 5]

[R ⁹ is the same as above. r represents the degree of polymerization and is usually 1 to 50. ] A chain aluminoxane represented by

[0034]

[Chemical 6]

[R ⁹ is the same as above. The preferred number of repeating units is 2 to 50. ] A cyclic alkylaluminoxane having a repeating unit represented by

The catalyst used in the method of the present invention contains, in addition to the above-mentioned components (A) and (B) as main components,
Some of the main components are the above-mentioned component (A), component (B) and component (C). In this case, the addition ratio of the component (A) and the component (B) is not particularly limited, but the molar ratio of the component (A) to the component (B) is 1: 0.01 to 1: 100, and particularly 1: 1 to 1: 1.
It is preferably 1:10. Further, the molar ratio of the monomer to the transition metal in the component (A), that is, the monomer / transition metal (molar ratio) is 1 to 10 ⁸ , preferably 1
00 to 10 ⁷ . In the present invention, the polymerization method may be any of bulk polymerization, solution polymerization, suspension polymerization and the like. When a solvent is used, aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, halogenated hydrocarbons such as benzene, toluene and xylene can be used. Two or more kinds of these solvents may be combined. The monomer / solvent ratio is arbitrary. Further, the polymerization conditions are not particularly limited, but the polymerization temperature should be −100 to 250 ° C., preferably 0 to 80 ° C., the polymerization time should be 5 minutes to 24 hours, preferably 1 hour or more. Although there is no particular limitation, it is effective to carry out in the presence of hydrogen to control the molecular weight.

Further, the components (A) and (B) may be contacted in advance, and the contact product may be separated and washed before use, or may be contacted in the polymerization system. Moreover, the usage-amount of (C) component is 0-100 mol normally with respect to 1 mol of (A) component. When the component (C) is used, the polymerization activity can be improved, but if the amount is too large, the effect corresponding to the added amount will not be exhibited. The component (C) may be used in contact with the contact product of the component (A), the component (B) or the component (A) and the component (B). This contact may be made in advance, or may be sequentially added into the polymerization system and brought into contact.

In producing the copolymer by the method of the present invention, two or more kinds of aryl styrene-based monomers are used, or the aryl styrene-based monomer and another styrene-based monomer are used. These various combinations form a copolymer composed of two or more types of structural repeating units. Further, depending on the above-mentioned aryl styrene-based monomers or a combination of the aryl styrene-based monomer and other styrene-based monomer, in addition to the binary copolymer, a multi-component copolymer such as a terpolymer and a quaternary copolymer. Etc. can also be manufactured. There are various types of this copolymer, and among them, a copolymer of p-phenylstyrene (4-vinylbiphenyl) and another styrene-based monomer is preferable, and the composition thereof is p-phenylstyrene unit. 5
0-99.9 mol% and especially 60-99.5 mol% are preferred.

On the other hand, the stereoregularity of the arylstyrene homopolymer obtained by the method of the present invention has a syndiotactic structure. In addition, in the arylstyrene-based copolymer obtained by the method of the present invention, not only the repeating units I (that is, the repeating units derived from the arylstyrene-based monomer) that are bonded to each other but also the repeating units I and II ( That is, the repeating units derived from other styrenic monomers) have a syndiotactic structure (co-syndiotactic structure) between them. In addition, this copolymer has a repeating unit I,
There are various embodiments of block copolymerization, random copolymerization or alternating copolymerization of II. The proportion of the repeating unit I in this copolymer is arbitrary, and any proportion can be produced by the method of the present invention.
A content of 50 mol% or more gives a copolymer having excellent heat resistance.

The (co) polymer obtained by the method of the present invention is
The stereoregularity has a syndiotactic structure. Here, the high syndiotactic structure is
The stereochemical structure is a syndiotactic structure, that is, it has a stereostructure in which a phenyl group or a substituted phenyl group, which is a side chain, is alternately located in the opposite direction with respect to the main chain formed from carbon-carbon bonds. Tacticity is quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon. ^The tacticity measured by the ¹³ C-NMR method is the proportion of a plurality of continuous constitutional units, for example, diad in the case of 2 and triad in the case of 3.
Individual cases can be indicated by a pentad. The styrene-based (co) polymer having a syndiotactic structure referred to in the present invention means, in a chain of styrene-based repeating units, preferably 75% or more in racemic dyad, more preferably 85% or more, or racemic pentad. Those having a syndiotacticity of preferably 30% or more, more preferably 50% or more are shown. However, the degree of syndiotacticity varies slightly depending on the type of substituent. Although the molecular weight of the (co) polymer obtained by the production method of the present invention varies depending on the polymerization conditions, the weight average molecular weight is usually 5,000 to 3,000,000.
It is preferably 10,000 or more.

[0041]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 (1) Tetra (pentafluorophenyl) boric acid tri-n-
Preparation of butylammonium pentafluorophenyllithium prepared from bromopentafluorobenzene (152 mmol) and butyllithium (152 mmol) in hexane at -78 ° C with 65 mmol boron trichloride in hexane at -78 ° C. Was added to the solid component obtained by separating the hexane-soluble component by filtration at −78 ° C., the temperature was raised to room temperature, and the hexane-soluble component was filtered off to remove tri (pentafluorophenyl) boron. Obtained as a hexane solution. This tri (pentafluorophenyl) boron (41 mmol) is separately reacted with pentafluorophenyllithium (41 mmol) prepared in the same manner in diethyl ether to convert lithium tetra (pentafluorophenyl) boron to white. Isolated as a solid. Next, the obtained lithium tetra (pentafluorophenyl) boron (16
By reacting tri-n-butylamine hydrochloride (16 mmol) with water to obtain 12.8 mmol of tri-n-butylammonium tetra (pentafluorophenyl) borate as a white solid.

(2) Production of p-phenylstyrene polymer In a dry reaction vessel under an argon atmosphere, 2 ml of toluene and triisobutylaluminum (Tl) were added at room temperature.
BA) 0.08 mmol and 8.8 ml of p-phenylstyrene solution prepared in a toluene solution having a concentration of 1 mol / l.
(8.8 × 10 ⁻³ mol) was added and the mixture was kept at 70 ° C. for 30 minutes. Next, 0.5 micromol of pentamethylcyclopentadienyltrimethyl titanium was added, and tetra (pentafluorophenyl) boron tri-n-prepared in the above (1) was added.
Butyl ammonium (0.5 μmol) was added and the reaction was carried out for 2 hours. Then, the reaction product was added to methanol to stop the reaction, and after filtration, the reaction product was further washed with methanol three times.
Drying under reduced pressure gave 0.85 g of polymer. This molecular weight was measured by gel permeation chromatography (GP
When measured by C), the weight average molecular weight (Mw) in terms of polystyrene was 124,000. Note that G
The PC measurement conditions were as follows. Apparatus: Waters ALS / GPC 150C Column: TSK HM + GMH6 × 2 (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: 1,2,4-trichlorobenzene (TCB) Flow rate: 1.0 ml / min. Further, this polymer poly (4-vinylbiphenyl) was subjected to extraction for 4 hours with methyl ethyl ketone as a solvent using a Soxhlet extractor, and it was 99% by weight.
Was insoluble. Further, the melting point of this polymer was 352 ° C. by differential scanning calorimetry, and it was found to be a crystalline polymer (heating rate 20 ° C./min, fast heating). ¹³ C-NMR (1 of the polymer obtained in Example 1
00MHz) was measured, and it was 141.0ppm, 14
A sharp peak based on the quaternary carbon of the side chain biphenyl ring was observed at 4.0 ppm, and it was confirmed that the structure had a syndiotactic structure. The syndiotacticity determined by ¹³ C-NMR was 93% for racemic pentad.

Examples 2 to 4 In Example 1 (2), as the styrene-based monomer,
The same operation as in Example 1 (2) was performed except that a predetermined amount of styrene was added at the same time as p-phenylstyrene,
A copolymer was obtained. The composition ratio of this copolymer was determined by a calibration curve method of infrared absorption spectrum (poly (4-vinylbiphenyl) obtained by radical polymerization and polystyrene having a syndiotactic structure synthesized by a known method were uniformly mixed in a predetermined amount. prepared which mixed, each of the infrared absorption spectrum was measured, the absorption of 696cm ^-1 and 814 cm ^-1
The peak intensity ratio of absorption was calculated, a calibration curve was created from the mixture ratio and the peak intensity ratio, and 696 cm of the obtained copolymer was obtained.
And the peak intensity ratio of absorption of the absorbent and 814 cm ^{-1 -1} by the calibration curve was determined the composition ratio of the copolymer. ). The results are shown in Table 1. It can be seen that each of these copolymers has a melting point of 300 ° C. or higher and has a syndiotactic structure.

Examples 5 and 6 Copolymerization was carried out in the same manner as in Example 3 except that p-methylstyrene or m-phenylstyrene was used as the styrene monomer. The copolymer composition was determined based on the amount of unreacted monomer recovered from the copolymerization reaction system, which was analyzed by gas chromatography. The results are shown in Table 1.

Comparative Examples 1 and 2 The catalyst components of Example 1 (2) and Example 3 were converted to methylaluminoxane (MAO), triisobutylaluminum (TlBA), pentamethylcyclopentadienyl titanium trimethoxide (Cp ^* Ti). It carried out similarly except having changed into (OMe) ₃ ). The results are shown in Table 1.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

According to the method of the present invention, since a highly active and relatively inexpensive catalyst is used, it is possible to reduce the amount of the catalyst used in the production of a styrene-based polymer or a copolymer, and at the same time obtain ( Since the residual catalyst in the (co) polymer can be reduced, the deashing step is unnecessary or simplified. Therefore, according to the method of the present invention, the cost of the catalyst can be reduced and the styrene-based (co) polymer can be efficiently produced. Moreover, the obtained styrene-based (co) polymer has improved physical properties. It's stable and the hue is improved, and moreover,
Since its three-dimensional structure has a high syndiotactic structure, it becomes a resin with excellent heat resistance and mechanical strength, and is effectively used as a material for various molded products.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08F 30/08 MNU 7242-4J

Claims (5)

[Claims] 1. A styrene-based monomer having an aryl substituent or a styrene-based monomer containing the styrene-based monomer having the aryl substituent and another styrene-based monomer is used as (A) transition metal compound and (B) the transition metal. A styrene-based polymer or a styrene-based copolymer having a syndiotactic structure characterized by being polymerized or copolymerized in the presence of a catalyst containing a compound which reacts with a compound to form an ionic complex Production method. 2. The method according to claim 1, wherein styrenic monomers having aryl substituents are copolymerized with each other. 3. A styrenic monomer having an aryl substituent has the general formula (I): [Wherein R ¹ is a hydrogen atom, a halogen atom or a carbon atom,
It represents a substituent containing at least one of oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom, silicon atom and tin atom, and m represents an integer of 1 to 5. However, among m R ¹ , at least ^one of them is an aryl group having a hydrogen atom, an aryl group having a halogen atom, or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom. An aryl group having a substituent containing at least one of the above. ] The method according to claim 1, which is an aryl styrene-based monomer represented by the following formula. 4. The other styrenic monomer has the general formula (I
I) [Chemical 2] [Wherein R ² is a hydrogen atom, a halogen atom or a carbon atom,
A substituent containing any one or more of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom is shown, and n is an integer of 1 to 5. However, when n is plural, each R ² may be the same or different. ] A styrenic monomer represented by
The method described. 5. The method according to claim 1, wherein the catalyst comprises a component (A), a component (B) and a (C) organoaluminum compound as a main component.