JP2923024B2 - Styrene copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a styrene-based copolymer containing an arylstyrene having a wide range of melt-moldable temperatures or excellent heat resistance as a material for films, electric products, and automobile parts. The present invention relates to coalescence and a method for producing the same.

[Problems to be solved by conventional technology and invention]

There is a demand for a resin having good heat resistance and moldability as a member of an electric product or a member of an automobile part. For this reason, polystyrene having a syndiotactic structure (JP-A-62-104818, JP-A-62-187708, etc.) has been mainly proposed, but the melt molding temperature range (difference between melting point and decomposition temperature) is high. There was a problem that it was narrow and difficult to mold.

Further, although the polystyrene has relatively good heat resistance, there has been a demand for a resin having higher heat resistance that can withstand more severe conditions.

It is an object of the present invention to solve such problems and to provide a resin having a wide melt-moldable temperature range, excellent moldability, and excellent heat resistance, and an efficient production method thereof.

[Means for Solving the Problems] That is, the first aspect of the present invention is a general formula [Wherein, R ¹ is a hydrogen atom, a halogen atom, or a substituent containing at least one 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 (provided that Excluding an aryl group), and m is 0.
Represents an integer of from 5 to 5. However, when m is plural, each R ¹ may be the same or different. And a structural unit [I] represented by the general formula: [Wherein, R ² represents a hydrogen atom, a halogen atom, or a substituent containing at least one 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, Among n R ² , at least one of an aryl group having a hydrogen atom, an aryl group having a halogen atom or any 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 Or an aryl group having at least one substituent. N represents an integer of 1 to 5. And the degree of polymerization is 5 or more, and the amount of the structural unit [II] is 0.1 mol% or more. The present invention provides a styrene-based copolymer having a stereoregularity of mainly a syndiotactic structure, which is a copolymer containing at least mol%.

The second aspect of the present invention is a compound represented by the general formula: [Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a substituent containing at least one 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, m shows the integer of 0-5. However, when m is plural, each R ¹ may be the same or different. ] And a structural unit [I] represented by the following general formula: [Wherein, R ² represents a hydrogen atom, a halogen 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, Among n R ² , at least one of an aryl group having a hydrogen atom, an aryl group having a halogen atom or any 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 Or an aryl group having at least one substituent. N represents an integer of 1 to 5. And the degree of polymerization is 5 or more, and the structural unit [II] is more than 20 mol%. The present invention provides a styrene-based copolymer containing not more than 99.9% by mole, the stereoregularity of which is mainly a syndiotactic structure.

Further, a third aspect of the present invention is to use, as a catalyst component, a contact product of (A) a transition metal component and (B) an organoaluminum compound with a condensing agent; [Wherein, R ¹ is a hydrogen atom, a halogen atom, or a substituent containing at least one 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 (provided that Excluding an aryl group), and m is 0.
Represents an integer of from 5 to 5. However, when m is plural, each R ¹ may be the same or different. ] A styrene monomer represented by the general formula [Wherein, R ² represents a hydrogen atom, a halogen atom, or a substituent containing at least one 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, Among n R ² , at least one of an aryl group having a hydrogen atom, an aryl group having a halogen atom or any 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 Or an aryl group having at least one substituent. N represents an integer of 1 to 5. ] (Excluding the same case as the styrene-based monomer represented by the above general formula [III]). An object of the present invention is to provide a first method for producing a styrene-based copolymer of the present invention.

A fourth aspect of the present invention is to use, as a catalyst component, a contact product of a transition metal component (A) and an organoaluminum compound (B) with a condensing agent, and a general formula: [Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a substituent containing at least one 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, m shows the integer of 0-5. However, when m is plural, each R ¹ may be the same or different. ] A styrene monomer represented by the general formula [Wherein, R ² represents a hydrogen atom, a halogen 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, Among n R ² , at least one of an aryl group having a hydrogen atom, an aryl group having a halogen atom or any 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 Or an aryl group having at least one substituent. N represents an integer of 1 to 5. The second styrene copolymer according to the present invention, characterized by copolymerizing an arylstyrene monomer represented by the following formula (with the exception of the same case as the styrene monomer represented by the general formula [III]): It is intended to provide a method for producing a united product.

The styrenic copolymer in the present invention has a structural unit [I] (repeating unit) represented by the general formula [I] and a structural unit [II] (repeating unit) represented by the general formula [II]. is there.

Here, R ¹ of the structural unit [I] represents a hydrogen atom, a halogen atom, or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom,
It indicates a substituent containing at least one of a phosphorus atom, a selenium atom, a silicon atom and a tin atom. Here, examples of the halogen atom include chlorine, fluorine, bromine and iodine. Specific examples of the substituent containing 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;
Aryl group having a substituent containing hydrogen atom, halogen atom, carbon atom, oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, selenium atom, silicon atom or tin atom in the benzene ring of up to 30; chloroethyl group, bromomethyl group And a bromoethyl group such as a halogen-substituted alkyl group having 1 to 20 carbon atoms. In the first embodiment of the present invention, the aryl group is excluded.

Here, a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom,
Examples of the aryl group having a substituent containing a phosphorus atom, a selenium atom, a silicon atom or a tin atom include, for example, a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, an indene ring, an azulene ring, a heptalene ring, a biphenylene ring, and as- Indacene ring, s-indacene ring, acenaphthylene ring, phenalene ring, fluoranthene ring, acephenanthrene ring, aceanthrylene ring, triphenylene ring, naphthacene ring, preiaden ring, picene ring, perylene ring, pentaphene ring, pentacene ring, rubicene ring , Corocene ring, pyranthrene ring, ovalene ring, and their alkyl substituents (eg, methyl, ethyl, isopropyl, tertiary butyl), halogen-substituted alkyl groups (eg, chloroethyl, bromoethyl), and oxygen atoms Substituent (meth Shi group, an ethoxy group, an isopropoxy group, a methoxycarbonyl group, and acyloxy groups), such substituent (trimethylsilyl group containing a silicon atom), substituent (trimethylstannyl group comprising tin atom,
Tributylstannyl group, triphenylstannyl group, etc.), nitrogen-containing substituents (dimethylamino group, diazo group, nitro group, cyano group, etc.), sulfur-containing substituents (sulfone group, sulfonic acid methyl ester group) , Phenylthio, methylthio, mercapto, etc.), selenium-containing substituents (methylseleno, phenylseleno, methylselenoxyl, phenylselenoxyl, etc.), and phosphorus-containing substituents (phosphomethyl ester group) Phosphite, dimethylphosphino, diphenylphosphino, methylphosphinyl, phenylphosphinyl, etc.) at any position.

Examples of the substituent containing an oxygen atom include a methoxy group, an ethoxy group, an isopropoxy group, a methoxycarbonyl group,
An acyloxy group and the like are exemplified, and a substituent containing a silicon atom is, for example, a trimethylsilyl group. Next, examples of the substituent containing a tin atom include a trimethylstannyl group, a tributylstannyl group, and a triphenylstannyl group. Examples of the substituent containing a nitrogen atom include a dimethylamino group, a diazo group, a nitro group, and a cyano group. Examples of the substituent containing a sulfur atom include a sulfone group, a sulfonic acid methyl ester group, a phenylthio group, and a methylthio group. And mercapto groups. Examples of the substituent containing a selenium atom include a methylseleno group, a phenylseleno group, a methylselenoxyl group, and a phenylselenoxyl group. Examples of the substituent containing a phosphorus atom include a phosphoric acid methyl ester group and a phosphite ester Group, dimethylphosphino group, diphenylphosphino group, methylphosphinyl group, phenylphosphinyl group and the like.

Further, in the structural unit [I] represented by the general formula [I], m is an integer of 0 to 5, and when m is plural, even if m is the same as each of R ¹ Or different.

Specific examples of the structural unit [I] having such a substituent include styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5
Alkyl styrenes such as -dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-tert-butylstyrene; p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m -Bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-
Halogenated styrenes such as methyl-p-fluorostyrene; vinyl biphenyls such as 4-vinyl biphenyl, 3-vinyl biphenyl and 2-vinyl biphenyl; 1- (4-vinyl phenyl) naphthalene, 2- (4-vinyl phenyl) Naphthalene, 1- (3-vinylphenyl) naphthalene, 2-
Vinylphenylnaphthalenes such as (3-vinylphenyl) naphthalene, 1- (2-vinylphenyl) naphthalene, and 2- (2-vinylphenyl) naphthalene; 1- (4-vinylphenyl) anthracene, 2- (4-vinyl Phenyl)
Anthracene, 9- (4-vinylphenyl) anthracene, 1- (3-vinylphenyl) anthracene, 2- (3-
(Vinylphenyl) anthracene, 9- (3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, 2- (2-vinylphenyl) anthracene, 9- (2
Vinylphenylanthracenes such as -vinylphenyl) anthracene; 1- (4-vinylphenyl) phenanthrene, 2- (4-vinylphenyl) phenanthrene, 3-
(4-vinylphenyl) phenanthrene, 4- (4-vinylphenyl) phenanthrene, 9- (4-vinylphenyl) phenanthrene, 1- (3-vinylphenyl) phenanthrene, 2- (3-vinylphenyl) phenanthrene, 3
-(3-vinylphenyl) phenanthrene, 4- (3-vinylphenyl) phenanthrene, 9- (3-vinylphenyl) phenanthrene, 1- (2-vinylphenyl) phenanthrene, 2- (2-vinylphenyl) phenanthrene, 3
Vinylphenylphenanthrenes such as-(2-vinylphenyl) phenanthrene, 4- (2-vinylphenyl) phenanthrene and 9- (2-vinylphenyl) phenanthrene; 1- (4-vinylphenyl) pyrene, 2- (4- Vinylphenylpyrenes such as vinylphenyl) pyrene, 1- (3-vinylphenyl) pyrene, 2- (3-vinylphenyl) pyrene, 1- (2-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-
vinyl terphenyls such as m-terphenyl, 3-vinyl-o-terphenyl, 2-vinyl-p-terphenyl, 2-vinyl-m-terphenyl, and 2-vinyl-o-terphenyl; Vinylphenyl terphenyls such as 4-vinylphenyl) -p-terphenyl; 4-vinyl-4 '
-Methylbiphenyl, 4-vinyl-3'-methylbiphenyl, 4-vinyl-2'-methylbiphenyl, 2-methyl-4
Vinylalkyl biphenyls such as -vinyl biphenyl, 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'-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 vinyl biphenyls such as, 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 '
Alkoxyvinylbiphenyls such as -ethoxybiphenyl, 4-vinyl-2'-ethoxybiphenyl, 4-vinyl-2-ethoxybiphenyl, 4-vinyl-3-ethoxybiphenyl; 4-vinyl-4'-methoxycarbonylbiphenyl, -Alkoxycarbonylvinyl biphenyls such as -vinyl-4'-ethoxycarbonylbiphenyl; alkoxyalkylvinylbiphenyls such as 4-vinyl-4'-methoxymethylbiphenyl; trialkylsilylvinyl such as 4-vinyl-4'-trimethylsilylbiphenyl Biphenyls; Trialkylstannylvinyl biphenyls such as 4-vinyl-4'-trimethylstannylbiphenyl and 4-vinyl-4'-tributylstannylbiphenyl; Trialkyls such as 4-vinyl-4'-trimethylsilylmethylbiphenyl Silylmethylvinylbiphenyls; arylstyrenes such as trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4'-trimethylstannylmethylbiphenyl and 4-vinyl-4'-tributylstannylmethylbiphenyl; p-chloro Halogen-substituted alkylstyrenes such as ethylstyrene, m-chloroethylstyrene, o-chloroethylstyrene; p-methoxystyrene, m-methoxystyrene, o-methoxystyrene, p-ethoxystyrene, m-ethoxystyrene, o-ethoxystyrene Alkoxystyrene such as p-methoxycarbonylstyrene and m-methoxycarbonylstyrene; acyloxystyrene such as acetyloxystyrene, ethanoyloxystyrene and benzoyloxystyrene; p-vinylbenzene Alkyl ether styrene such as Le propyl ether; p
Alkyl silyl styrenes such as trimethylsilylstyrene; alkylstannyl styrenes such as p-trimethylstannylstyrene, p-tributylstannylstyrene, p-triphenylstannylstyrene; ethyl vinylbenzenesulfonate, vinylbenzyldimethoxyphosphide, p -Vinyl styrene such as vinyl styrene.

Moreover, as with R ¹ of R ² structural units of the structural unit [II] [I], a hydrogen atom, a halogen atom or a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, phosphorus atom, selenium atom, silicon atom and it is shown one substituent comprising one or more tin atoms, n pieces of at least one R of R ^2
2 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,
An aryl group having a substituent containing at least one of a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom is required. N represents an integer of 1 to 5.

Incidentally, specific examples of the substituents of R ² are the same as those shown in the case of the R ^1.

However, as described above, at least one R ² out of n R ²
Is an aryl group having a hydrogen atom, an aryl group having a halogen atom or a substituent containing at least one 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. It is necessary that the aryl group has an aryl group. For such aryl groups having a substituent, the same as that shown in the case of the R ¹ is used.

In the present invention, the above structural units [I] and [II] are different kinds, and a copolymer composed of two or more kinds of structural units is constituted by various combinations thereof.

Further, since the structural units [I] and [II] do not necessarily represent only one kind, but also represent two or more kinds of structural units, the copolymer of the present invention may be used in addition to a binary copolymer. And terpolymers and quaternary copolymers.

Here, the first aspect of the present invention is that the content of the structural unit [II] is from 0.1 mol% to 20 mol% of the whole. For this reason, the melt-moldable temperature range is wide and the moldability is excellent. If the content of the structural unit [II] is less than 0.1 mol% of the whole, the melt-moldable temperature is narrow and molding is difficult.

On the other hand, in the second aspect of the present invention, the content of the structural unit [II] is more than 20 mol% and not more than 99.9 mol%. Therefore, the glass transition point is high and the heat resistance is excellent.
If the content of the structural unit [II] exceeds 99.9 mol% of the whole, the heat resistance is improved, but the melt-moldable temperature is narrowed, the polymer is hardly soluble in a solvent, and the utilization range of the polymer is unpreferably narrow.

The styrenic copolymer of the present invention has the structural units (repeating units) as described above, and further has a stereoregularity mainly in a syndiotactic structure, that is, a main structure formed from carbon-carbon bonds. Substituted phenyl groups which are side chains with respect to the chain have a steric structure alternately located in the opposite direction, and their tacticity is quantified by nuclear magnetic resonance (NMR).

Specifically, the C ₁ carbon signal, methine / methylene carbon signal, or ¹ H-NMR proton signal of the aromatic ring is analyzed by ¹³ C-NMR method (nuclear magnetic resonance spectroscopy using the same steric carbon). Tacticity quantified by NMR is the abundance ratio of a plurality of consecutive structural units (ie, the abundance ratio of the relative conformational relationship of continuous structural units). Can be represented by a triad, and in the case of five, it can be represented by a pentad.However, in the present invention, having a syndiotactic structure mainly means that the degree of syndiotacticity depends on the type of substituent and the content of each repeating unit. Although varying, in a chain of styrenic repeating units,
A compound having a syndiotacticity of 75% or more, preferably 85% or more in racemic dyad, or 30% or more, preferably 50% or more in racemic pentad.

In the styrenic copolymer of the present invention, not only between the bonded structural units [I] and between the bonded structural units [II],
Each of the structural units [I] and [II] has a syndiotactic structure (co-syndiotactic structure). In addition, this copolymer has various modes such as block copolymerization, random copolymerization and alternating copolymerization of the structural units [I] and [II].

The styrenic copolymer mainly having a syndiotactic structure in the present invention does not necessarily have to be a single copolymer. As long as the syndiotacticity falls within the above range, it may be a mixture with a styrene-based copolymer having an isotactic or atactic structure or a compound incorporated in a polymer chain. Further, the styrene-based copolymer of the present invention may be a mixture having different molecular weights, and has a polymerization degree of at least 5 or more, preferably 10 or more. In terms of weight average molecular weight, preferably 5,
The number is from 1,000 to 100,000, more preferably from 8,000 to 800,000. There is no particular limitation on the molecular weight distribution.

As described above, the first styrene-based copolymer of the present invention can be efficiently produced by, for example, the third method of the present invention, and the second styrene-based copolymer of the present invention can be produced by, for example, It can be manufactured efficiently by the fourth method of the present invention.

The third of the present invention and the fourth of the present invention both use (A) a transition metal component and (B) a contact product of an organoaluminum compound and a condensing agent as catalyst components, It is the same in that the styrene monomer represented by the general formula [IV] and the arylstyrene monomer represented by the general formula [IV] (except for the same case as the styrene monomer represented by the general formula [III]) are copolymerized. However, the third aspect of the present invention is the above-mentioned general formula [III]
The fourth R of the present invention differs in that there is no such limitation, whereas the R ^{1 in} it does not contain an aryl group.

In other words, two or more styrene-based monomers represented by the general formula [III] and the arylstyrene-based monomer represented by the general formula [IV] are used as raw materials, and these are used. In the presence of a catalyst comprising a contact product of (A) a transition metal component and (B) an organoaluminum compound with a condensing agent,
It is copolymerized.

Here, there are various transition metal compounds as the component (A) of the catalyst. [Wherein, R ^{3 to} R ¹⁴ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms. An arylalkyl group, an aryloxy group having 6 to 20 carbon atoms,
It represents an acyloxy group having 1 to 20 carbon atoms, acetylacetonyl group, cyclopentadienyl group, substituted cyclopentadienyl group or indenyl group. A, b, and c each represent an integer of 0 or more that satisfies 0 ≦ a + b + c ≦ 4;
d and e each represent an integer of 0 or more satisfying 0 ≦ d + e ≦ 3, f represents an integer of 0 or more satisfying 0 ≦ f ≦ 2,
g and h each represent an integer of 0 or more that satisfies 0 ≦ g + h ≦ 3. Further, M ¹ and M ² represent titanium, zirconium, hafnium or vanadium, and M ³ and M ⁴ represent vanadium. At least one selected from transition metal compounds represented by
Species of compound. Among these transition metal compounds,
Preferably, M ¹ in the general formula [V] is titanium or zirconium.

Here, among those represented by R ^{3 to} R ¹⁴ in the above formula,
Specific examples of the halogen atom include chlorine, bromine, iodine and fluorine. Further, a substituted cyclopentadienyl group is
For example, a cyclopentadienyl group substituted by at least one alkyl group having 1 to 6 carbon atoms, specifically, a methylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a pentamethylcyclopentadiene group Enyl group and the like.

R ^{3 to} R ¹⁴ in the above formula are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (specifically, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, amyl group) Group, isoamyl group, octyl group, 2-ethylhexyl group, etc., 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.), aryl group having 6 to 20 carbon atoms (specifically, phenyl group, naphthyl group, etc.), arylalkyl group having 6 to 20 carbon atoms (specifically, benzyl group, It may be a phenethyl group, a 9-anthrylmethyl group, etc.) or an acyloxy group having 1 to 20 carbon atoms (specifically, an acetyloxy group, a stearoyloxy group, etc.). These R ^{3 to} R ¹⁴ may be the same or different as long as the above conditions are satisfied.

Specific examples of the titanium compound among the transition metal compounds represented by the aforementioned general formulas [V], [VI], [VII] or [VIII] include tetramethoxytitanium, tetraethoxytitanium, tetra-n- Butoxytitanium, tetraisopropoxytitanium, cyclopentadienyltrimethyltitanium, cyclopentadienyltriethyltitanium, cyclopentadienyltripropyltitanium, cyclopentadienyltributyltitanium, methylcyclopentadienyltrimethyltitanium, 1,2-dimethyl Cyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltrimethyltitanium, pentamethylcyclopentadienyltriethyltitanium, pentamethylcyclopentadienyltripropyltitanium, pentamethylcyclopentadienyltributyltitanium, cycle Lopentadienylmethyltitanium dichloride, cyclopentadienylethyltitanium dichloride, pentamethylcyclopentadienylmethyltitanium dichloride, pentamethylcyclopentadienylethyltitanium dichloride, cyclopentadienyldimethyltitanium monochloride, cyclopentadienyldiethyl Titanium monochloride, cyclopentadienyl titanium trimethoxide, cyclopentadienyl titanium triethoxide,
Cyclopentadienyl titanium tripropoxide, cyclopentadienyl titanium triphenoxide, pentamethylcyclopentadienyl titanium trimethoxide, pentamethylcyclopentadienyl titanium triethoxide, pentamethylcyclopentadienyl titanium tripropoxide, Pentamethylcyclopentadienyltitanium tributoxide, pentamethylcyclopentadienyltitanium triphenoxide, cyclopentadienyltitanium trichloride, pentamethylcyclopentadienyltitanium trichloride, cyclopentadienylmethoxytitanium chloride,
Cyclopentadienyldimethoxytitanium chloride, pentamethylcyclopentadienylmethoxytitanium dichloride, cyclopentadienyltribenzyltitanium, pentamethylcyclopentadienylmethyldiethoxytitanium,
Examples include indenyl titanium trichloride, indenyl titanium trimethoxide, indenyl titanium triethoxide, indenyl trimethylmethane, indenyl tribenzyl titanium and the like.

Among these titanium compounds, compounds containing no halogen atom are preferable, and in particular, a four-coordinate titanium compound in which at least one ligand is an unsaturated π-electron ligand as described above is preferable. preferable.

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

Further, similarly, specific examples of the hafnium compound include:
Cyclopentadienyl hafnium trimethoxide, pentamethylcyclopentadienyl hafnium trimethoxide, cyclopentadienyl tribenzyl hafnium, pentamethylcyclopentadienyl tribenzyl hafnium, bisindenyl hafnium dichloride, hafnium dibenzyl chloride, hafnium Tetrabenzyl, tributoxy hafnium chloride, triisopropoxy hafnium chloride and the like can be mentioned.

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

On the other hand, (B) a contact product of an organoaluminum compound and a condensing agent, which is another component of the catalyst used in the third or fourth method of the present invention, is described in, for example, JP-A-62-187708. It is of the same kind as the one described in detail below.

That is, the contact product is obtained by bringing various organic aluminum compounds into contact with a condensing agent.

Here, as the organoaluminum compound, a general formula AlR ¹⁵ ₃ [wherein, R ¹⁵ represents an alkyl group having 1 to 8 carbon atoms. ], Specifically, trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, among which trimethylaluminum is preferable.

As the condensing agent, water is typically exemplified, and in addition, various agents such as those which cause the above-mentioned trialkylaluminum to undergo a condensation reaction, for example, copper sulfate pentahydrate, water adsorbed on inorganic or organic substances, and the like are also exemplified.

Representative examples of the third or contact product of an organoaluminum compound and a condensing agent as the component (B) of the catalyst used in the fourth invention, the trialkyl aluminum and water, represented by the general formula AlR ¹⁵ ₃ There is a contact product of
Specifically, the general formula [In the formula, p represents a degree of polymerization and is 0 to 50, and R ¹⁵ represents an alkyl group having 1 to 8 carbon atoms. Or a linear alkylaminoxan represented by the general formula Wherein R ¹⁵ is the same as described above. And the like, and cyclic alkylaluminoxanes having a repeating unit represented by the formula (2 to 50 repeating units).

Generally, the contact product of alkyl aluminum such as trialkyl aluminum and water is, together with the above-described chain alkyl aluminoxane and cyclic alkyl aluminoxane,
Unreacted trialkylaluminum, a mixture of various condensation products, and molecules in which these are intricately associated, are various products depending on the contact conditions between the trialkylaluminum and water as 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 performed 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 a method in which water is added later, and further contained in a metal salt or the like Crystal water,
There is a method of reacting water adsorbed on inorganic or organic substances with an organic aluminum compound. Although this reaction proceeds even without solvent, it is preferable to carry out the reaction in a solvent. Suitable solvents include aliphatic hydrocarbons such as hexane, heptane and decane and aromatic hydrocarbons such as benzene, toluene and xylene. Can be mentioned. The water contains amines such as ammonia and ethylamine, sulfur compounds such as hydrogen sulfide, and phosphorus compounds such as phosphite.
%.

In the third or fourth aspect of the present invention, the contact product (for example, alkylaluminoxane) of the organoaluminum compound and the condensing agent used as the component (B) of the catalyst is obtained by using a hydrated compound or the like after the above-mentioned contact reaction. At a temperature of 30 to 200 ° C. under normal pressure or reduced pressure, preferably at a temperature of 40 to 150 ° C. for 20 minutes to 8 hours, preferably 30 minutes to 5 hours. It is preferable to perform heat treatment while distilling off the solvent.

In this heat treatment, the temperature may be appropriately determined depending on various conditions, but is usually in the above range. Generally, at temperatures below 30 ° C, no effect is exhibited and
If it exceeds, thermal decomposition of the alkylaluminoxane itself occurs, and both are not preferred.

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

A preferred example of the contact product of an organoaluminum compound used as the component (B) of the catalyst and a condensing agent, particularly a preferred example of an alkylaluminoxane is an aluminum-methyl group (Al-CH 2) observed by proton nuclear magnetic resonance. ₃ ) The high magnetic field component in the methyl proton signal region based on the bond is 50% or less. That is, when the above contact product is observed for its proton nuclear magnetic resonance ( ¹ H-NMR) spectrum in a toluene solvent at room temperature, the methyl proton signal based on Al—CH ₃ is found to be tetramethylsilane (TMS).
It is found in the range of 1.0 to -0.5 ppm by standard. Because TMS proton signals (0 ppm) is in the methyl protons observation area based on the Al-CH _3, methyl proton signal based on the Al-CH _3, measured relative to the methyl proton signal 2.35ppm toluene in TMS standard , A high magnetic field component (i.e., -0.1 to 0.5 ppm) and another magnetic field component (i.e., 1.0
(-0.1 ppm), the high field component is 50% or less of the total, preferably 45 to 5% of the catalyst (B).
It can be suitably used as a component.

The catalyst used in the method of the present invention comprises the above-mentioned components (A) and (B) as main components. In addition to the above, other catalyst components such as a general formula AlR ¹⁶ ₃ [wherein R ¹⁶ represents an alkyl group having 1 to 8 carbon atoms. ], Or other organometallic compounds represented by the formula:

In the third or fourth embodiment of the present invention, the styrene monomer and the arylstyrene monomer are copolymerized using the catalyst obtained as described above.
Any method such as solution polymerization and suspension polymerization may be used. And in these cases, the solvents are pentane, hexane,
Aliphatic hydrocarbons such as heptane; alicyclic hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene are used. Of these, aromatic hydrocarbons are preferred, and ethylene and xylene are particularly preferred. In this case, the monomer / solvent ratio can be arbitrarily selected.

The polymerization conditions are not particularly limited, but generally, the polymerization temperature is 0 to 120 ° C, preferably 10 to 80 ° C, and the polymerization time is 5 minutes to 24 hours, preferably 1 hour or more. is there.

Further, it is effective to adjust the molecular weight of the obtained styrenic copolymer in the presence of hydrogen.

Further, when using this catalyst, the ratio of the component (A) to the component (B) in the catalyst depends on the type of each component,
It depends on the type of the styrene monomer and the arylstyrene monomer as raw materials and other conditions, and it is difficult to define them uniquely. However, usually, the aluminum in the catalyst component (B) and the transition in the (A) transition metal component are usually used. The ratio to the metal, ie, aluminum / transition metal (molar ratio), is 1 /
10 ^6/1 (molar ratio), preferably 10 / 1-10 ^4/1 (molar ratio).

Further, the charge ratio of the raw materials is not particularly limited, and can be determined according to the composition of the target product. Further, the order of charging the raw materials and the catalyst components is not particularly limited, and they can be performed in any order.

As described above, the first or second styrenic copolymer of the present invention can be produced. This copolymer is
Although it has a high syndiotacticity as described above, after polymerization, if necessary, it is subjected to deashing treatment with a washing solution containing hydrochloric acid and the like, further washed, dried under reduced pressure, and washed with a solvent such as methyl ethyl ketone to obtain a soluble component. , A high-purity styrene-based copolymer having extremely large syndiotacticity can be obtained.

〔Example〕

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

Example 1 (1) of methylaluminoxane toluene 200ml glass vessel was purged with argon internal volume 500ml of copper sulfate pentahydrate _{(CuSO 4 · 5H 2 O)} 17.7g (71 mmol) and trimethyl aluminum 24 ml (250 mmol ) Was added and reacted at 40 ° C. for 8 hours. Thereafter, the solid component was removed, and toluene was further distilled off from the resulting solution under reduced pressure to obtain 6.7 g of a contact product. Its molecular weight measured by the freezing point depression method was 610.

When the proton nuclear magnetic resonance spectrum of a high magnetic field component by ¹ H-NMR measurement, that is, its proton nuclear magnetic resonance spectrum is observed in a toluene solvent at room temperature, the methyl proton signal based on the (Al—CH ₃ ) bond is based on tetramethylsilane. 1.
It is found in the range of 0 to -0.5 ppm. Since the proton signal of tetramethylsilane (0 ppm) is in the observation region based on the methyl proton based on the Al-CH ₃ bond, this Al-CH
Methyl proton signal of toluene based on methyl bond signal based on _three bonds based on tetramethylsilane.
Measured based on 2.35 ppm, the high magnetic field component (ie,
−0.1 to −0.5 ppm) and other magnetic field components (that is, 1.0 to −0.5 ppm).
0.1ppm), the high magnetic field component is 43% of the total
Met.

(2) Styrene having co-syndiotactic structure
Production of 4-vinylbiphenyl copolymer In an atmosphere of argon, place 2 ml of toluene, 8 × 10 3 of TIBA (triisobutylaluminum) in a dry reaction vessel at room temperature.
^-4 mol (2 mol / -toluene solution) and catalyst component (B)
As the methylaluminoxane 8 × obtained in the above (1)
10 ^-4 mol (2.6 mol / -toluene solution) was added, and then
The temperature was kept at 70 ° C. The catalyst component (A) is added to the reaction solution.
1,2,3,4,5-pentamethylcyclopentadienyl titanium trimethoxide (Cp ^* Ti (OMe) ₃ ) 4 × 1
0 ^-6 mol (0.01 mol / -toluene solution) and 1 mol /-
4-vinyl biphenyl / styrene mixed solution prepared in a toluene solution [4-vinyl biphenyl / styrene = 8/2
(Monomer charge ratio)] 8.75 ml (Total monomer 8.75 x 10
^-3 mol) and reacted for 2 hours.

Thereafter, the reaction product was poured into a methanol-hydrochloric acid mixture to stop the reaction, demineralized, filtered, and washed three times with methanol. This was dried under reduced pressure to obtain 0.59 g of a styrene-4-vinylphenyl copolymer.

When the molecular weight of the copolymer was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 1.2 × 10 ^{5 in} terms of polystyrene (PS).
And the number average molecular weight (Mn) was 4.8 × 10 ⁴ in terms of PS. Further, when this copolymer was extracted for 4 hours using methyl ethyl ketone (MEK) as a solvent using a Soxhlet extractor, 98 wt% was insoluble. The glass transition point (Tg) and the melting point (Tm) of this copolymer determined by differential scanning calorimetry (DSC) were 143 ° C. and 29 ° C., respectively.
Decomposition temperature (Td) determined by thermogravimetry (where Td is the temperature before decomposition (d
The temperature at the intersection of the tangent at the point ((TG) / dt = 0) and the tangent at the inflection point during decomposition is shown. ] Was 417 ° C. In addition, the composition ratio of this copolymer is determined by measuring 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 in a predetermined amount. Prepare a homogeneous mixture, measure the infrared absorption spectrum of each, determine the peak intensity ratio between the absorption at 696 cm ^{-1 and} the absorption at 814 cm ^-1 and create a calibration curve from the mixture ratio and the peak intensity ratio. , the peak intensity ratio of the absorption of the absorption of 696cm ^-1 of the resulting copolymer and 814 cm ^-1, to determine the composition ratio of the copolymer by the calibration curve.) the obtained where 4-vinyl biphenyl / styrene = 67/33. Table 1 shows the measurement results.

 The GPC measurement conditions were as follows.

・ Apparatus: Waters ALC / GPC 150C ・ Column: TSK HM + GMH 6 × 2 ・ Flow rate: 1.0 ml / min ・ Temperature: 135 ° C. ・ Solvent: TCB ・ Inflow: 400 μm Examples 2 to 6 and Reference Examples 1, 24 The procedure was performed in the same manner as in Example 1 except that the monomer charge ratio of vinyl biphenyl / styrene was 5/5, 4/6, 3/7, 1/9, 0.5 / 9.5, 10/0, 0/10, respectively. . The results are shown in Table 1.

Confirmation of Structure of Copolymer Next, it was confirmed by the following method that both of the styrene-based copolymers obtained in Examples 1 to 6 had a syndiotactic structure.

(1) ¹³ C-NMR measurement results Reference Example 1, Examples 1, 2, 3, and 5 of the polymer obtained in Reference Example 2
¹³ C-NMR (100 MHz, solvent: 1,2,4-trichlorobenzene /
The measurement results of heavy benzene = 8/2 (molar ratio) are shown in FIGS. 1 to 6, respectively.

In FIG. 1 (a), three sharp peaks (138.6, 14
1.0, 144.0 ppm) represent three quaternary carbons of syndiotactic poly (4-vinylbiphenyl), and the two sharp peaks (40.8, 44.6 ppm) in FIG.
Shows methylene carbon.

The sharp peak (145.1 ppm) in FIG. 6 (a) indicates the quaternary carbon of syndiotactic polystyrene, and the two sharp peaks (41.0, 44.3 ppm) in FIG. 6 (b) indicate methine and methylene, respectively. Indicates carbon.

From FIG. 1 to FIG. 6, it can be seen that by copolymerization, a new peak appears and the peak intensity ratio changes, and these copolymers have a co-syndiotactic structure.

(2) ¹ H-NMR measurement results Example 1 and ¹ obtained in Example 1,2,3,5 H-NMR (40
0 MHz) The measurement results are shown in FIGS. 7 to 11, respectively.

According to these figures, it can be confirmed that there is only one type of peak corresponding to methine and methylene, respectively, and that the shift of the chemical shift value is confirmed, and that the copolymer is a copolymer.

(3) Molecular weight distribution The molecular weight distribution of Examples 1 to 6 has a single peak in GPC, suggesting that these are copolymers.

(4) Monomer reactivity ratio It is known that the monomer reactivity ratios r ₁ and r ₂ are important indicators of the distribution of monomer chains in the copolymer chain (“copolymerization” 1, reaction analysis P .6-8, edited by The Society of Polymer Science, Japan).

Based on the ratio of the charged monomers and the composition of the obtained copolymer, a monomer reactivity ratio (r ₁ = styrene, r ₂ = 4-vinylbiphenyl) was determined, and the product r ₁ · r _{2 was obtained.} Was found to be less than 1.

This indicates that the copolymers obtained in Examples 1 to 6 were random copolymers, and furthermore, ¹³ C-NMR
Supports the results of the aromatic ring quaternary carbon signal.

As described above, the results of (1), (2), (3), and (4) were comprehensively determined, and the styrene-based copolymers obtained in Examples 1 to 6 had substantially three-dimensional structures. Syndiotactic and its tacticity is 95% racemic dyad
As mentioned above, it was recognized that it was 80% or more in racemic pentad.

Example 7 (1) Production of m-phenylstyrene 1.70 g (0.07 mol) of granular metallic magnesium in diethyl ether (100 ml) while stirring under an inert gas stream.
One drop of 1,2-dibromoethane was dropped into the solution, and the Grignard reagent reaction was started by heating. The temperature of the solution was raised to reflux, followed by 7.37 ml (0.07 ml) of benzene bromide.
mol) in diethyl ether (70 ml) over 30 minutes,
It was dripped slowly. After completion of the dropwise addition, the mixture was left under reflux for 1 hour. The reaction solution was cooled to room temperature, and at room temperature, a solution of 6.51 ml (0.05 mol) of m-bromostyrene and 0.32 g (0.6 mmol) of nickel chloride- (1,3-diphenylphosphinopropane) complex in diethyl ether (100 ml) was added. It was dropped. After the completion of the dropwise addition, the mixture was refluxed for 4 hours. The reaction solution was poured into 500 ml of ice water, and the pH was adjusted to be weakly acidic. Extracted with hexane, washed, dried, evaporated, and purified by silica gel column chromatography to give m-phenylstyrene.
7.32 g (80% yield) was obtained.

^The results of ¹ H-NMR (solvent: deuterated chloroform, 90 MHz) measurement were as follows.

δ5.26 (2H, dd, HC = C- [trans]), δ5.80 (2H, dd, HC = C- [cis]), δ6.78 (1H, dd, C = CH- [α position] ), Δ 7.00 to 7.90 (9H, benzene ring) (2) Production of p-phenylstyrene / m-phenylstyrene copolymer having a co-syndiotactic structure Under an argon atmosphere, in a dry reaction vessel at room temperature, Toluene 2ml, triisobutylaluminum 4 × 10 ^-4 mol
(2.0 mol / -toluene solution) and methylaluminoxane 4 obtained in Example 1 (1) as catalyst component (B)
× 10 ^-4 mol (2.6 mol / -toluene solution [per aluminum atom]) was added, and at 70 ° C, 1,2,3,4,5-pentamethylcyclohexane was added as a catalyst component (A) to the reaction solution. Pentadienyl titanium trimethoxide (Cp ^* Ti (OMe)
₃ ) 2 × 10 ^-6 mol (0.01 mol / -toluene solution) and 1
A mixed solution of p-phenylstyrene and m-phenylstyrene (obtained in (1) above) prepared in a mol / -toluene solution [p-phenylstyrene / m-phenylstyrene = 95/5 (monomer charged) Ratio), monomer total
8.75 × 10 ⁻³ mol] and reacted for 4 hours.

Thereafter, the reaction product was added to a methanol-hydrochloric acid mixed solution to stop the reaction, deashed, filtered, and then washed three times with methanol. This is dried under reduced pressure, 0.90 g
Of p-phenylstyrene / m-phenylstyrene copolymer was obtained.

When the molecular weight of this copolymer was measured by gel permeation chromatography (GPC), the weight average molecular weight (Mw) was 1,000,00 in terms of polystyrene (PS).
It was 0 and the number average molecular weight (Mn) was 230,000 in terms of PS.

 The GPC measurement conditions were as follows.

・ Equipment: Waters ALC / GPC 150C ・ Column: TSK HM + GMH 6 × 2 ・ Flow rate: 1.0 ml / min ・ Temperature: 135 ° C. ・ Solvent: TCB ・ Inflow: 400μ Furthermore, for this copolymer, differential scanning calorimetry (DS)
C) [Measurement conditions: The temperature was raised to 30 to 360 ° C. (fast heating) at 20 ° C./min.]. The glass transition point (Tg) of this copolymer was 160 ° C. (T
m) is 335 ° C, and the decomposition temperature (T
d) [where Td indicates the temperature at the intersection of the tangent at the point before decomposition (d (TG) / dt = 0) and the tangent at the inflection point during decomposition in the TG (thermogravimetric change) curve. Is 416 ° C
Met.

In addition, ¹³ C-NMR spectrum of this copolymer (100 MHz,
Solvent: 1,2,4-trichlorobenzene / deuterated benzene = 8/2, 130.6 ppm of deuterated benzene, 130 ° C) is shown in FIG.

From this, when the composition ratio of this copolymer was determined, p
-Phenylstyrene part / m-phenylstyrene part = about 99/1
Met. Table 2 shows the measurement results.

Example 8 In Example 7 (2), p-phenylstyrene / m-
Example 7 (2) except that a solution of p-phenylstyrene / m-phenylstyrene = 92/8 was used instead of p-phenylstyrene / m-phenylstyrene = 95/5 as the phenylstyrene mixed solution. Was carried out in the same manner as described above to obtain a p-phenylstyrene / m-phenylstyrene copolymer.

The yield of this copolymer was 0.83 g. Further, the differential scanning calorimetry (DSC) was carried out in the same manner as in Example 7 (2). The glass transition point (Tg) of this copolymer was
The melting point (Tm) was 150 ° C., the melting point (Tm) was 318 ° C., and the decomposition temperature (Td) determined by thermogravimetry was 419 ° C.

When the molecular weight of this copolymer was measured by GPC, the weight average molecular weight (Mw) was 680,000 in terms of polystyrene (PS), and the number average molecular weight (Mn) was 11 in terms of PS.
It was 0,000.

When the composition ratio of this copolymer was determined in the same manner as in Example 7, the ratio was p-phenylstyrene / m-phenylstyrene = about 98/2. Table 2 shows the measurement results.

Example 9 (Production of p-phenylstyrene / m-phenylstyrene / styrene terpolymer having a cosyndiotactic structure) In Example 7 (2), p-phenylstyrene / m-
Except that a mixed solution of p-phenylstyrene / m-phenylstyrene / styrene = 93/3/4 (1 mol / -toluene solution) was used instead of the phenylstyrene mixed solution,
In the same manner as in Example 7 (2), a terpolymer of p-phenylstyrene / m-phenylstyrene / styrene was obtained.

 The yield of this copolymer was 0.82 g.

When differential scanning calorimetry (DSC) was performed in the same manner as in Example 7 (2), the glass transition point (Tg) of this copolymer was 149 ° C., and the melting point (Tm) was 326 ° C. The decomposition temperature (Td) determined by thermogravimetry was 409 ° C.

When the molecular weight of this copolymer was measured by GPC, the weight average molecular weight (Mw) was 1,030,000 in terms of polystyrene (PS), and the number average molecular weight (Mn) was 2 in terms of PS.
It was 50,000.

FIG. 13 shows the ¹³ C-NMR spectrum of this copolymer.

From this, when the composition ratio of this copolymer was determined, p
-Phenylstyrene part / m-phenylstyrene part / styrene part = about 98/1/1. Table 2 shows the measurement results.

Example 10 (Production of m-phenylstyrene / styrene copolymer having a cosyndiotactic structure) In a dry reaction vessel under an argon atmosphere, 2 ml of toluene and catalyst component (B) were prepared in Example 1 (1) at room temperature. )
8 × 10 ^-4 mol (2.6 mol /
-Toluene solution (per aluminum atom))
At 70 ° C., 1,2,
3,4,5-pentamethylcyclopentadienyl titanium trimethoxide (Cp ^* Ti (OMe) ₃ ) 4 × 10 ⁻⁶ mol (0.01
mol) /-toluene solution) and m-phenylstyrene prepared in a 1 mol / -toluene solution (Example 7 (1)
(M-phenylstyrene / styrene = 2/8 (monomer preparation ratio), total of 8.75 × 10 ⁻³ mol of monomers) and reacted for 4 hours.

Thereafter, the reaction product was added to a methanol-hydrochloric acid mixed solution to stop the reaction, deashed, filtered, and then washed three times with methanol. This is dried under reduced pressure, 0.56g
M-phenylstyrene / styrene copolymer was obtained.

When the molecular weight of this copolymer was measured by GPC, the weight average molecular weight (Mw) was 320,000 in terms of polystyrene (PS), and the number average molecular weight (Mn) was 49,00 in terms of PS.
It was 0.

In addition, the differential scanning calorimetry (DS
C), the glass transition temperature (T
g) was 96 ° C, the melting point (Tm) was 206 ° C, and the decomposition temperature (Td) determined by thermogravimetry was 414 ° C.

FIG. 14 shows the ¹³ C-NMR spectrum of this copolymer.

From this, when the composition ratio of this copolymer was determined, m
-Phenylstyrene part / styrene part = about 5/95.
Table 2 shows the measurement results.

Example 11 In Example 10, m-phenylstyrene / styrene = 2 /
In the same manner as in Example 10 except that m-phenylstyrene / styrene = 1/9 was used instead of 8, a m-phenylstyrene / styrene copolymer was obtained.

 The yield of this copolymer was 0.84 g.

Further, in the same manner as in Example 10, the differential scanning calorimetry (DS
C), the glass transition temperature (T
g) was 99 ° C, the melting point (Tm) was 226 ° C, and the decomposition temperature (Td) determined by thermogravimetry was 415 ° C.

When the molecular weight of this copolymer was measured by GPC, the weight average molecular weight (Mw) was 410,000 in terms of polystyrene (PS), and the number average molecular weight (Mn) was 70,
000.

FIG. 15 shows the ¹³ C-NMR spectrum of this copolymer.

From this, when the composition ratio of this copolymer was determined, m
-Phenylstyrene part / styrene part = about 3/97.
Table 2 shows the measurement results.

Example 12 (1) Production of 4-vinyl-4'-methylbiphenyl 1.70 g (0.07 mol) of granular magnesium metal in diethyl ether (100 ml) was stirred under an inert gas stream while stirring.
One drop of 1,2-dibromoethane was dropped into the solution, and the Grignard reagent reaction was started by heating. The temperature of the solution was raised to reflux, followed by 8.61 ml of p-toluene bromide.
A solution of (0.07 mol) in diethyl ether (70 mol) was slowly added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was left under reflux for 1 hour. The reaction solution was cooled to room temperature and 6.54 ml (0.05 mol) of p-bromostyrene and nickel chloride- (1,3
-Diphenylphosphinopropane) complex 0.32 g (0.6 mmo
It was added dropwise to a solution of l) in diethyl ether (100 ml). After the completion of the dropwise addition, the mixture was refluxed for 4 hours. The reaction solution was poured into 500 ml of ice water, and the pH was adjusted to be weakly acidic. Extracted with hexane, washed, dried, evaporated and purified by silica gel column chromatography to give 4-vinyl-4'-
7.28 g (yield 75%) of methyl biphenyl was obtained.

^The results of ¹ H-NMR (solvent: deuterated chloroform, 90 MHz) measurement were as follows.

_{δ2.33 (3H, s, -CH 3} ), δ5.21 (2H, dd, HC = C- [trans]), δ5.72 (2H, dd, HC = C- [cis]), δ6.71 (1H, dd, C = CH- [α position]), δ 7.00 to 7.80 (8H, benzene ring) (2) 4-vinyl-4'-methylbiphenyl / styrene copolymer having a cosyndiotactic structure In Example 7 (2), p-phenylstyrene / m-
Instead of a phenylstyrene mixed solution, 4-vinyl-
4'-methylbiphenyl (obtained in (1) above)
The procedure of Example 7 (2) was repeated, except that a mixed solution of / styrene = 1/19 was used, to obtain a 4-vinyl-4'-methylbiphenyl / styrene copolymer.

 The yield of this copolymer was 0.58 g.

When the molecular weight of this copolymer was measured by GPC, the weight average molecular weight (Mw) was 360,000 in terms of polystyrene (PS), and the number average molecular weight (Mn) was 11 in terms of PS.
It was 0,000.

Further, the copolymer was subjected to differential scanning calorimetry (DSC) in the same manner as in Example 7 (2). The copolymer had a glass transition point (Tg) of 105 ° C. and a melting point (Tm). ) Was 221 ° C., and the decomposition temperature (Td) determined by thermogravimetry was 410 ° C.

FIG. 16 shows the ¹³ C-NMR spectrum of this copolymer.

From this, the composition ratio of this copolymer was determined in the same manner as in Example 7 (2). As a result, the ratio of 4-vinyl-4'-methylbiphenyl / styrene was about 3/97. Table 2 shows the measurement results.

[Effects of the Invention] The first aspect of the present invention has a syndiotactic structure, and 0.1 to 20 mol of the structural unit [II] (arylstyrene).
% Of the styrene-based copolymer has a wide melt-moldable temperature range and is easy to form a film.

Further, the present invention has a second predominantly syndiotactic structure, wherein the structural unit [II] (arylstyrene) is 20 to
The styrene copolymer containing 99.9 mol% has a glass transition point (T
g) is high and has excellent heat resistance, so it is extremely useful as a heat resistant resin.

Furthermore, by using the third production method of the present invention, the first copolymer of the present invention can be produced very efficiently, and by using the fourth production method of the present invention, the above-mentioned present invention can be produced. Can be produced very efficiently.

Therefore, the styrenic copolymer of the present invention can be effectively used as a heat-resistant resin, a film raw material and the like.

[Brief description of the drawings]

1 (a) and 1 (b) show the results of ¹³ C-NMR measurement of the copolymer obtained in Reference Example 1. FIGS. 2 (a) and 2 (b) show the results of ¹³ C-NMR measurement of the copolymer obtained in Example 1. FIGS. 3 (a) and 3 (b) show the results of ¹³ C-NMR measurement of the copolymer obtained in Example 2. FIGS. 4 (a) and 4 (b) show the results of ¹³ C-NMR measurement of the copolymer obtained in Example 3. 5 (a) and 5 (b) show the results of ¹³ C-NMR measurement of the copolymer obtained in Example 5. FIGS. 6A and 6B show the results of ¹³ C-NMR measurement of the copolymer obtained in Reference Example 2. FIGS. 7 to 11 show ¹ H-NMR measurement results of the copolymers obtained in Reference Example 1, Example 1, Example 2, Example 3, and Example 5, respectively. 12, 13, 14, 15, and 16 are the copolymers obtained in Example 7, Example 9, Example 10, Example 11, and Example 12, respectively.
^{It is a 13} C-NMR measurement result.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-109405 (JP, A) JP-A-63-241009 (JP, A) JP-A-63-120707 (JP, A) (58) Investigation Field (Int.Cl. ⁶ , DB name) C08F 212/02-212/32

Claims (6)

(57) [Claims] (1) General formula [Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a substituent containing at least one 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 (provided that Excluding an aryl group), and m is 0.
Represents an integer of from 5 to 5. However, when m is plural, each R ¹ may be the same or different. ] And a structural unit [I] represented by the following general formula: [Wherein, R ² represents a hydrogen atom, a halogen 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, Among n R ² , at least one of an aryl group having a hydrogen atom, an aryl group having a halogen atom or any 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 Or an aryl group having at least one substituent. N represents an integer of 1 to 5. Wherein the degree of polymerization is 5 or more, and the content of the structural unit [II] is 0.1 mol% or more. A styrene-based copolymer having a stereoregularity of mainly a syndiotactic structure, which is a copolymer containing at least mol%. 2. The copolymer according to claim 1, which has two different types of structural units [II] as the structural units [II]. 3. The general formula [Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a substituent containing at least one 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, m shows the integer of 0-5. However, when m is plural, each R ¹ may be the same or different. ] And a structural unit [I] represented by the following general formula: [Wherein, R ² represents a hydrogen atom, a halogen 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, Among n R ² , at least one of an aryl group having a hydrogen atom, an aryl group having a halogen atom or any 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 Or an aryl group having at least one substituent. N represents an integer of 1 to 5. And the degree of polymerization is 5 or more, and the structural unit [II] is more than 20 mol%. A styrenic copolymer containing not more than 99.9 mol%, whose stereoregularity is mainly a syndiotactic structure. 4. The copolymer according to claim 3, which has two different types of structural units [II] as the structural units [II]. 5. A catalyst product comprising a contact product of (A) a transition metal component and (B) an organoaluminum compound with a condensing agent, [Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a substituent containing at least one 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 (provided that Excluding an aryl group), and m is 0.
Represents an integer of from 5 to 5. However, when m is plural, each R ¹ may be the same or different. ] A styrene monomer represented by the general formula [Wherein, R ² represents a hydrogen atom, a halogen 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, Among n R ² , at least one of an aryl group having a hydrogen atom, an aryl group having a halogen atom or any 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 Or an aryl group having at least one substituent. N represents an integer of 1 to 5. An arylstyrene-based monomer represented by the following general formula (III) except that the same is the same as the styrene-based monomer represented by the general formula [III].
The method for producing a styrene copolymer according to the above. 6. A catalyst product comprising a contact product of (A) a transition metal component and (B) an organoaluminum compound with a condensing agent. [Wherein, R ¹ represents a hydrogen atom, a halogen atom, or a substituent containing at least one 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, m shows the integer of 0-5. However, when m is plural, each R ¹ may be the same or different. ] A styrene monomer represented by the general formula [Wherein, R ² represents a hydrogen atom, a halogen 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, Among n R ² , at least one of an aryl group having a hydrogen atom, an aryl group having a halogen atom or any 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 Or an aryl group having at least one substituent. N represents an integer of 1 to 5. An arylstyrene-based monomer represented by the following general formula (III) except for the same case as the styrene-based monomer represented by the general formula [III] is copolymerized.
The method for producing a styrene copolymer according to the above.