JPH03166204A - Styrene-based copolymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer excellent in heat resistance and moldability and suitable for electric appliances, etc., by copolymerizing a styrene-based monomer and an acenaphthylene-based monomer using a transition metal component and a product compound of a catalytic reaction between an organoaluminum compound and a condensation agent as a catalyst. CONSTITUTION:Using a transition metal component and a product compound of a catalytic reaction between an organoaluminum compound and a condensation agent as catalyst components, a styrene-based monomer represented by formula I (R<1> is substituent containing one or more of H, halogen, C, O, N, S, P, Se, Si, Sn, etc., m is 1-3) and an acenaphthylene-based monomer represented by formula II (R<3>-R<4> are same kind as R<1>; n is 1-6) are copolymerized to obtain the objective copolymer having a structural unit represented by formula III, a structural unit represented by formula IV, >=5 polymerization degree and a styrene chain part having a stereoregularity mainly composed of syndiotactic structure.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a styrenic copolymer and a styrene copolymer with good heat resistance and shapeability, which can be suitably used as a material for electrical products, automobile parts, etc. The present invention relates to a manufacturing method thereof.

[Prior Art and Problems to be Solved by the Invention] There is a demand for resins with good heat resistance and moldability as members for electrical products and automobile parts.

For this reason, polystyrene, which mainly has a syndiocctic structure (Japanese Patent Application Laid-open No. 104818/1983.
-187708, etc.) have been proposed. Although this polystyrene mainly having a jindiotactic structure has excellent heat resistance, it has a drawback that certain cycles tend to be long due to a low crystallization rate.

The purpose of the present invention is to solve these conventional problems and provide a styrenic copolymer that has excellent heat resistance, a high crystallization rate, and excellent moldability, and an efficient method for producing the same. It is something to do.

[Means to solve the problem]

That is, the first aspect of the present invention is a general formula [wherein R1 is a hydrogen atom]. Halogen atom, or carbon atom, oxygen atom, nitrogen atom, sulfur atom, or phosphorus atom. It represents a substituent containing at least one of a selenium atom, a silicon atom, and a tin atom, and m represents an integer of 1 to 3. However, when m is plural, each RI may be the same or different. ] At least one structural unit CI)
and the general formula (wherein R2, R3, R4 are hydrogen atoms, halogen atoms,
Or carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom. It represents a substituent containing at least one of a silicon atom and a tin atom, and n represents an integer of 1 to 6. However, when n is plural, each R4 may be the same or different. ], the degree of polymerization is 5 or more, and the stereoregularity of the styrene chain portion is mainly a syndiotactic structure. .

In addition, the second aspect of the present invention uses as a catalyst component a contact mixture of (A) a transition metal component and (B) an organic altanium compound with a condensing agent; , halogen atom, or carbon atom, oxygen atom. Nitrogen atom, sulfur atom, phosphorus atom, selenium atom. It represents a substituent containing at least one of a silicon atom and a tin atom, and m represents an integer of 1 to 3. However, when m is plural, each R may be the same or different. ] at least one styrenic monomer and a general monomer (wherein R2, R3.R' are hydrogen atoms, halogen atoms,
Or carbon, oxygen, nitrogen, or sulfur atoms. It represents a substituent containing at least one of a phosphorus atom, a selenium atom, a silicon atom, and a tin atom, and n represents an integer of 1 to 6. However, when n is plural, each R4 may be the same or different. The present invention provides the first method for producing a styrenic copolymer, which comprises copolymerizing an acenaphthylene compound represented by the following.

The styrenic copolymer in the present invention has the general formula [[
It has a structural unit [■] (repeating unit) represented by ] and a structural unit [■] (repeating unit) represented by general formula (n).

Here, R1 to R4 in the structural unit [I] and (I[) are hydrogen atoms, halogen atoms, carbon atoms, oxygen atoms, 2 nitrogen atoms. Indicates a substituent containing one or more of a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom, and a tin atom.

Here, examples of halogen atoms include chlorine, fluorine, and bromine. Iodine can be mentioned.

Further, specific examples of substituents containing carbon atoms include alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, isoprobyl group, and tertiary butyl group; hydrogen atoms in benzene rings having 6 to 30 carbon atoms; Aryl group with a substituent containing a halogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom, silicon atom, or tin atom; a carbon 1- to chloroethyl group, bromomethyl group, promoethyl group, etc. and 20 halogen-substituted alkyl groups.

Here, in the Hensen ring having 6 to 30 carbon atoms, hydrogen atom, halogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom,
Phosphorus atom, selenium atom. Examples of the aryl group having a substituent containing a silicon atom or a tin atom include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Inden ring. Azulene ring, heptalene ring. Biphenylene ring, aS indacene ring, S-indacene ring, acenaphthylene ring, phenalene ring, fluoranthene ring, acephenanthrene ring. Aceantrylene ring. Triphenylene ring, naphthacene ring. Pleiadene ring, picene ring, perylene ring, pentaphene ring, pentacene ring, rubicene ring. Corocene ring, pyrantrene ring, obalene ring, and their alkyl substituents (methyl group, ethyl group, isoprobyl group, tert-butyl group, etc.). Halogen-substituted alkyl groups (chloroethyl group, promoethyl group, etc.), substituents containing oxygen atoms (methoxy group, ethoxy group, isoproboxy group, methoxycarbonyl group, acetyloxy group, etc.), substituents containing silicon atoms (trimethylsilyl group, etc.) ), substituents containing tin atoms (trimethylstannyl group, tributylstannyl group, triphenylstannyl group, etc.), substituents containing nitrogen atoms (dimethylamino group, diazo group, nitro group, cyano group, etc.), sulfur Substituents containing atoms (sulfone group, sulfonic acid methyl ester group, phenylthio group, methylthio group, merkabuto group, etc.), substituents containing selenium atoms (methylseleno group, phenylseleno group, methylselenoxyl group, phenylselenoxyl group, etc.) Substituents containing 1 phosphorus atom (phosphoric acid methyl ester group, phosphite group, dimethylphosphino group, diphenylphosphino group, methylphosphinyl group, phenylphosphinyl group, etc.) can be substituted at any position. Includes things that have been done.

In addition, substituents containing an oxygen atom include a methoxy group, an ethoxy group, an isoproboxy group, a methoxycarbonyl group,
Examples of the substituent include an acyloxy group, and examples of the substituent containing a silicon atom include a trimethylsilyl group. Next, examples of substituents containing a tin atom include a 1.limethylscunnyl group, a tributylstannyl group, and a triphenylscunnyl group. Furthermore, substituents containing a nitrogen atom include dimethylamino group, diazo group, nitro group,
Examples include a cyano group, and examples of substituents containing a sulfur atom include a sulfone group, a sulfonic acid methyl ester group, a phenylthio group, a methylthio group, and a merkabuto group. In addition, examples of substituents containing a selenium atom include methylseleno group, phenylseleno group, methylselenoxyl group, and phenylselenoxyl group, and examples of substituents containing a phosphorus atom include methyl phosphate group and phosphite ester group. group, dimethylphosphino group, diphenylphosphino group, methylphosphinyl group, phenylphosphinyl group, etc.

Furthermore, in the structural unit (1) represented by the -a formula (1), m is an integer of I to 3, and in the structural unit (II) represented by the general formula (Ir), n is an integer of 1 to 6. It is. Here, when m and n are each plural, there are m R
The 1 or n R4's may be the same or different.

Specific examples of the structural unit (1) having such a substituent include styrene, P-methylstyrene, m-methylstyrene, O-methylstyrene 1, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3. 4-Dimethylstyrene 2 Alkyl styrenes such as 3,5-dimethylstyrene, P-tert-butylstyrene; p-chlorostyrene, m-chlorostyrene, O-kr:Ir:I styrene, p-promostyrene, m-promo Styrene, 0-
Furomostyrene, P-fluorostyrene, m-fluorostyrene, O-fluorostyrene. Halogenated styrenes such as 0-methyl p-fluorostyrene; vinylbiphenyls such as 4-vinylbiphenyl, 3-vinylbiphenyl, and 2-vinylbiphenyl; 1-(4-vinylphenyl)naphthalene, 2-(4-vinylphenyl)naphthalene: /, 1-(3-vinylphenyl)naphthalene 7.2-(
Vinylphenylnaphthalenes such as 3-vinylphenyl)naphthalene, 1-(2-vinylphenyl)naphthalene, 2-(2-vinylphenyl)naphthalene; l(4-vinylphenyl)anthracene, 2-(4-vinylphenyl)anthracene, ! -(4-vinylphenyl)anthracene, 1-(3-vinylphenyl)anthracene, 2
-(3-vinylphenyl)anthracene, 9-(3-vinylphenyl)anthracene, 1-(2-vinylphenyl)anthracene, 2-(2-vinylphenyl)anthracene, 9-(2-vinylphenyl)anthracene, etc. Vinylphenylanthracene [;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. l-(2-vinylphenyl)phenanthrene, 2-(
2-vinylphenyl)phenanthrene, 3-(2-vinylphenyl)phenanthrene, 4-(2-vinylphenyl)phenanthrene, 9-vinylphenylphenanthrene, etc.; 1;
-(4-vinylphenyl)pyrene, 2-(4-vinylphenyl)pyrene, 1-(3-vinylphenyl)pyrene,
Vinylphenylpyrene neck, such as 2-(3-vinylphenyl)pyrene, 1-(2-vinylphenyl)pyrene, 2-(2-vinylphenyl)pyrene; 4-vinyl-p-terphenyl, 4-vinyl-m-terphenyl, 4- vinyl 10-terphenyl, 3-hinyl-p-terphenyl, 3
-vinyl-terphenyl, 3-vinyl-terphenyl, 2-vinyl-terphenyl, 2-vinyl-terphenyl
Vinyl terphenyl iJt such as terphenyl, 2-vinyl 101 terphenyl; 4-(4-vinylphenyl)
Vinyl phenyl terphenyl such as 1p-terphenyl; 4-vinyl-4°-methylbiphenyl. 4-vinyl-3゜methylbiphenyl, 4-vinyl-2''-methylbiphenyl.2-methyl-4-vinylbiphenyl, 3-
Vinylalkylbiphenyls such as 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
Vinyl halides such as ゜-promobiphenyl, 4-vinyl-3"-bromobiphenyl, 4-vinyl-2'-7' lomobiphenyl, 4-vinyl-2-promobiphenyl, 4-vinyl-3-7' lomobiphenyl 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 Alkoxyvinylbiphenyl such as 4-vinyl-3-ethoxybiphenyl; alkoxyvinylbiphenyl such as 4-vinyl-4-methoxylponylbiphenyl, 4-vinyl-4-methoxylponylbiphenyl, etc. Rubonylvinylbiphenyls; alkoxyalkylvinylbiphenyls such as 4-vinyl-4-methoxymethylbiphenyl; 4-vinyl-4" trialkylsilylvinylbiphenyls such as trimethylsilylbiphenyl; 4-vinyl-4" Trialkylstannylvinylbiphenyl such as monotrimethylstannylbiphenyl, 4-vinyl-4=triptylstanylbiphenyl, etc.: Trialkylsilylmethylvinylbiphenyl such as 4-vinyl-4゜1trimethylsilylmethylbiphenyl, 4 -Arylstyrenes such as trialkylscunnylmethylvinylbiphenyls such as vinyl-4゜-trimethylstannylmethylbiphenyl, 4-vinyl-4゜-tributylstannylmethylbiphenyl; p-chloroethylstyrene. m
Halogen-substituted alkylstyrene such as chloroethylstyrene, 0-chloroethylstyrene; p-methoxystyrene, m-methoxystyrene, 0-methoxystyrene, p
monoethoxystyrene, m-ethoxystyrene, 0-
Alkoxystyrenes such as ethoxystyrene; alkoxycarbonylstyrenes such as p-methoxycarbonylstyrene and m-methoxycarbonylstyrene; acyloxystyrenes such as acetyloxystyrene, ethanoyloxystyrene, and penzoyloxystyrene; p-vinylbenzylpropyl Alkyl ether styrenes such as ethers; alkylsilylstyrenes such as p-trimethylsilylstyrene;
Alkyl stannylstyrenes such as P-}liptylstannylstyrene and ρ-triphenylstannylstyrene; vinylstyrenes such as ethyl vinylbenzenesulfonate, vinylbenzyl dimethoxy phosphide, and P-vinylstyrene. Examples include:

Specific examples of the structural unit (n) include acenaphthylene, 1-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 6-methylacenaphthylene. l,4-dimethylacenaphthylene, 1,
5-dimethylacenaphthylene, ■,6-dimethylacenaphthylene, ■,8 dimethylacenaphthylene, l,9-dimethylacenaphthylene, 1.10-dimethylacenaphthylene, 4-ethylacenaphthylene, 5-ethylacenaphthylene, 6-ethylacenaphthylene, 4-n-probylacenaphthylene, 5-n-probylacenaphthylene, 6
-Alkyl-substituted acenaphthylenes such as n-probylacenaphthylene; 4-chloroacenaphthylene. 5-chloroacenaphthylene, 6-chloroacenaphthylene, 4-promoacenaphthylene, 5-promoacenaphthylene. 6-promoacenaphthylene, 4-iodoacenaphthylene, 5-iodoacenaphthylene, 6-iodoacenaphthylene. 4-
Fluoroacenaphthylene, 5-fluoroacenaphthylene, 6-fluoroacenaphthylene, 4,5-dichloroacenaphthylene, 4.6-dichloroacenaphthylene, 4.8
-dichloroacenaphthylene 4 9-dichloroacenaphthylene, 4.10 dichloroacenaphthylene. 5.6-dichloroacenaphthylene, 5.8-dichloroacenaphthylene 95.9-dichloroacenaphthylene, 6,8-dichloroacenaphthylene, 4,5-dibromoacenaphthylene,
4,6-dibromoacenaphthylene. 4.8 dibromoacenaphthylene, 4,9-dibromoacenaphthylene, 4,t
o-dibromoacenaphthylene, 5 6-dibromoacenaphthylene. 5.8-dibromoacenaphthylene, 5,9-
dibromoacenaphthylene, 6.8 dibromoacenaphthylene with a \rogen-substituted acenaphthylene neck; 4-phenylacenaphthylene, 5-phenylacenaphthylene, 6-
Aryl-substituted acenaphthylenes such as phenylacenaphthylene; alkoxy-substituted acenaphthylenes such as 4-methoxyacenaphthylene, 5-methoxyacenaphthylene, and 6-methoxyacenaphthylene; 4-methoxycarbonylacenaphthylene, 5-methoxy Carbonyl-substituted acenaphthylenes such as carbonyl acenaphthylene and 6-methoxycarbonyl acenaphthylene; 4-methyl luponyloxyacenaphthylene, 5-methyl luponyloxyacenaphthylene, 6-methyl luponyloxy Azyloxy-substituted acenaphthylene U such as acenaphthylene
N i 4-trimethylsilylacenaphthylene, 5
-Trimethylsilylacenaphthylene Alkylsilyl-substituted acenaphthylenes such as 6-trimethylsilylacenaphthylene i4-Tri10butylscunnylacenaphthylene, 5-tri101butylscunnylacenaphthylene, 6
Examples include alkylstannyl-substituted acenaphthylene necks such as -tri-n-butylstannylacenaphthylene.

In addition, the polymer obtained in the present invention has the general formula [
A polymer obtained by polymerizing a styrenic heptanomer represented by (2)], and may be a copolymer or a highly dispersed mixture of each homopolymer. Furthermore, since the above structural units (1) and (]I) do not necessarily represent only one type of structural unit, but also represent two or more types of structural units, the copolymer of the present invention is a binary copolymer. In addition, it also includes multi-component copolymers such as ternary copolymers and quaternary copolymers.

Here, the first aspect of the present invention is that the content of the structural unit (n) is preferably 0.1 to 70 mol% of the total, more preferably O. It is 1 to 40 mol%. Therefore, it has a high crystallization temperature and excellent shapeability. Generally, if the content of the structural unit (n) is less than 0.1 mol % of the total, the crystallization temperature is low and it is difficult to form a crystal.

The styrenic copolymer of the present invention has the above structural units (
repeating unit) and has a degree of polymerization of 5 or more, but furthermore, the stereoregularity of the styrene linkage is mainly due to the syndiotactic chain structure, that is, the styrene or acenaphthylene moiety is formed from a carbon-carbon bond. It has a three-dimensional structure in which substituted phenyl groups as side chains are alternately positioned in opposite directions with respect to a certain main chain, and its tacticity is determined by nuclear magnetic resonance (NMR).

Specifically, the CI carbon signal of the aromatic ring by l''C-NMR method (nuclear magnetic resonance spectrum using carbon isotope),
By analysis of methine/methylene carbon signals or 'H-NMR proton signals. Tacticity quantified by NMR is defined as the abundance ratio of a plurality of consecutive structural units (i.e., the existence ratio of relative conformational relationships of consecutive structural units), for example, in the case of two, guiando, 3
In the case of 5 units, it can be indicated by a triad, and in the case of 5 units, it can be indicated by a bentad, but in the present invention, having a mainly syndiotactic structure means that the syndiotacticity depends on the type of substituents and the content ratio of each repeating unit. Although the degree varies slightly, in the chain of styrenic repeating units, it is usually at least 75% for racemic dyads, preferably at least 85% for racemic bentads, or 30% for racemic bentads.
The above refers to those having preferably syndiotacticity of 50% or more.

Note that the styrenic copolymer mainly having a syndiotactic structure as used in the present invention does not necessarily have to be a single copolymer. As long as the syndiotacticity is within the above range, it may be a mixture with a styrene copolymer having an isotactic or actuctic structure, or it may be incorporated into a polymer chain.

Furthermore, the styrenic copolymer of the present invention may be a mixture of different molecular weights, and the degree of polymerization is at least 5 or more, preferably 10 or more. In terms of weight average molecular weight (Mw), preferably 5,000 to 100
10,000, more preferably 10,000 to 800,000. Note that there is no particular restriction on the molecular weight distribution.

The first styrenic copolymer of the present invention as described above can be efficiently produced, for example, by the second method of the present invention.

The first styrenic copolymer of the present invention as described above can be efficiently produced, for example, by the second method of the present invention.

That is, the second aspect of the present invention uses (A) a transition metal component and (B) a contact product of an organoaluminum compound and a condensing agent as a catalyst, and a styrenic monomer represented by the general formula (ITI). and General formula (IV)
It is characterized by copolymerizing acenaphthylene monomers represented by:

In other words, at least one styrenic heptanomer represented by the general formula (III) and the general formula (IV
) using two or more types of acenaphthylene monomers represented by (A) as raw materials.
Copolymerization is carried out in the presence of a catalyst consisting of a transition metal component and (B) a contact product of an organic aluminum compound and a condensing agent.

There are various transition metal compounds that are component (A) of the catalyst, but preferably the general formula M'R', R'bR'cR8[4-(a+b+cl+
+ - (V)M2R',I R".R"+:+-<d
or. 1, ... [■] M3R", RI3,, 11 0 [■] or M'R 1, R"H R"H- (ta・h)
1 '''11 0 [■] [In the formula, R5 to Rl6 are a hydrogen atom and a halogen atom, respectively. An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms , carbon number 6
-20 arylalkyl group, C6-20 aryloxy group, C1-20 acyloxy group, acetylacetonyl group, cyclopentadienyl group, substituted cyclopentadienyl group or indenyl group. Also, a
, b, c each indicate an integer greater than or equal to O that satisfies 0≦a+b+c≦4, d and e each indicate an integer greater than or equal to O that satisfies 0≦d+e≦3, and f satisfies 0≦f≦2. O
Indicates an integer greater than or equal to g, h are each 0≦g + h
Indicates an integer greater than or equal to 0 that satisfies ≦3. Furthermore, M1,
M2 represents titanium, zirconium, hafnium or vanadium, and M:I, lvl4 represents vanadium. ] At least one selected from the transition metal compounds represented by
It is a species compound. Among these transition metal compounds,
It is preferable to use a material in which M1 in the general formula [■] is titanium or zirconium.

Here, among those represented by R5 to R16 in the above formula, specific examples of the halogen atom include chlorine, bromine, iodine, and fluorine. In addition, the substituted cyclopentadienyl group is, for example, a cyclopentadienyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, specifically, a methylcyclopentadienyl group, a 12-dimethylcyclopentadienyl 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 group having 1 to 20 carbon atoms (specifically,
Methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy 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.),
Arylalkyl group having 6 to 20 carbon atoms (specifically, benzyl group, 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 R3 to Rl6 may be the same or different as long as they meet the above conditions.

Such general formulas (V), (VI), (■
] or [■] Among the transition metal compounds, specific examples of titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetra-n-butoxytitanium, tetraisopropoxytitanium, cyclopentadienyltrimethyltitanium, cyclopenta Dienyltriethyl titanium.
Cyclopentadienyl tripyr titanium. Cyclopentadienyltributyl titanium. Methylcyclopentadienyltrimethyltitanium. 1l2-dimethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltributyl titanium, pentamethylcyclopentadienyltributyltitanium, Cyclopentadienylmethyl titanium dichloride, cyclopentadienyl ethyl titanium dichloride, pentamethyl pentadienyl methyl titanium dichloride, pentamethyl pentadienyl ethyl titanium dichloride, cyclopentadienyl dimethyl titanium monochloride, cyclopentadienyl titanium dichloride enyl diethyl titanium monochloride, cyclopentadienyl titanium trimethoxide, cyclopentadienyl titanium triethoxide, cyclobentadienyl titanium triproxide, cyclobentadienyl titanium triphenoxide. bentamethylcyclobentadienyl titanium trimethoxide,
Pentamethylcyclopentadienyl titanium triethoxide, pentamethylcyclopentadienyl titanium tribropoxide, pentamethylcyclopentadienyl titanium tributoxide. Bentamethyl cyclopentadienyl titanium triphenoxide, cyclopentadienyl titanium trichloride, pentamethyl cyclopentadienyl titanium}
IJ chloride, cyclopentadienylmethoxytitanium chloride, cyclopentadienyldimethoxytitanium chloride, bentamethylcyclopentadienylmethoxytitanium dichloride, cyclopentadienyltribenzyltitanium. Bentamethylcyclobentadienylmethyldiethoxytitanium. Examples include indenyl titanium trichloride, indenyl titanium trimethoxide, indenyl titanium triethoxide, indenyl trimethyl titanium, and indenyl tribenzyl titanium.

Among these titanium compounds, compounds that do not contain a halogen atom are preferred, and in particular, four-coordinated titanium compounds in which at least the l ligand is an unsaturated π-electron system ligand as described above are preferred. Compounds are preferred.

Further, among the transition metal compounds represented by the general formula (V), (VIA, (■) or [■]), specific examples of zirconium compounds include cyclopentadienyl zirconium trimethoxide, pentamethyl zirconium Dienylzirconium trimethoxide, cyclopentadjunyltribenzylzirconium, penkmethylpentadienyltribenzylzirconium, bisindenylzirconium dichloride, zirconium dibenzyl dichloride, zirconium tetrabenzyl, tributoxyzirconium chloride, triisoproboxyzirconium chloride, etc. can be mentioned.

Similarly, specific examples of hafnium compounds include cyclobentadienyl hafnium trimethoxide, pentamethylcyclopentadienyl hafnium trimethoxide, cyclopentadienyltribenzyl hafnium, and pentamethylcyclopentadienyltribenzyl. Examples include hafnium, bisindenylhafnium dichloride, hafnium dibenzyl chloride, hafnium tetrahendyl, tributoxyhafnium chloride, triisobroboxyhafnium chloride, and the like.

Similarly, specific examples of vanadium compounds include vanadium trichloride, vanadyl trichloride, vanadium triacetylacetonate, vanadium tetrachloride, vanadyl triptoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, etc. can be mentioned.

On the other hand, the other part of the catalyst used in the second method of the present invention (B), the contact product of the organic aluminum compound and the condensing agent, is the product described in, for example, JP-A-62-187708. The details are as follows.

That is, this contact product is obtained by bringing various organoaluminum compounds into contact with a condensing agent.

Here, the organoaluminum compound usually has the general formula AIR173 [wherein Rl7 represents an alkyl group having 1 to 8 carbon atoms]. ] Organoaluminum compounds represented by these, specifically trialkylaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, etc., are mentioned, and trimethylaluminum is especially preferred.

As for the condensing agent, water is typically used, but various other agents that can undergo a condensation reaction with the trialkylaluminium, such as copper sulfate pentahydrate, water adsorbed on inorganic substances or organic substances, and the like can also be used.

As a representative example of the contact product of the organic aluminum compound, which is the component (B) of the catalyst used in the second aspect of the present invention, and the condensing agent, the general formula A/! There is a reaction product of trialkylaldanium represented by the formula R'' and water, specifically, a compound of the general formula [where p indicates the degree of polymerization and is from 0 to 50, and R l?
represents an alkyl group having 1 to 8 carbon atoms. ] or a linear alkylaminoxane represented by the general formula -+-Al-0-→--R17 [wherein Rl7 is the same as above. ] There are cyclic alkylalkyl ξnoxanes (number of repeating units from 2 to 50) having a repeating unit represented by the following.

1a, a mixture of unreacted trialkylaluminium, various condensation products, as well as the above-mentioned chain alkylaluminoxane and cyclic alkylaluminoxane, is a mixture of alkylaluminium such as trialkylaluminium and water in contact with water; Furthermore, these molecules are complexly associated,
These products form various products depending on the contact conditions between trialkylaluminum and water, which is a condensing agent.

The reaction between the alkyl aluminum and the condensing agent at this time is not particularly limited, 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 it is contained in a metal salt, etc. There are methods such as reacting water of crystallization, water adsorbed on inorganic substances or organic substances, with an organic aluminium compound. Although this reaction proceeds without a solvent, it is preferable to conduct it in a solvent. Suitable solvents include aliphatic hydrocarbons such as hexane, hebutane, and decane, or aromatic hydrocarbons such as benzene toluene and xylene. can be mentioned. In addition, the above water contains 20% of ammonia, sulfur compounds such as ethylamine, sulfur compounds such as hydrogen sulfide, and phosphorus compounds such as phosphorous esters.
It may be contained to some extent.

In the second aspect of the present invention, the contact reaction product (for example, alkylaluminoxane) between the organoaluminum compound and the condensing agent used as the (Fl) component of the catalyst can be The solid residue is separated by filtration, and the filtrate is heated under normal pressure or reduced pressure at a temperature of 30 to 200°C, preferably 40 to 150°C, for 20 minutes to 8 hours, preferably 30 minutes to 5 hours. It is preferable to carry out the heat treatment while distilling off the solvent.

In this heat treatment, the temperature may be determined as appropriate depending on various circumstances, but it is usually carried out within the above range. in general,
At temperatures below 30°C, the effect will not be expressed, and at temperatures below 200°C.
If the temperature exceeds °C, thermal decomposition of the alkylaluminoxane itself occurs, which is not preferable.

Depending on the treatment conditions of the heat treatment, the reaction raw material 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 the organic aluminum compound and the condensing agent used as component (B) of such a catalyst, particularly an alkylaluminoxane, is an aluminum-methyl group (Al- The high magnetic field component in the methyl proton signal region based on CH3) bond is 50% or less. In other words, when observing the proton nuclear magnetic resonance ('F{-NMR) spectrum of the above-mentioned contact compound in a toluene solvent at room temperature, the methyl proton signal based on AlC}+3 is found to be tetramethylsilane. (TMS) standard 1.0
It is found in the range of ~-0.5 ppm. Since the TMS proton signal (O ppm) is in the methyl proton observation region based on Aj2CH3, this A f - C
The methyl proton signal based on H3 was compared to the methyl proton signal of toluene at 2.35p in TMS standard.
The high magnetic field component (i.e. 10.1
~0. 5 ppm) and other magnetic field components (i.e. 1.0
= 0.1 ppm), the high magnetic field component is
50% or less of the total amount, preferably 45 to 5%, can be suitably used as the (B) component of the catalyst.

The catalyst used in the method of the present invention has the above-mentioned components (II) and (B) as main components, and in addition to the above-mentioned components, other catalyst components may be added if desired, such as the general formula A/! In the formula R''C, R1 represents an alkyl group having 1 to 8 carbon atoms.] Trialkylaluminum or other organometallic compounds represented by the following can also be added.

In the second aspect of the present invention, a styrene monomer and an acenaphthylene heptanomer are copolymerized using the catalyst obtained as described above, and the polymerization method is bulk polymerization, solution polymerization,
Any method such as suspension polymerization may be used. In these cases, the solvent is pentane or hexane. Aliphatic hydrocarbons such as heptane; alicyclic hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as benzene, toluene, and xylene are used. Among these, aromatic hydrocarbons are preferred, with toluene and xylene being particularly preferred. In this case, the monomer/solvent (volume ratio) is arbitrary! t
It is possible to make a lot of money.

Furthermore, there are no particular restrictions on the polymerization conditions, but generally the polymerization temperature is 0 to 120°C, preferably 10 to 70°C, and the polymerization time is 5 minutes to 24 hours, preferably 1 hour or more. It is.

Furthermore, in order to control the molecular weight of the obtained styrenic copolymer, it is effective to carry out the reaction in the presence of hydrogen.

Furthermore, when using this catalyst, (A
) The ratio of the (B) precept varies depending on the extraction of each component, the type of styrene monomer and acenaphthylene monomer used as raw materials, and other conditions, and it is difficult to determine it unambiguously. Usually, the ratio of aluminum in the catalyst fraction (B) to the transition metal in the transition metal fraction (A);
That is, as aluminum/transition metal (molar ratio),
1 to 106 (molar ratio), preferably 10 to 104 (molar ratio).

Further, the charging ratio of the raw materials, that is, the styrene monomer/acenaphthylene monomer (molar ratio) is not limited to '18 and can be determined depending on the composition of the target product, but is preferably 1 or more. Further, the ratio between the monomer and aluminum in the catalyst component (B), that is, the total amount of monomers/aluminum (molar ratio), is 1 to 106 (molar ratio).

Furthermore, the order of charging the raw materials and catalyst components is not particularly limited and can be carried out in any order.

The first styrenic copolymer of the present invention can be produced as described above. This copolymer has high syndiotacticity as described above, but after polymerization,
If necessary, deashing with a cleaning solution containing hydrochloric acid, etc., followed by washing and drying under reduced pressure, followed by washing with a solvent such as methyl ethyl ketone to remove soluble components, produces a highly pure styrene-based product with extremely high syndiotality. Copolymers can be prepared manually.

〔Example] Next, the present invention will be explained in detail with reference to examples.

Example 1 (1) Methynoleanole ξnoxane manufactured by Kanshu Co., Ltd. In a glass container with an internal volume of 500 ml and replaced with argon, 200 d of toluene and copper sulfate pentahydrate (CuS○4.5Hz○) 1
7.7 g (71 mmol) and 250 mmol of trimethylaluminium 24dC) were added and heated at 40°C.
Allowed time to react. Thereafter, some of the solids were removed, and toluene was further distilled off under reduced pressure from the resulting solution to obtain the contact product 6.
7g was obtained. The molecular weight of this product was 610 as measured by freezing point depression method.

Also. ' High magnetic field analysis by H-NMR measurement, that is, when observing the proton nuclear magnetic resonance spectrum in toluene solvent at room temperature, (Af-Clf3)
The methyl proton signal based on the bond ranges from 1.0 to -0.0 on the basis of tetramethylsilane. Found in the 5 ppm range. The proton signal of tetramethylsilane (O ppm) is A/2-CH. This Al-CH
2. The methyl proton signal based on the 3 bonds is the methyl proton signal of toluene based on tetramethylsilane. When measured on the basis of 35 ppm and divided into high magnetic field part (i.e. 10.1 to -0.5 pllIn) and other magnetic field part (i.e. 1.0 to -0.1 ppm) The high magnetic field precept accounted for 43% of the total.

(2) Production of styrene-acenaphthylene copolymer In a dry reaction vessel under an argon atmosphere, toluene 2d and triisobutylaluminum (T I B
A) 2 x lO-3 mol (2 mol/2-toluene solution) and 2 x 10-3 mol (2.6 mol/l) of methylaluminoxane obtained in (1) above as catalyst component (B)
1 toluene solution) was added and then maintained at a temperature of 70°C. This reaction solution was added with L2 as the catalyst component (A).
,3,4.5-pentamethylcyclopentadienyltitanium trimethoxide (Cp” Ti (OMe)z
) IXIO-' mol (0.01 mol/2-toluene solution) and acenaphthylene/styrene mixed solution prepared to a total monomer concentration of 2 mol #2-toluene solution [acenaphthylene/styrene-5/5 (monomer charge ratio). A total amount of monomers of 1.75 x 10-' mol] was added and reacted for 2 hours.

After that, pour the reactant into the methanol-hydrochloric acid mixture,
The reaction was stopped, deashed, filtered, and diluted with methyl ethyl ketone.
Washed twice with methanol and then three times with methanol. This was dried under reduced pressure to obtain 0.34 g of styrene/acenaphthylene copolymer.

When the molecular weight of this copolymer was measured by gel permeation chromatography (CPC), the weight average molecular weight (Mw) was 13 in terms of polystyrene (ps).
,000, and the number average molecular weight (Mn) is 5 in terms of PS.
,400.

In addition, differential scanning calorimetry (DSC) (measurement conditions ■300
'C, held for 5 minutes, cooled at 7°C/min to 30'C (
The glass transition point (Tg) and The melting point (Tm) is 106, respectively.
．． 6°C, 266.6°C, and the crystallization temperature during cooling (
Tc) was 232.8°C. In addition, the composition ratio of this copolymer was determined using the infrared absorption spectrum calibration curve method (polyacenaphthylene obtained by radical polymerization and boristyrene having a syndiotactic structure synthesized by a known method) were uniformly mixed in a predetermined amount. Prepare a mixture, measure the infrared absorption spectrum of each, determine the peak intensity ratio of absorption at 696 cm-' and absorption at 814 cm-', create a calibration curve from the mixture ratio and peak intensity ratio, The composition ratio of the copolymer was determined from the peak intensity ratio of the absorption at 696 cm-' and the absorption at 814 cm-' of the obtained copolymer and its calibration curve. It was 62. These measurement results are the first
Shown in the table.

Note that the GPC measurement conditions were as follows.

・Apparatus: Waters ALC/GPC 150°C ・Column: TSK I{M-1-GM}f 6X2 ・Flow rate: 1. OrIdt/sin.・Temperature = 135°C ・I medium: 1.2.4-}licrobenzene ・Inflow amount: 400 μl In addition, "C-NMR (67
MHz, solvent (double chloroform) measurement results are shown.

Macromolecules, 3, 175 (
(1970), t45,2p in IIC-NMR
It has been shown that the peak of pm can be assigned to the phenyl CI carbon based on the racemic pentad arrangement, but since there is also a sharp peak at the position of 145.2 ppm in Figure 1, this peak can be assigned to the phenyl CI carbon based on the racemic pentad arrangement. It can be seen that it has a geeky structure.

Further, from the half-width of the CI peak in FIG. 1, it was found that this polymer was 90% or more racemic pentad.

Examples 2 to 5 and Comparative Example 1 The monomer charging ratio of acenaphthylene/styrene was 4/6. 3/7. 2/8. 1/9. 0/1
The same procedure as in Example 1 was carried out except that the value was set to 0. The results are shown in Table 1.

Using the syndiotactic polystyrene (SPS) obtained in Comparative Example 1 as the stone-cut polystyrene in the north, polyacenaphthylene (synthesized by radical polymerization: MW = 11
,000, MN=4,500)
The thermal behavior was measured in the same manner as in Example 1. The results are shown in Table 2 as Reference Examples 1 to 3.

Comparing the results of the polymerization system according to Table 2, Table 1 and the mixed system according to Table 2, it is found that the polymerization system has improved Tc compared to the mixed system.
A decrease in Tm and a decrease in Tg were observed, which indicates that the polymers obtained in Examples 1 to 5 contain a copolymer.

〔Effect of the invention〕

By copolymerizing acenaphthylene, the first copolymer of the present invention has a higher crystallization rate than jindiotactic polystyrene. Therefore, by using this copolymer, molding cycles such as injection molding can be shortened.

Moreover, this copolymer has sufficient heat resistance.

Therefore, the first conjugate of the present invention can be used very effectively for forming materials.

Further, by using the second production method of the present invention, the above copolymer can be produced extremely efficiently.

[Brief explanation of the drawing]

Figure 1 shows the copolymer (7) obtained in Example 1 of the present invention.
13C-NMR (67MHz) is a chart showing the results of foot measurement f+'j. Sai1 Ward

Claims (2)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼……(I) [In the formula, R^1 is a hydrogen atom, a halogen atom, or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, It represents a substituent containing at least one of a selenium atom, a silicon atom, and a tin atom, and m represents an integer of 1 to 3. 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 [I] represented by [I] and general formula ▲ Numerical formula, chemical formula, table, etc. ▼... (II) [In the formula, R^2, R^3, R^4 are hydrogen atoms, halogen represents an atom or a substituent containing any one or more of 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, and n represents an integer of 1 to 6. However, when n is plural, each R^4 may be the same or different. ] Structural unit represented by [
II], the degree of polymerization is 5 or more, and the stereoregularity of the styrene chain portion is mainly a syndiotactic structure. (2) As catalyst components, (A) transition metal component and (B
) Using the contact product of an organoaluminum compound and a condensing agent, the general formula ▲ has mathematical formulas, chemical formulas, tables, etc. ▼... (III) [In the formula, R^1 is a hydrogen atom, a halogen atom, or a carbon atom, It represents 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, and m represents an integer of 1 to 3. However, m
When there is a plurality of R^1's, each R^1 may be the same or different. [In the formula, R^2, R^3, R^4 are hydrogen atoms, halogen atoms, or a substituent containing any one or more of 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, and n represents an integer of 1 to 6. However, when n is plural, each R^4 may be the same or different. ] The method for producing a styrenic copolymer according to claim 1, characterized in that an acenaphthylene monomer represented by the following is copolymerized.