JP2007023111A - Method for producing aromatic vinyl polymer having isotacticity - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for produce aromatic vinyl polymer having isotacticity. <P>SOLUTION: Aromatic vinyl compound is allowed to polymerize at less than 30°C in the presence of a catalyst including at least one selected from ion pair forming compounds prepared by reaction between a single transition metal compound represented by (A) general formula (I) (wherein M means Ti, Zr or Hf) and (B) (B-1) an organic metal compound, (B-2) an organic aluminum oxy compound and (B-3) a transition metal and the aromatic polymer has an isotactic triad tacticity of more than 60% mm fraction according to<SP>13</SP>C NMR. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an aromatic vinyl compound polymer having isotacticity.

Aromatic vinyl compound polymer with stereoregularity is crystalline, unlike atactic polystyrene produced by radical process, and has excellent heat resistance and chemical resistance. Is expected as a new material.
Conventionally, an aromatic vinyl compound polymer having isotacticity is composed of a titanium compound and an organoaluminum compound, as disclosed in Angew. Chem., 1956 (68), 393, etc. A method using a heterogeneous Ziegler-Natta catalyst is known.

  Later, a method using a zirconium complex having a carbon-bridged bisindenyl ligand was reported in Polym. Prepr. 1998 (39), 220 as a method for producing isotactic polystyrene using a molecular catalyst.

Recently, as a new method for producing isotactic polystyrene using a molecular catalyst, J. Am. Chem. Soc., 2003 (125), 4964, etc., catalyzed a group 4 transition metal compound having a bisphenolate ligand. The method used as is described. In addition, as a method for producing a mixture of isotactic polystyrene and syndiotactic polystyrene from a single catalyst, Macromolecules, 1990 (23), 1558, Macromol. Chem. Rapid. Commun., 1993 (14), 511, etc. It is disclosed.
However, there are not enough types of catalysts capable of producing aromatic vinyl compound polymers having isotacticity. Therefore, when producing isotactic polystyrene using conventional catalysts, it is desirable with respect to physical properties and molding processability. It is not enough in that it is difficult to control to the area. Under such circumstances, the appearance of a catalyst component excellent in the properties of the obtained aromatic vinyl compound has been desired.

  In general, it is known that when the transition metal compound used for the polymerization is different, the properties of the obtained polymer are greatly different.

  As a recent new olefin polymerization catalyst, JP-A-11-315109 describes a transition metal compound having a salicylaldoimine ligand represented by the general formula (I), and this complex exhibits high olefin polymerization activity. Are listed. Furthermore, in JP-A-12-119313, the transition metal compound and the organometallic compound are pre-contacted in the absence of olefin and then contacted with olefin. It is described that an ethylene (co) polymer having a narrow composition distribution is formed. Furthermore, WO 01-55231 discloses that syndiotactic polypropylene is produced by the transition metal compound having a fluorine atom as a substituent.

However, until now, there has been no known method for producing an aromatic vinyl compound polymer having isotacticity by using a transition metal compound having the salicylaldoimine ligand.
JP 11-315109 A JP-A-12-119313 WO 01-55231 Publication Angew. Chem., 1956 (68), 393 Polym. Prepr. 1998, 39 (1), 220 J. Am. Chem. Soc., 2003 (125), 4964 Macromolecules, 1990 (23), 1558 Macromol. Chem. Rapid. Commun., 1993 (14), 511

   In general, aromatic vinyl compound polymers are used in various fields such as for various molded products because they are excellent in good electrical characteristics, good moldability, etc. In recent years, there has been a demand for physical properties for aromatic vinyl compound polymers. A variety of aromatic vinyl compound polymers having various properties are desired. Under such circumstances, a novel polymerization catalyst capable of producing an aromatic vinyl compound polymer having excellent properties satisfying diversifying demands for physical properties and excellent polymerization performance of aromatic vinyl compounds. The appearance was desired.

  The present inventors diligently studied a transition metal compound having a novel structure for synthesizing an aromatic vinyl compound polymer that has solved the above problems and a polymerization method using the same, and are represented by the general formula (1). The present inventors have found that the above-mentioned problems can be solved by using the transition metal compound (A) and polymerizing at a temperature of 30 ° C. or lower, thereby completing the present invention.

  That is, an object of the present invention is to provide a method for polymerizing an aromatic vinyl compound using an olefin polymerization catalyst comprising a novel transition metal compound represented by the general formula (I).

(In the formula, M represents Ti, Zr, or Hf, and R ^{1 to} R ⁶ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, or an oxygen-containing group. , A nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of them are connected to each other to form a ring N is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, phosphorus A containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X are the same or different from each other It may be In the plurality of groups may be bonded to each other to form a ring represented.

  The novel transition metal compound according to the present invention can be used as a catalyst component for the polymerization of an aromatic vinyl compound. When an aromatic vinyl compound is polymerized, an aromatic vinyl compound polymer having stereoregularity is formed. And it is extremely industrially valuable.

  Hereinafter, a novel transition metal compound according to the present invention, an aromatic vinyl compound polymerization catalyst comprising the transition metal compound, and a method for polymerizing an aromatic vinyl compound using the same will be described in detail.

First, the novel transition metal compound according to the present invention will be described.
[Transition metal compound (A), an essential component of olefin polymerization catalyst]
The catalyst for olefin polymerization according to the present invention is a novel transition metal compound (A) represented by the following general formula (I).

In the formula (I), M represents Ti, Zr, or Hf, and Ti is particularly preferable. R ^{1 to} R ⁶ in formula (I) may be the same as or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, or a phosphorus-containing group. , A heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of these may be connected to each other to form a ring.

Specific examples of the hydrocarbon group represented by R ^{1 to} R ⁶ in formula (I) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, n- A linear or branched alkyl group having 1 to 30, preferably 1 to 20 carbon atoms such as hexyl; 2 to 30 carbon atoms such as vinyl, allyl, isopropenyl, preferably 2 to 20 straight-chain or branched alkenyl groups; straight-chain or branched alkynyl groups having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl and propargyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl A cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopentadienyl, indenyl, fluorenyl, etc. -30 cyclic unsaturated hydrocarbon groups; phenyl, benzyl, naphthyl, biphenylyl, terphenylyl, phenanthryl, anthryl, etc. aryl groups having 6-30 carbon atoms, preferably 6-20 carbon atoms; methylphenyl, isopropylphenyl , Alkyl-substituted aryl groups such as t-butylphenyl, dimethylphenyl, diisopropylphenyl, di-t-butylphenyl, trimethylphenyl, triisopropylphenyl, and tri-t-butylphenyl.

  In the hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl, and chlorophenyl. Can be mentioned.

  The hydrocarbon group may be substituted with another hydrocarbon group, and examples thereof include aryl group-substituted alkyl groups such as benzyl and cumyl.

  n is a number satisfying the valence of M, and M is Ti, Zr or Hf, preferably Ti.

  In the formula (I), X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic group A compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X may be the same or different from each other, and a plurality of groups represented by X Groups may be linked together to form a ring.

  Specific examples of the transition metal compound represented by the general formula (I) are shown below, but are not limited thereto. In the formula, M represents Ti, Zr, and Hf, Ph represents a phenyl group, and Ad represents an adamantyl group.

[Optional components constituting the olefin polymerization catalyst]
The transition metal compound (A) can be used alone or in combination as a catalyst for polymerizing an aromatic vinyl compound, but the catalyst for polymerizing an aromatic vinyl compound according to the present invention, if necessary,
(B) (B-1) Organometallic compound,
(B-2) an organoaluminum oxy compound, and
(B-3) It may contain at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form ion pairs. Next, each component of (B) component used as needed is demonstrated.

(B-1) Organometallic compound Specific examples of the organometallic compound (B-1) include the following organometallic compounds of Groups 1, 2 and 12, 13 of the periodic table.

(B-1a) General formula R ^a _m Al (OR ^b ) _n H _p X _q
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3).

(B-1b) General formula M ² AlR ^a ₄
(Wherein, ^{M 2} represents a Li, Na or K, ^{R a} is C 1 -C
-15, preferably 1-4 hydrocarbon groups. ) A complex alkylated product of a Group 1 metal and aluminum.

(B-1c) General formula R ^a R ^b M ³
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound of a Group 2 or Group 12 metal represented by:

  Examples of the organoaluminum compound belonging to (B-1a) include the following compounds.

General formula R ^a _m Al (OR ^b ) _3-m
(In the formula, R ^a and R ^b may be the same or different from each other and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m. ≦ 3.) An organoaluminum compound represented by

General formula R ^a _m AlX _3-m
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 <m <3). Organoaluminum compounds,

General formula R ^a _m AlH _3-m
(Wherein R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3),

General formula R ^a _m Al (OR ^b ) _n X _q
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is a number 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3).

More specific examples of the organoaluminum compound belonging to (B-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum Tri-n-alkylaluminum; triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methyl Pentyl aluminum, tri-3-methylpentyl aluminum, tri-4-methylpentyl aluminum, tri-2-methylhexyl aluminum, tri-3-methylhexyl aluminum, tri-2-ethylhexyl aluminum Tri-branched alkyl aluminum such as tricyclohexyl aluminum, tricycloalkyl aluminum such as tricyclohexyl aluminum; triaryl aluminum such as triphenyl aluminum and tolyl aluminum; dialkyl aluminum hydride such as diethyl aluminum hydride and diisobutyl aluminum hydride _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≦ 2x.) tri isoprenylaluminum represented by like Trialkenyl aluminum such as isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide and the like; Average ^{_{R a 2.5 Al (OR b)}} 0.5 represented by like; mini um methoxide, diethylaluminum ethoxide, dialkylaluminum alkoxides such as dibutyl aluminum butoxide; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide Partially alkoxylated alkylaluminum with composition: diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl- Dialkylaluminum aryloxy such as 4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide) De; Dialkylaluminum halides such as methylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides such as propylaluminum dichloride and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Ethylaluminum dihydride and propylaluminum dihydride Other partially hydrogenated alkylaluminums such as any alkylaluminum dihydride; including partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycycloride, ethylaluminum ethoxybromide, etc. .

A compound similar to (B-1a) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Examples of the compound belonging to (B-1b) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

  In addition, as the organometallic compound (B-1), methyl lithium, ethyl lithium, propyl lithium, butyl lithium, methyl magnesium bromide, methyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium chloride, propyl magnesium bromide, propyl magnesium Chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

  A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used. Of the organometallic compounds (B-1), organoaluminum compounds are preferred. The organometallic compound (B-1) as described above is used singly or in combination of two or more.

( B-2) Organoaluminum oxy compound The organoaluminum oxy compound ( B-2) used as necessary in the present invention may be a conventionally known aluminoxane or exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound. A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
[1] Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or water of crystallization with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension. [2] A method in which water, ice or water vapor directly acts on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. [3] A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specific examples of the organoaluminum compound used in preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. The above organoaluminum compounds are used singly or in combination of two or more.

  Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane; cyclopentane , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons (for example, Hydrocarbon solvents such as chlorinated products, brominated products, etc.). Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy compound is one in which the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms, that is, with respect to benzene. Those that are insoluble or sparingly soluble are preferred. Examples of the organoaluminum oxy compound also include an organoaluminum oxy compound (G-1) containing boron represented by the following general formula (II).

(In the formula, R ²⁰ represents a hydrocarbon group having 1 to 10 carbon atoms. R ²¹ represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same as or different from each other. The organoaluminumoxy compound (G-1) containing boron represented by the general formula (II) includes an alkyl boronic acid (G-2) represented by the following general formula (III),

(Wherein R ²⁰ represents the same group as described above.)
It can be produced by reacting an organoaluminum compound in an inert solvent under an inert gas atmosphere at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

  Specific examples of the alkyl boronic acid (G-2) represented by the general formula (III) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, Examples thereof include n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid. Among these, methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferable. These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to (B-1a). Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

  The (B-2) organoaluminum oxy compounds as described above are used singly or in combination of two or more.

(B-3) Ionized ionic compound The ionized ionic compound (B-3) is a compound that reacts with the transition metal compound (A) to form an ion pair. Examples of such compounds include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-1-501950, JP-A-1-502036, JP-A-3-17905, US5321106, and the like. Etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, methyl group, trifluoromethyl group, or fluorine) is exemplified. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, Examples include tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron.
Examples of the ionic compound include compounds represented by the following general formula (IV).

In the formula, ^examples of R ²²⁺ include H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal. R ^{23 to} R ²⁶ may be the same as or different from each other, and each represents an organic group, preferably an aryl group or a substituted aryl group.

  Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation. Specific examples of the ammonium cation include trialkylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-dialkylanilinium cation such as N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as di (isopropyl) ammonium cation and dicyclohexylammonium cation Etc.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

R ²²⁺ is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and triarylphosphonium salts.

  Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, and trimethylammonium tetra (p-tolyl). Boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra ( m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditrifluoromethylphenyl) boron, tri (n -Butyl) Ammonia Such as tetra (o- tolyl) boron and the like.

  Specific examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6 -Pentamethylanilinium tetra (phenyl) boron and the like. Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

  Further, as ionic compounds, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenyl Examples also include cyclopentadienyl complexes, N, N-diethylanilinium pentaphenylcyclopentadienyl complexes, and boron compounds represented by the following formula (V) or (VI).

(In the formula, Et represents an ethyl group.)

  Specific examples of the borane compound include decaborane; bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis Salts of anions such as [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate; -Butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III), etc. Can be mentioned.

  Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonarborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-dicarbanonaborane, dodecahydride- 1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane, Undecahydride-7,8-dimethyl-7,8-dicarboundecarborane, dodecahydride-11-methyl-2,7-dicarboundeborane, tri (n-butyl) ammonium 1-carbadecaborate, tri ( n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammo Nitrobromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 7-carbaundecaborate, tri ( n-Butyl) ammonium 7,8-dicarbaundecaborate, tri (n-butyl) ammonium 2,9-dicarbaound decaborate, tri (n-butyl) ammonium dodecahydride-8-methyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaound decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaound decaborate , Tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium Salts of anions such as decahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; tri (n-butyl ) Ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (III ), Tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaun) Decaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri n-Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicar Bound Decaborate) Ferrate (III), Tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), Tri (n-butyl) ) Ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate) cobaltate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromic acid Salt (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bi (Undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV), etc. Examples thereof include salts of metal carborane anions.

  The heteropoly compound is composed of atoms composed of silicon, phosphorus, titanium, germanium, arsenic or tin and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanovanadic acid, arsenic vanadic acid, phosphoniobic acid, germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid, titanium molybdic acid, germanomolybdic acid, arsenic molybdic acid, tin molybdic acid, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomolybdo tungstovanadate, phosphomolybdo Tungstic acid, phosphomolybniobic acid, salts of these acids, such as metals of Group 1 or 2 of the periodic table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, With barium etc. And organic salts such as triphenylethyl salt, and isopoly compounds, and the like. The heteropoly compound and the isopoly compound are not limited to one of the above compounds, and two or more of them can be used.

  The ionized ionic compound (B-3) as described above is used singly or in combination of two or more.

[Method of polymerizing aromatic vinyl compound]
Examples of the aromatic vinyl compound used as a monomer in the present invention include styrene, α-methylstyrene, o, m, p-methylstyrene, o, p-dimethylstyrene, ethylstyrenes, isopropylstyrenes, and butylstyrene. Vinyl-substituted or nucleus-substituted alkylstyrenes, vinyl-substituted or nucleus-substituted halogenated styrenes such as α, o, m, p-bromostyrene, and chlorostyrenes, and halogenated alkylstyrenes. Among these, styrene, paramethylstyrene, and α-methylstyrene are particularly preferable.

In the method for producing an aromatic vinyl compound polymer according to the present invention, an aromatic vinyl compound is added in the presence of a catalyst comprising the above components (A) and (B), and if necessary, other transition metal compounds. Polymerize. During the polymerization, the method of adding the component (A) to the polymerization vessel, the usage method of each component, the addition method, and the order of addition are arbitrarily selected, and the following methods are exemplified.
(1) A method in which component (A) and component (B) are added to the polymerization vessel in any order.
(2) A method in which a catalyst in which the component (A) and the component (B) are contacted in advance is added to the polymerization reactor.
(3) A method in which the catalyst component in which the component (A) and the component (B) are contacted in advance and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the component (B) may be the same or different.

  The polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, Examples include alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane or mixtures thereof. The compound itself can also be used as a solvent.

Using a catalyst as described above, when performing the polymerization of the aromatic vinyl compound, component (A) per liter of the reaction volume, usually 10 ^-13 to 10 ^-2 mol, preferably 10 ^-11 to 10 ^-2 It is used in such an amount that it becomes a mole.

  Component (B-1) has a molar ratio [(B-1) / M] of the component (B-1) and the transition metal atom (M) in the component (A) of usually 0.01 to 100,000, Preferably it is used in an amount of 0.05 to 50000.

  Component (B-2) has a molar ratio [(B-2) / M] of the aluminum atom in component (B-2) and the transition metal atom (M) in component (A) usually from 1 to 1. The amount used is 500,000, preferably 10 to 100,000.

  Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) usually from 1 to 10, preferably It is used in such an amount as to be 1-5. When component (D is used, when component (B) is component (B-1), the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0. In the case of component (B-2) in an amount of 1 to 5, the molar ratio of component (D) to aluminum atoms in component (B-2) [(D) / (B-2 )] Is usually 0.001 to 2, preferably 0.005 to 1 in the case of component (B-3), the molar ratio [(D) / (B-3)] is The amount is usually 0.01 to 10, preferably 0.1 to 5.

  There is no restriction | limiting in particular in the quantity of the aromatic vinyl compound with which it superposes | polymerizes, According to the kind of aromatic vinyl compound to be used, it selects suitably.

The polymerization temperature using such a polymerization catalyst is usually in the range of −50 to 30 ° C., preferably 0 to 20 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. it can. Further, the polymerization can be carried out in two or more stages having different reaction conditions.

  The molecular weight and molecular weight distribution of the aromatic vinyl compound obtained in the present invention can be adjusted by changing the polymerization temperature.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In this example, the molecular weight and molecular weight distribution of the obtained polymer were determined by high temperature GPC. The melting point (Tm) was measured using a DSC-7 model manufactured by Perkin-Elmer. ¹ H-NMR and ¹³ C-NMR were measured at 120 ° C. using ECP500 type manufactured by JEOL Ltd. and tetrachloroethane-d ₂ as a solvent.

<Polymerization of styrene using Bis [N- (3-trimethylsilylsalicylidene) -2,3,4,5,6-pentafluoroanilinato] titanium Dichloride>
100 ml of purified styrene in a glass flask having an internal volume of 500 ml sufficiently purged with nitrogen, and 20 toluene solution of DMAO (2.5 mol / l dry methylaluminoxane: methylaluminoxane was dried and dissolved again in toluene) 0.0 ml (50 mmol in terms of aluminum atom) was inserted and kept at 0 ° C. with stirring under a nitrogen atmosphere. Next, 20 ml of a toluene solution (2.5 mol / l) of Bis [N- (3-trimethylsilylsalicylidene) -2,3,4,5,6-pentafluoroanilinato] titanium dichloride was added to the flask to initiate polymerization (total toluene Amount 30 ml). After reacting at 0 ° C. for 360 minutes under a nitrogen atmosphere, the polymerization was stopped by adding a small amount of isobutyl alcohol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered. The polymer was thoroughly washed with methanol and then dried under reduced pressure at 130 ° C. for 10 hours to obtain 4.10 g of polystyrene. Subsequently, methyl ethyl ketone (200 ml) was added to 4.06 g of the obtained polystyrene, vigorously stirred for 24 hours, filtered through a membrane filter, and further washed with 30 ml of methyl ethyl ketone. It was dried under reduced pressure over time to obtain crystalline polystyrene. The ratio of crystalline polystyrene that is insoluble in methyl ethyl ketone to polystyrene before extraction with methyl ethyl ketone was 40.2%. As a result of measuring DSC of the obtained crystalline polystyrene, Tm in 1st scan was 185.0, 206.0, 217.0 ° C., and Tm in 2nd scan was not observed. As a result of measuring ¹³ C-NMR (tetrachloroethane-d2) of the crystalline polystyrene, the mm fraction of triad tacticity was 73%. The results are shown in Table 1, and the ¹³ C-NMR spectrum of crystalline polystyrene is shown in FIG.

<Polymerization of styrene using Bis [N- (3-trimethylsilylsalicylidene) -2,3,4,5,6-pentafluoroanilinato] titanium Dichloride>
In Example 1, polymerization and post-treatment were performed in the same manner as in Example 1 except that the polymerization temperature was changed to 20 ° C. and the polymerization time was changed to 60 minutes, to obtain 3.29 g of polystyrene. Crystalline polystyrene was obtained after removal of the methyl ethyl ketone-dissolved component in the same manner as in Example 1. The ratio of crystalline polystyrene that is insoluble in methyl ethyl ketone to polystyrene before extraction with methyl ethyl ketone was 61.7%. As a result of measuring DSC of the obtained crystalline polystyrene, Tm in 1st scan was 180.7, 202.0, 213.3 ° C., and Tm in 2nd scan was not observed. Further, as a result of measuring ¹³ C-NMR (tetrachloroethane-d 2) of the crystalline polystyrene, the mm fraction of triad tacticity was 81%. The results are shown in Table 1, and the ¹³ C-NMR spectrum of crystalline polystyrene is shown in FIG.

[Comparative Example 1]
180 ml of styrene was charged into a glass reactor having an internal volume of 500 ml which had been sufficiently purged with nitrogen, and kept at 25 ° C. with stirring. Next, 26.67 ml (40 mmol in terms of aluminum atom) of MAO in toluene (1.5 mol / l) and 75 ml of cyclopentadienyltitanium trichloride in toluene (0.67 mmol / l) were mixed with good stirring. The solution that had been reacted for 10 minutes was added to the reactor, and polymerization was started (total amount: 102 ml). After reacting at 25 ° C. for 60 minutes under a nitrogen atmosphere, the polymerization was stopped by adding a small amount of isobutyl alcohol. After completion of the polymerization, the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer, and then hydrochloric acid was added and filtered. The polymer was thoroughly washed with methanol and then dried under reduced pressure at 130 ° C. for 10 hours to obtain 8.95 g of polystyrene. The results are shown in Table 1. As a result of measuring ¹ H-NMR (tetrachloroethane-d 2) of the crystalline polystyrene, the ratio of isotactic polystyrene / syndiotactic polystyrene was 0/100. As a result of measuring ¹³ C-NMR (tetrachloroethane-d 2) of the crystalline polystyrene, the rr fraction of triad tacticity calculated for the aromatic ring C ₁ carbon signal was 94%.

  When the transition metal compound according to the present invention is used as a polymerization catalyst for an aromatic vinyl compound, an aromatic vinyl compound polymer having high isotacticity can be obtained, which is extremely valuable industrially.

3 is a ¹³ C-NMR (tetrachloroethane-d 2) spectrum of polystyrene insoluble in methyl ethyl ketone obtained in Example 1. FIG. 3 is a ¹³ C-NMR (tetrachloroethane-d 2) spectrum of polystyrene insoluble in methyl ethyl ketone obtained in Example 2.

Claims (2)

(A) a transition metal compound having a structure represented by the following general formula (I):
(B) (B-1) Organometallic compound
(B-2) an organoaluminum oxy compound, and
(B-3) A fragrance at a temperature of 30 ° C. or lower by a catalyst comprising at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form ion pairs. Aromatic vinyl compound polymer is produced by polymerizing an aromatic vinyl compound and having a triad tacticity mm fraction measured by ¹³ C NMR of the aromatic vinyl compound unit chain part composed of head-to-tail bonds of 60% or more. Method.

(In the formula, M represents Ti, Zr, or Hf, and R ^{1 to} R ⁶ may be the same as or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, or an oxygen-containing group. , A nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, and two or more of them are connected to each other to form a ring N is a number satisfying the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, phosphorus A containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and when n is 2 or more, a plurality of groups represented by X are the same or different from each other It may be In the plurality of groups may be bonded to each other to form a ring represented.) ¹³ C NMR of an aromatic vinyl compound unit chain part comprising a head-to-tail bond by polymerizing an aromatic vinyl compound at a temperature of 30 ° C. or lower in the presence of a catalyst in which the transition metal atom M is Ti in claim 1. A method for producing an aromatic vinyl compound polymer, wherein the mm fraction of triad tacticity measured in step (b) is 70% or more.

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