JP2001081121A - Method for producing syndiotactic styrenic polymer - Google Patents

Abstract

(57) [Summary] (Modifications) [PROBLEMS] To provide a production method capable of producing a high-molecular-weight syndiotactic styrene-based polymer having high syndiotacticity and high efficiency. As A (i) the catalyst component, (A) the general formula (1) and / or formula _{^{(2) MR 1 a R 2}} b R 3 c X 1 4- (a + b + c) (1) a transition metal compound represented by the _{^{MR 1 d R 2 e X 1}} 3- (d + e) (2), (B) (a) ~ (d)
(A) an organic aluminum oxy compound, (b) an ionic compound capable of producing a cationic transition metal compound by reacting with the transition metal compound, and (c) a cationic transition metal compound capable of producing a cationic transition metal compound by reacting with the transition metal compound. Lewis acid compounds, (d) organometallic compounds of metals of Groups 1, 2 and 13 of the Periodic Table, and those having a reaction product with a co-catalyst as a main catalyst component, having a dielectric constant of 3 .0
The styrene monomer of the general formula (3) is polymerized in the presence of a halogenated aromatic hydrocarbon solvent having a molecular weight of from 5.5 to 5.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for efficiently producing a high-molecular-weight syndiotactic styrene-based polymer having a high syndiotactic structure, starting from styrene or a derivative thereof. It is.

[0002]

2. Description of the Related Art Styrene-based polymers conventionally produced by a radical polymerization method or the like are molded into various shapes by various molding methods, and are used in household electric appliances, office equipment, household goods, packaging containers, toys, It is widely used as furniture, synthetic paper, and other industrial materials, but has a drawback that its three-dimensional structure has an atactic structure and is inferior in heat resistance and chemical resistance. As a solution to the drawbacks of the styrene polymer having an atactic structure, a styrene polymer having a high syndiotactic structure and a styrene copolymer obtained by copolymerizing the styrene monomer and other components are available. (JP-B-3-7685, JP-B1-37403, JP-A-63-24)
No. 1009). These polymers are excellent in heat resistance, chemical resistance and electrical properties, and are expected to be applied in various fields.

It is well known that a syndiotactic polystyrene-based polymer is usually obtained by polymerizing styrene or a derivative thereof using a titanium compound as a catalyst and methylalumoxane as a co-catalyst (Japanese Patent Publication No. 3-76).
No. 85, Japanese Patent Publication No. 1-37403, Japanese Patent Publication No. 2-42843). Although the above-mentioned patent publications state that various solvents can be used, examples of the polymerization solvents disclosed in the examples include aromatic hydrocarbons such as toluene, benzene and P-xylene, and Isopar-E (trademark). , And cyclic aliphatic hydrocarbons such as methylcyclohexane. Moreover, when the solvents disclosed in the examples of these publications are used, a high-molecular-weight syndiotactic polystyrene-based polymer can be efficiently produced because many side reactions occur during the polymerization reaction. It was difficult. In addition, special fairness
JP-A-2-42843 discloses that halogenated aromatic hydrocarbons can be used as a polymerization solvent, but none of the Examples used halogenated aromatic hydrocarbons.

On the other hand, J. Polym. Sci., (A), Polym. Che
m., 1991, Vol. 29, pp. 1243-1125, describes the results of syndiotactic polystyrene polymerization at 60 ° C. using chlorobenzene or dichlorobenzene as a halogenated aromatic solvent and a mixed solvent with toluene. I have. However, this document only describes that the polymerization activity of a mixed solvent of chlorobenzene or dichlorobenzene and toluene is lower than that of a case where toluene is used alone.

Also, Makromol. Chem., 1991, Vol. 192,
Pages 223 to 231 show the results of syndiotactic polystyrene polymerization at 50 ° C using 1,2,4-trichlorobenzene, chlorobenzene, o-dichlorobenzene or m-dichlorobenzene as a halogenated aromatic solvent. Is described.

However, the polymer obtained by polymerization under the temperature conditions described in these documents has a low molecular weight. Therefore, there has been a demand for the development of a production method for efficiently obtaining a high-molecular-weight syndiotactic styrene-based polymer having a high syndiotactic structure.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a highly syndiotactic structure which is excellent in heat resistance, moldability, and useful as a high-performance resin and a functional resin.
Another object of the present invention is to provide a method for efficiently producing a high molecular weight syndiotactic styrene-based polymer.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have determined that a reaction product with a specific transition metal component and a cocatalyst component is used as a catalyst component, The present inventors have found that the object of the present invention can be solved by polymerizing a styrene-based monomer at a specific temperature range using the catalyst in the presence of a halogenated aromatic hydrocarbon solvent having a dielectric constant of Was completed.

That is, the present invention provides a method for polymerizing a styrene monomer using a catalyst in the presence of a solvent, wherein the catalyst component comprises (A) the following general formula (1) and / or general formula (2): ^{_{1 a R 2 b R 3 c}} X 1 4- (a + b + c) (1) MR 1 d R 2 e X 1 3- (d + e) (2) ( wherein, R ^1, R ^2, And R ³ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, an acyloxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. Group, thioalkoxy group having 1 to 20 carbon atoms, 6 to 6 carbon atoms
20 thioaryloxy groups, cyclopentadienyl groups,
It represents a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group. M is titanium (Ti), zirconium (Zr)
Alternatively, a transition metal selected from the group consisting of hafnium (Hf) and X ¹ represents a halogen atom. These R ¹ , R ² and R ³ may be the same or different. A, b, and c each represent an integer of 0 to 4,
D and e each represent an integer of 0 to 3. A) a transition metal compound represented by

(B) the following (a) to (d): (a) an organoaluminum oxy compound; (b) an ionic compound capable of forming a cationic transition metal compound by reacting with the transition metal compound; Reaction with at least one cocatalyst selected from a Lewis acid compound capable of forming a cationic transition metal compound by reacting with a metal compound, and (d) an organometallic compound of a metal belonging to Group 1, 2 or 13 of the periodic table. It contains the product as a main catalyst component, and the solvent is a halogenated aromatic hydrocarbon having a dielectric constant in the range of 3.0 to 5.5, and -50 ° C to 4 ° C.
The present invention relates to a method for producing a syndiotactic styrene-based polymer, characterized in that one or more styrene-based monomers represented by the following general formula (3) are polymerized at a temperature of 0 ° C.

[0011]

Embedded image (Wherein, R is a hydrogen atom, a halogen atom, a carbon number of 1 to 30)
Or a substituent containing at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom, and m represents an integer of 0 to 5. However, when m is plural, each R may be the same or different. )

[0012]

Embodiments of the present invention will be described below in detail. In the method for producing a syndiotactic styrene polymer according to the present invention, the catalyst component is selected from the compounds represented by the general formulas (1) and (2) of the component (A). A compound containing, as a main catalyst component, a reaction product of at least one transition metal compound and at least one cocatalyst selected from components (A) to (d) of component (B) described above.

The transition metal compound of the component (A) is at least one compound selected from the group consisting of the transition metal compounds represented by the general formulas (1) and (2). R ¹ , R ² , and R ³ in the general formula (1) or (2) each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (specifically, a methyl group, an ethyl group, a propyl group, a butyl group). Group, amyl group, isoamyl group, isobutyl group, octyl group, 2-
An ethylhexyl group, etc.), an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group (specifically, a phenyl group, a tolyl group, a xylyl group, a benzyl group, etc.), an acyloxy group having 1 to 20 carbon atoms (specifically, Typically a heptadecylcarbonyloxy group), having 1 to 20 carbon atoms
An alkoxy group (specifically, a methoxy group, an ethoxy group,
Propoxy group, butoxy group, amyloxy group, hexyloxy group, 2-ethylhexyloxy group, etc.), carbon number 1
To 20 thioalkoxy groups (specifically, thiomethoxy group and the like), C6 to C20 thioaryloxy groups (specifically, thiophenoxy group and the like), cyclopentadienyl group, substituted cyclopentadienyl group ( Specifically, methylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, etc.),
It represents an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group.

M is titanium (Ti), zirconium (Zr)
Alternatively, a transition metal selected from the group consisting of hafnium (Hf), and X ¹ represents a halogen atom (specifically, chlorine, bromine, iodine, or fluorine). R ¹ in the general formulas (1) and (2),
R ² and R ³ may be the same or different. A, b, and c each represent an integer of 0 to 4, and d and e each represent an integer of 0 to 3.

Among these transition metal compounds, a titanium compound is most preferably used in terms of polymerization activity.
More preferred titanium compounds include a mono (cyclopentadiyl) titanium compound, a mono (indenyl) titanium compound and a mono (fluorenyl) titanium compound represented by the general formula (4). TiR ⁴ XYZ (4) (wherein, R ⁴ represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, etc., and X, Y and Z each independently represent a hydrogen atom , An alkyl group having 1 to 12 carbon atoms,
12 alkoxy groups, thioalkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, thioaryloxy group having 6 to 20 carbon atoms, 6 to 20 carbon atoms Represents an arylalkyl group or a halogen atom. )

The substituted cyclopentadienyl group represented by R ⁴ in the formula is, for example, an alkyl group having 1 to 6 carbon atoms,
A cyclopentadienyl group substituted by at least two, specifically a methylcyclopentadienyl group; a 1,3-dimethylcyclopentadienyl group; a 1,2,4-trimethylcyclopentadienyl group; 3,4-tetramethylcyclopentadienyl group;
Trimethylsilylcyclopentadienyl group; 1,3-di (trimethylsilyl) cyclopentadienyl group; tert-butylcyclopentadienyl group; 1,3-di (tertiarybutyl) cyclopentadienyl group; pentamethylcyclopenta And a dienyl group.

X, Y and Z each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (specifically, methyl, ethyl, propyl, n-butyl, isobutyl, amyl, Isoamyl group, octyl group, 2-ethylhexyl group, etc., and alkoxy group having 1 to 12 carbon atoms (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group, octyloxy group, 2 -Ethylhexyloxy group), having 1 to 1 carbon atoms
20 thioalkoxy groups (specifically, thiomethoxy group and the like), C6-C20 aryl groups (specifically, phenyl group, naphthyl group and the like), and C6-C20 aryloxy group (specifically, phenoxy group) Group), C6-20
A thioaryloxy group (specifically, a thiophenol group, etc.), an arylalkyl group having 6 to 20 carbon atoms (specifically, a benzyl group) or a halogen atom (specifically, chlorine, bromine, iodine or fluorine). Show.

Specific examples of the titanium compound represented by the general formula (4) include cyclopentadienyltrimethyltitanium; cyclopentadienyltriethyltitanium;
Cyclopentadienyl tripropyl titanium; cyclopentadienyl tributyl titanium; methyl cyclopentadienyl trimethyl titanium; 1,2-dimethylcyclopentadienyl trimethyl titanium; 1,2,4-trimethyl cyclopentadienyl trimethyl titanium; 1 , 2,3,4-tetramethylcyclopentadienyltrimethyltitanium; pentamethylcyclopentadienyltrimethyltitanium; pentamethylcyclopentadienyltriethyltitanium;

Pentamethylcyclopentadienyltripropyltitanium; pentamethylcyclopentadienyltributyltitanium; cyclopentadienylmethyltitanium dichloride; cyclopentadienylethyltitanium dichloride; pentamethylcyclopentadienylmethyltitanium dichloride; Cyclopentadienyl ethyl titanium dichloride; cyclopentadienyl dimethyl titanium monochloride; cyclopentadienyl diethyl titanium monochloride; cyclopentadienyl titanium trimethoxide; cyclopentadienyl titanium triethoxide;

Cyclopentadienyl titanium tripropoxide; cyclopentadienyl titanium triphenoxide;
Pentamethylcyclopentadienyl titanium trimethoxide; pentamethylcyclopentadienyl titanium triethoxide; pentamethylcyclopentadienyl titanium tripropoxide; pentamethylcyclopentadienyl titanium tributoxide; pentamethylcyclopentadienyl titanium Trifenoxide;

Cyclopentadienyl titanium trichloride; pentamethylcyclopentadienyl titanium trichloride; cyclopentadienyl methoxy titanium dichloride; cyclopentadienyl dimethoxy titanium chloride;
Pentamethylcyclopentadienylmethoxytitanium dichloride; cyclopentadienyltribenzyltitanium; pentamethylcyclopentadienylmethyldiethoxytitanium; indenyltitanium trichloride; indenyltitaniumtrimethoxide; indenyltitaniumtriethoxide; Nyltrimethyltitanium; indenyltribenzyltitanium; pentamethylcyclopentadienyltitanium trithiomethoxide; pentamethylcyclopentadienyltitanium trithiophenoxide and the like.

Further, as the titanium compound, a condensed titanium compound represented by the following general formula (5) may be used.

[0023]

Embedded image

(Wherein, R ⁵ and R ⁶ each represent a halogen atom, an alkoxy group or an acyloxy group having 1 to 20 carbon atoms, and k represents an integer of 2 to 20). The trivalent titanium compound is typically a titanium trihalide such as titanium trichloride or a cyclopentadienyl titanium compound such as cyclopentadienyl titanium dichloride. Obtained ones are listed. These trivalent titanium compounds may be those which form a complex with an ester, an ether or the like.

Further, zirconium compounds as transition metal compounds include tetrabenzyl zirconium, zirconium tetraethoxide, zirconium tetrabutoxide,
Bisindenyl zirconium dichloride, triisopropoxy zirconium chloride, zirconium benzyl dichloride, tributoxy zirconium chloride and the like, and the hafnium compound is tetrabenzyl hafnium,
Examples include hafnium tetraethoxide and hafnium tetrabutoxide, and vanadium compounds include vanadyl bisacetylacetonate, vanadyl triacetylacetonate, triethoxyvanadyl, and tripropoxyvanadyl. Among these transition metal compounds, titanium compounds are particularly preferred. Further, as the above-mentioned titanium compound or the like, a compound which forms a complex with an ester or an ether may be used.

The transition metal compound as the component (A) is a group consisting of a transition metal compound having two ligands having conjugated π electrons, for example, a transition metal compound represented by the following general formula (6). There is at least one compound selected from M ¹ R ⁷ R ⁸ R ⁹ R ¹⁰ (6) (wherein, M ¹ represents titanium, zirconium or hafnium, and R ⁷ and R ⁸ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group Or R ⁹ and R ¹⁰ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an amino group, or a thioalkoxy group having 1 to 20 carbon atoms. Wherein R ⁷ and R ⁸ are a hydrocarbon group having 1 to 5 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms and 1 to 5 silicon atoms, or a carbon group having 1 to 2 carbon atoms.
It may be cross-linked by 0 and germanium-containing hydrocarbon groups having 1 to 5 germanium. )

In the general formula (6), R ⁷ and R ⁸ are a cyclopentadienyl group or a substituted cyclopentadienyl group (specifically, a methylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl) 1,2,4-trimethylcyclopentadienyl group; 1,2,3,4-tetramethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group; 1,3- Di (trimethylsilyl) cyclopentadienyl group; 1,2,4-tri (trimethylsilyl) cyclopentadienyl group; tert-butylcyclopentadienyl group; 1,3-di (tert-butyl) cyclopentadienyl group A 1,2,4-tri (tert-butyl) cyclopentadienyl group), an indenyl group, a substituted indenyl group (specifically, a methylindenyl group; a dimethylindenyl group; A methylindenyl group, etc.), a fluorenyl group or a substituted fluorenyl group (for example, a methylfluorenyl group), R8 and R9 may be the same or different, and R7 and R8 are an alkylidene group having 1 to 5 carbon atoms (specifically, Methine, ethylidene, propylidene, dimethylcarbyl, etc.)
It may have a structure cross-linked by an alkylsilyl group having 1 to 20 silicon atoms or 1 to 5 silicon atoms (specifically, a dimethylsilyl group, a diethylsilyl group, a dibenzylsilyl group, etc.).

On the other hand, R ⁹ and R ¹⁰ are as described above, but more specifically, each is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (methyl group, ethyl group, propyl group, n- A butyl group, an isobutyl group, an amyl group, an isoamyl group, an octyl group, a 2-ethylhexyl group and the like; an aryl group having 6 to 20 carbon atoms (specifically, a phenyl group and a naphthyl group); Arylalkyl group (specifically, benzyl 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.), an aryloxy group having 6-20 carbon atoms (specifically, a phenoxy group, etc.), an amino group or a thioalkoxy group having 1-20 carbon atoms. Shows the sheet group.

Specific examples of the transition metal compound represented by the general formula (6) include biscyclopentadienyl titanium dimethyl; biscyclopentadienyl titanium diethyl; biscyclopentadienyl titanium dipropyl; Cyclopentadienyl titanium dibutyl; bis (methylcyclopentadienyl) titanium dimethyl; bis (tertiary butyl cyclopentadienyl) titanium dimethyl;
Bis (1,3-dimethylcyclopentadienyl) titanium dimethyl; bis (1,3-ditert-butylcyclopentadienyl) titanium dimethyl; bis (1,2,4-trimethylcyclopentadienyl) titanium dimethyl; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dimethyl; biscyclopentadienyltitanium dimethyl; bis (trimethylsilylcyclopentadienyl) titanium dimethyl;

Bis (1,3-di (trimethylsilyl) cyclopentadienyl) titanium dimethyl; bis (1,2,4-tri ((trimethylsilyl) cyclopentadienyl) titanium dimethyl; bisindenyltitanium dimethyl; bisflu Oleynyl titanium dimethyl; methylene biscyclopentadienyl titanium dimethyl; ethylidene biscyclopentadienyl titanium dimethyl; methylene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl; ethylidene bis (2,3, 4,5-tetramethylcyclopentadienyl)
Dimethylsilylbis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl; methylenebisindenyltitanium dimethyl; ethylidenebisindenyltitanium dimethyl; dimethylsilylbisindenyltitanium dimethyl;

Methylenebisfluorenyltitanium dimethyl; ethylidenebisfluorenyltitanium dimethyl; dimethylsilylbisfluorenyltitanium dimethyl; methylene (tert-butylcyclopentadienyl) (cyclopentadienyl) titanium dimethyl; Pentadienyl) (indenyl) titanium dimethyl; ethylidene (cyclopentadienyl) (indenyl) titanium dimethyl; dimethylsilyl (cyclopentadienyl) (indenyl) titanium dimethyl; methylene (cyclopentadienyl) (fluorenyl) titanium dimethyl; Ethylidene (cyclopentadienyl) (fluorenyl) titanium dimethyl; dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium dimethyl; methylene (indenyl)
(Fluorenyl) titanium dimethyl;

Ethylidene (indenyl) (fluorenyl) titanium dimethyl; dimethylsilyl (indenyl)
(Fluorenyl) titanium dimethyl; biscyclopentadienyltitanium dibenzyl; bis (tert-butylcyclopentadienyl) titanium dibenzyl; bis (methylcyclopentadienyl) titanium dibenzyl; bis (1,3-
Dimethylcyclopentadienyl) titanium dibenzyl; bis (1,2,4-trimethylcyclopentadienyl) titanium dibenzyl; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dibenzyl; bis Pentamethylcyclopentadienyltitanium dibenzyl; bis (trimethylsilylcyclopentadienyl) titanium dibenzyl; bis (1,
3-di- (trimethylsilyl) cyclopentadienyl) titanium dibenzyl;

Bis (1,2,4-tri (trimethylsilyl) cyclopentadienyl) titanium dibenzyl; bisindenyl titanium dibenzyl; bisfluorenyl titanium dibenzyl; methylenebiscyclopentadienyl titanium dibenzyl; ethylidene Biscyclopentadienyltitanium dibenzyl; methylenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl; ethylidenebis (2,3,
4,5-tetramethylcyclopentadienyl) titanium dibenzyl; dimethylsilylbis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl; methylenebisindenyltitanium dibenzyl; ethylidenebisindenyl Titanium dibenzyl; dimethylsilylbisindenyltitanium dibenzyl; methylenebisfluorenyltitanium dibenzyl;

Ethylidenebisfluorenyltitanium dibenzyl; dimethylsilylbisfluorenyltitanium dibenzyl; methylene (cyclopentadienyl) (indenyl)
Titanium dibenzyl; ethylidene (cyclopentadienyl) (indenyl) titanium dibenzyl; dimethylsilyl (cyclopentadienyl) (indenyl) titanium dibenzyl; methylene (cyclopentadienyl) (fluorenyl) titanium dibenzyl; ethylidene (cyclo Pentadienyl) (fluorenyl) titanium dibenzyl; dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium dibenzyl; methylene (indenyl) (fluorenyl)
Titanium dibenzyl; ethylidene (indenyl) (fluorenyl) titanium dibenzyl; dimethylsilyl (indenyl) (fluorenyl) titanium dibenzyl;

Biscyclopentadienyltitanium dimethoxide; biscyclopentadienyltitanium diethoxide;
Biscyclopentadienyl titanium dipropoxide; biscyclopentadienyl titanium dibutoxide; biscyclopentadienyl titanium diphenoxide; bis (methylcyclopentadienyl) titanium dimethoxide; bis (1,3-
Dimethylcyclopentadienyl) titanium dimethoxide;
Bis (1,2,4-trimethylcyclopentadienyl) titanium dimethoxide; bis (1,2,3,4-taylamethylcyclopentadienyl) titanium dimethoxide; bispentamethylcyclopentadienyltitanium dimethoxide; Bis (trimethylsilylcyclopentadienyl) titanium dimethoxide; bis (1,3-di (trimethylsilyl) cyclopentadienyl) titanium dimethoxide;

Bis (1,2,4-tri (trimethylsilyl) cyclopentadienyl) titanium dimethoxide; bisindenyltitanium dimethoxide; bisfluorenyltitanium dimethoxide; methylenebiscyclopentadienyltitanium dimethoxide; ethylidene Biscyclopentadienyl titanium dimethoxide; methylene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide; ethylidene bis (2,3,4,5-tetramethylcyclopentadienyl)
Titanium dimethoxide; dimethylsilyl bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide; methylenebisindenyl titanium dimethoxide; methylenebis (methylindenyl) titanium dimethoxide; ethylidenebisindenyl titanium Dimethoxide; dimethylsilylbisindenyltitanium dimethoxide;

Methylenebisfluorenyltitanium dimethoxide; methylenebis (methylfluorenyl) titanium dimethoxide; ethylidenebisfluorenyltitanium dimethoxide; dimethylsilylbisfluorenyltitanium dimethoxide; methylene (cyclopentadienyl) ( Ethylene (cyclopentadienyl) (indenyl) titanium dimethoxide; dimethylsilyl (cyclopentadienyl) (indenyl) titanium dimethoxide; methylene (cyclopentadienyl) (fluorenyl) titanium dimethoxide; ethylidene (Cyclopentadienyl) (fluorenyl) titanium dimethoxide; dimethylsilyl (cyclopentadienyl) (fluorenyl) titanium dimethoxide; methylene (indenyl)
(Fluorenyl) titanium dimethoxide; ethylidene (indenyl) (fluorenyl) titanium dimethoxide; dimethylsilyl (indenyl) (fluorenyl) titanium dimethoxide.

Examples of the zirconium compound include ethylidene biscyclopentadienyl zirconium dimethoxide, dimethylsilyl biscyclopentadienyl zirconium dimethoxide, and further, as the hafnium compound, ethylidene biscyclopentadienyl hafnium dimethoxide, And dimethylsilylbiscyclopentadienylhafnium dimethoxide. Among these, a titanium compound is particularly preferred. Further, in addition to these combinations, 2,2'-thiobis (4-methyl-6-t-butylphenyl) titanium diisopropoxide; 2,2'-thiobis (4-methyl-6-t-butylphenyl) titanium 2 such as dimethoxide
It may be a coordination complex.

Among these transition metal compounds, a transition metal compound having one π ligand as shown by the above-mentioned general formula (4) is particularly preferably used. In the polymerization catalyst used in the present invention, the transition metal compound as the component (A) may be used alone or in combination of two or more.

The catalyst component in the present invention is the above-mentioned transition metal compound (A) and the co-catalyst (B).
The reaction product with the component is contained as a main catalyst component, and as the component (B), which is a cocatalyst, at least one cocatalyst selected from the following (a) to (d) is used. (A) an organoaluminum oxy compound (b) an ionic compound capable of producing a cationic transition metal compound by reacting with the transition metal compound (c) a Lewis acid capable of producing a cationic transition metal compound by reacting with the transition metal compound Compounds (d) Organometallic compounds of metals from Groups 1, 2 and 13 of the Periodic Table

First, the organoaluminum oxy compound (a) is preferably a linear or cyclic polymer represented by the following general formula (7), and is a so-called aluminoxane. (—Al (R ¹¹ ) O—) _n (7) wherein R ¹¹ is a hydrocarbon group having 1 to 10 carbon atoms, and R ¹¹ itself is substituted by a halogen atom and / or an R ¹² —O group. May be used. Here, specific examples of R ¹¹ or R ¹² include alkyl groups such as methyl, ethyl, propyl, and isobutyl, and among them, a methyl group is preferable. n represents the degree of polymerization, and is preferably 5 or more, more preferably 10 to 100, and most preferably 10 to 50. If the degree of polymerization n is less than 5, the polymerization activity is undesirably reduced, and if it is more than 100, problems such as a decrease in polymerization activity and difficulty in demineralization are caused.

The ionic compound (b) capable of forming a cationic transition metal compound by reacting with the transition metal compound represented by the general formula (1) and / or the general formula (2) is a non-coordinating compound. Examples include anions and cations. Here, as the non-coordinating anion, for example, tetra (phenyl) borate, tetra (fluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( (Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (triyl) borate, tetra (xyyl) borate, triphenylpentafluorophenyl borate, tris (pentafluorophenyl) phenyl borate and the like.

Among these non-coordinating anions, those which are tetrakis (pentafluorophenyl) borate are particularly preferred. Specific examples include, for example, triphenylcarbenium tetrakis (pentafluorophenyl) borate; 4,4 ', 4 "-tri (methoxyphenyl) carbenium tetrakis (pentafluorophenyl) borate; tri (tolyl) carbenium tetrakis (pentane) Fluorophenyl) borate; 4,4 ', 4 "-tri (chlorophenyl)
Carbenium tetrakis (pentafluorophenyl) borate; triphenylsilyltetrakis (pentafluorophenyl) borate; trimethoxysilyltetrakis (pentafluorophenyl) borate; tri (thioisopropyl) silyltetrakis (pentafluorophenyl) borate; trimethylsilyltetrakis (penta Fluorophenyl) borate; 4,4 ', 4 "-tri (methoxyphenyl) silyltetrakis (pentafluorophenyl)
Borate; tri (tolyl) silyltetrakis (pentafluorophenyl) borate; 4,4 ', 4 "-tri (chlorophenyl) silyltetrakis (pentafluorophenyl)
Borate and the like.

Examples of the cation include a) a carbonium cation, b) an oxonium cation, c) an ammonium cation, d) a phosphonium cation, and e) a ferrocenium cation having a transition metal. a) Specific examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a trisubstituted phenylcarbonium cation. Specific examples of the tri-substituted phenylcarbonium cation include a tri (methylphenyl) carbonium cation and a tri (dimethylphenyl) carbonium cation.

B) Specific examples of the oxonium cation include alkyloxonium cations such as hydroxonium cation OH ³⁺ , methyloxonium cation CH ₃ OH ²⁺ , and dimethyloxonium cation (CH ₃ ) ₂ O
Examples thereof include a dialkyloxonium cation such as H ⁺ , a trialkyloxonium cation (CH ₃ ) ₃ O ⁺ , and a trialkyloxonium cation such as a triethyloxonium cation (C ₂ H ₅ ) ₃ O ⁺ .

C) Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, N, N-diethylanilinium cation, and N, N-2. N, N-dialkylanilinium cations such as 1,4,6-pentamethylanilinium cation, di (i-propyl) ammonium cations, and dialkylammonium cations such as dicyclohexylammonium cation.

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

As the ionic compound (b), those arbitrarily selected and combined from the non-coordinating anions and cations exemplified above can be used. Of the above, especially triphenylcarbonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetra (pentafluorophenyl) borate and the like Ionic compounds can be more preferably used.

Specific examples of the Lewis acid compound (c) capable of forming a cationic transition metal compound by reacting with the transition metal compound represented by the above general formula (1) and / or general formula (2) include tris (Pentafluorophenyl) boron, tris (monofluorophenyl) boron, tris (difluorophenyl) boron, and triphenylboron.

The organometallic compounds of Group 1, 2 and 13 element metals in the Periodic Table (d) include not only organic metal compounds in a narrow sense but also organometallic halogen compounds of Group 1, 2 and 13 element metals. And hydrogenated organometallic compounds. Here, the element metals of the periodic table 1 are: Li, Na. The element metals of the periodic table 2 are: Mg, Be. The element metals of the periodic table 13 are: Al and B. Of these, preferred element metals are Li, M
g, Al, particularly preferably Al.

Examples of the organometallic compound (d) include methyllithium, butyllithium, phenyllithium, dibutylmagnesium, trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum. Is preferred.
Examples of the organometallic halogen compound (d) include ethyl magnesium chloride, butyl magnesium chloride, dimethyl aluminum chloride, diethyl aluminum chloride, sesquiethyl aluminum chloride, and ethyl aluminum dichloride. Examples of the hydrogenated organometallic compound (d) include diethyl aluminum hydride and sesquiethyl aluminum hydride.

In the present invention, the above-mentioned (a) to
(D) may be used alone or in combination.
Preferred promoters are (a) alone, (c) alone, (a) and (d), (b) and (d), and (c) and (d). In particular, (a) alone is preferred.

The catalyst for producing a syndiotactic styrene resin used in the present invention contains the above components (A) and (B) as the main components of the catalyst. In addition, the effect of the present invention is impaired. Other catalyst components may be added within the range not present. The mixing ratio of the component (A) and the component (B) in the catalyst of the present invention varies depending on the type of the compound and various polymerization conditions, and cannot be unambiguously determined, but is usually determined independently of the component (B). Each compound (a), (b),
It is desirable that the molar ratio of the transition metal compound of the components (c), (d) and (A) be within the following range.

The molar ratio of aluminum / (A) transition metal compound in the (a) organoaluminum oxy compound is usually 1
~ 1000,000, preferably 10-50000, more preferably 1
00 to 5,000. The molar ratio of (b) the ionic compound / (A) the transition metal compound is usually from 0.01 to 100, preferably from 0.1 to 10. The molar ratio of (c) Lewis acidic compound / (A) transition metal compound is usually 0.01 to 100, preferably 0.1 to 10. Here, when a Lewis acid compound is used as the co-catalyst component, it is preferable to use an organometallic compound of a metal belonging to Group 1 or 2 of the periodic table in combination. When (d) an organometallic compound is used, the molar ratio of (d) the organometallic compound / (A) the transition metal compound is usually 0.1
1010,000, preferably 11,0001,000. Outside the above range, the polymerization activity is undesirably reduced.

In the present invention, the mixing ratio of the component (A) and the styrene monomer in the catalyst varies depending on the type of the compound and various polymerization conditions, and is not uniquely determined. It is desirable that the molar ratio of the transition metal compound to the styrene monomer be in the following range. That is, usually 0.1 to 10,000,000, preferably 1 to 5,000,000,
More preferably, it is 10 to 500,000. If the mixing ratio of the component (A) and the styrene-based monomer is less than 0.1, the polymerization rate is lowered, and the productivity of the polymer is undesirably reduced. Further, when the mixing ratio of the component (A) and the styrene-based monomer is larger than 10,000,000,
Since the molecular weight of the produced polymer is small, the strength of the syndiotactic styrene resin is undesirably reduced.

In the present invention, the metal hydride compound may be further used in combination with the above-mentioned organometallic compounds of the metals of Group 1, 2, and 13 of the periodic table, organometallic halogen compounds, hydrogenated organometallic compounds, and the like. A system monomer may be polymerized. Here, as the metal hydride compound, for example, N
aH, LiH, and the like _{CaH 2, LiAlH 4, NaBH 4} . Examples of the organometallic compounds, organometallic halogen compounds, and hydrogenated organometallic compounds of the main element metals of the Group 1, 2, and 13 element metals include those described above.

In the present invention, the transition metal compound represented by the general formula (1) and / or (2) alone,
Alternatively, the carrier and at least one cocatalyst selected from the above (a) to (d) can be used by being supported on a carrier. Examples of the carrier include an inorganic compound and an organic polymer compound. As the inorganic compound, inorganic oxides, inorganic chlorides, inorganic hydroxides and the like are preferable, and a small amount of carbonate,
Those containing sulfate may be used. Preferred are inorganic oxides such as silica, alumina, magnesia, titania, zirconia and calcia, and inorganic chlorides such as magnesium chloride. These inorganic compounds are preferably porous fine particles having an average particle diameter of 5 to 150 μm and a specific surface area of ² to 800 m ² / g, and can be used after being heat-treated at, for example, 100 to 800 ° C.

The organic polymer compound preferably has an aromatic ring, a substituted aromatic ring, or a functional group such as a hydroxy group, a carboxyl group, an ester group, or a halogen atom in the side chain. Specific examples of the organic polymer compound include α, which has a functional group obtained by chemically modifying a polymer having units such as ethylene, propylene, and butene.
-Olefin homopolymers, α-olefin copolymers, polymers having units of acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, divinylbenzene, and the like, and chemically modified products thereof. These organic polymer compounds have an average particle size of 5 to 25.
0 μm spherical fine particles are used. By supporting the transition metal compound and the co-catalyst on a simple substance, it is possible to prevent contamination due to adhesion of the catalyst to the polymerization reactor.

The styrene monomer used in the method for producing a syndiotactic styrene polymer of the present invention includes:
One or more styrene monomers represented by the following general formula (3) are used.

[0060]

Embedded image

(Wherein R is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or any one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom) And m represents 0 or more.
Represents an integer of from 5 to 5. However, when m is plural, each R may be the same or different. )

Here, as the halogen atom, fluorine,
Chlorine, bromine and iodine can be mentioned. Also,
Specific examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, an isopropyl group, and a tertiary butyl group; a hydrogen atom on a benzene ring having 6 to 30 carbon atoms; Aryl groups having a substituent containing a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom or a tin atom, a chloroethyl group, a bromomethyl group, and a bromoethyl group; And 20 halogen-substituted alkyl groups.

Here, a substituent containing a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom or a tin atom is added to a benzene ring having 6 to 30 carbon atoms. The aryl group having, for example, benzene ring, naphthalene ring, phenanthrene ring, anthracene ring, indene ring, azulene ring, heptalene ring, biphenylene ring, as-indacene ring, s-indacene ring, acenaphthylene ring, phenalene ring, fluoranthene ring, Acephenanthrene ring, aceanthrylene ring, triphenylene ring, naphthacene ring, pleiadene ring, picene ring, perylene ring, pentaphene ring, pentacene ring, rubicene ring, corocene ring, pyranthrene ring, ovalene ring, and their alkyl substituents ( Methyl group, ethyl group, isopropyl group Such as a tertiary butyl group),

Halogen-substituted alkyl groups (chloroethyl group, bromoethyl group, etc.), oxygen-containing substituents (methoxy, ethoxy, isopropoxy, methoxycarbonyl, acyloxy groups, etc.), silicon-containing substituents (trimethylsilyl group, etc.) And other substituents containing a tin atom (trimethylstannyl, tributylstannyl,
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 group, methylthio group) Group,
A selenium atom-containing substituent (methylseleno group, phenylseleno group, methylselenoxyl group,
Phenyl selenoxyl group, etc.), and substituents containing a phosphorus atom (eg, methyl phosphate group, phosphite group, dimethyl phosphino group, diphenyl phosphino group, methyl phosphinyl group, phenyl phosphinyl group), etc. At any position.

The substituent containing an oxygen atom includes a methoxy group, an ethoxy group, an isopropoxy group, a methoxycarbonyl group, an acyloxy group and the like. Examples of the substituent containing a silicon atom include a trimethylsilyl group. 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, a methylthio group, and a mercapto group. 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, a phosphite ester group, a dimethylphosphino group, a diphenylphosphino group, a methylphosphinyl group, and a phenylphosphinyl group.

In the structural unit represented by the general formula (3), m is an integer of 0 to 5, and when m is plural, m Rs are the same. Or different ones. Specific examples of the styrene monomer represented by the general formula (3) having such a substituent include styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene,
Alkylstyrenes such as 3,5-dimethylstyrene and p-tert-butylstyrene; p-chlorostyrene, m-
Halogenation of chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene styrene;

Vinyl biphenyls such as 4-vinyl biphenyl, 3-vinyl biphenyl and 2-vinyl biphenyl;
(4-vinylphenyl) naphthalene, 2- (4-vinylphenyl) naphthalene, 1- (3-vinylphenyl) naphthalene,
Vinylphenylnaphthalenes such as 2- (3-vinylphenyl) naphthalene, 1- (2-vinylphenyl) naphthalene, 2- (2-vinylphenyl) naphthalene; 1- (4-vinylphenyl) anthracene, 2- (4 -Vinylphenyl) anthracene, 9- (4-vinylphenyl) anthracene, 1-
(3-vinylphenyl) anthracene, 2- (3-vinylphenyl) anthracene, 9- (3-vinylphenyl) anthracene, 1- (2-vinylphenyl) anthracene, 2- (2-vinylphenyl) anthracene, 9- (2-vinylphenyl)
Vinyl anthracenes such as 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-vinylphenyl) pyrene, 1- (3-vinylphenyl) pyrene, 2- (3-vinylphenyl) pyrene, 1- (2-vinylphenyl) pyrene, 2 Vinylphenylpyrenes such as-(2-vinylphenyl) pyrene;

4-vinyl-p-terphenyl, 4-vinyl-m-
Terphenyl, 4-vinyl-o-terphenyl, 3-vinyl-
p-terphenyl, 3-vinyl-m-terphenyl, 3-vinyl-o-terphenyl, 2-vinyl-p-terphenyl, 2-vinyl-m-terphenyl, 2-vinyl-o-terphenyl, etc. Vinyl terphenyls; 4- (4-vinylphenyl) -p-
Vinylphenyl terphenyls such as terphenyl; 4-
Vinyl-4'-methylbiphenyl, 4-vinyl-3'-methylbiphenyl, 4-vinyl-2'-methylbiphenyl, 2-methyl-4-
Vinyl alkyl biphenyls such as vinyl biphenyl and 3-methyl-4-vinyl biphenyl; 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 Halogenated vinyl biphenyls such as, 4-vinyl-3'-bromobiphenyl, 4-vinyl-2'-bromobiphenyl, 4-vinyl-2-bromobiphenyl, 4-vinyl-3-bromobiphenyl; 4-vinyl- 4'-methoxybiphenyl,
4-vinyl-3'-methoxybiphenyl, 4-vinyl-2'-methoxybiphenyl, 4-vinyl-2-methoxybiphenyl, 4-vinyl-3-methoxybiphenyl, 4-vinyl-4'-ethoxybiphenyl, 4- Vinyl-3'-ethoxybiphenyl, 4-vinyl
Alkoxybiphenyls such as -2'-ethoxybiphenyl, 4-vinyl-2-ethoxybiphenyl and 4-vinyl-3-ethoxybiphenyl; 4-vinyl-4'-methoxycarbonylbiphenyl,

Alkoxycarbonylvinylbiphenyls such as 4-vinyl-4'-ethoxycarbonylbiphenyl;
Alkoxyalkylvinylbiphenyls such as vinyl-4'-methoxymethylbiphenyl; trialkylsilylvinylbiphenyls such as 4-vinyl-4'-trimethylsilylbiphenyl;4-vinyl-4'-methylstannylbiphenyl;
Trivinylstannylvinylbiphenyls such as 4-vinyl-4'-tributylstannylbiphenyl; 4-vinyl-
Trialkylsilylmethylvinylbiphenyls such as 4'-trimethylsilylmethylbiphenyl; trialkylstannylmethylvinylbiphenyls such as 4-vinyl-4'-trimethylstannylmethylbiphenyl and 4-vinyl-4'-tributylstannylmethylbiphenyl Arylstyrenes such as chloroethylstyrene; halogen-substituted alkylstyrenes such as p-chloroethylstyrene, m-chloroethylstyrene and o-chloroethylstyrene;

P-methoxystyrene, m-methoxystyrene, o-methoxystyrene, p-ethoxystyrene, m-
Alkoxystyrenes such as ethoxystyrene and o-ethoxystyrene; alkoxycarbonylstyrenes such as p-methoxycarbonylstyrene and m-methoxycarbonylstyrene; acyloxystyrenes such as acetyloxystyrene, ethanoyloxystyrene and benzoyloxystyrene; p-vinylbenzyl Alkyl ether styrenes such as propyl ether; alkyl silyl styrenes such as p-trimethylsilyl styrene; alkyl stannyl styrenes such as p-trimethylstannyl styrene, p-tributylstannyl styrene, p-triphenylstannyl styrene; vinylbenzene sulfonic acid Examples include vinyl styrene such as ethyl, vinylbenzyl dimethoxy phosphide, and p-vinyl styrene. Among these styrene monomers, styrene and alkylstyrene are preferably used from the viewpoint of cost and polymerization activity.

The syndiotactic styrenic polymer produced by the production method of the present invention may be any one or more of the styrenic monomers represented by the above general formula (3). Or a copolymer comprising a combination of In other words, the syndiotactic styrene-based polymer produced by the production method of the present invention does not necessarily show only one kind, but also contains two or more kinds of monomers. Homopolymer and 2
In addition to the terpolymer, multicomponent copolymers such as a terpolymer and a quaternary copolymer are also included.

Further, in the production method of the present invention, if necessary, the other monomeric copolymerizable with the styrene monomer in the syndiotactic styrene polymer may be used as long as the effects of the present invention are not impaired. The body can be copolymerized. Other monomers copolymerizable with the styrene monomer in this case include ethylene, propylene, olefins such as 1-butene, cyclopentene, cyclic olefins such as 2-norbornene, 1,3-butadiene, and 2-olefin. Conjugated dienes such as methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,5- Hexadiene, 1,6-heptadiene, 1,7-
Octadiene, dicyclopentadiene, 5-ethylidene-2
-Non-conjugated dienes such as norbornene, and (meth) acrylates such as methyl methacrylate and methyl acrylate.

Here, the syndiotactic styrene-based polymer produced by the production method of the present invention contains the above-mentioned monomer as a repeating unit. Mainly a syndiotactic structure, that is, a steric structure in which phenyl groups having or not having a substitution that is a side chain with respect to a main chain formed from carbon-carbon bonds are alternately located in opposite directions,
The tacticity is quantified by nuclear magnetic resonance (NMR). Specifically, ¹³ C-NMR method C1 carbon signal of the aromatic ring by (nuclear magnetic resonance method spectrum by carbon isotope), methine-methylene carbon signals or, ¹
Based on the analysis of the proton signal of H-NMR.

The tacticity determined by NMR is the abundance ratio of a plurality of continuous structural units (that is, the abundance ratio of a relative conformational relationship of continuous structural units). In the case of a triad, and in the case of five, it can be indicated by a pentad, but having mainly a syndiotactic structure in the present invention means that the degree of syndiotacticity depends on the type of substituent and the content ratio of each repeating unit. Is slightly variable, but is usually 75% or more, preferably 85% by racemic dyad in a chain of styrenic repeating units.
Those having a syndiotacticity of 30% or more, preferably 50% or more as a racemic pentad are shown.

In the syndiotactic styrenic polymer produced by the production method of the present invention, the repeating unit bonded is not only between one kind of structural unit but also between two or more kinds of both structural units. Have a syndiotactic structure (cosyndiotactic structure).
In addition, copolymers composed of these structural units include various modes such as block copolymerization, random copolymerization, and alternating copolymerization.

The styrenic polymer mainly having a syndiotactic structure according to the present invention is not necessarily required to be a single polymer. As long as the syndiotacticity is within the above range, a mixture with an isotactic or atactic styrene-based polymer or an atactic styrene-based polymer may be incorporated in the polymer chain.

The number average molecular weight (Mn) of the syndiotactic styrenic polymer obtained by the production method of the present invention is preferably 100,000 to 10,000,000, more preferably 100,000 to 5,000,000, and still more preferably 100,000.
~ 2,000,000. If the molecular weight is too small, the physical properties as a polymer such as low mechanical strength become insufficient, and conversely,
If the molecular weight is too large, there is a problem that molding becomes difficult.

The weight average molecular weight (Mw) of the syndiotactic styrene polymer obtained by the production method of the present invention
And the molecular weight distribution (Mw /
The preferred range of Mn) is 15 or less, more preferably 10
Or less, and most preferably 3.0 or less. If the molecular weight distribution is too wide, problems such as deterioration of physical properties such as abrasion resistance occur, which is not preferable.

In the method for producing a syndiotactic styrene-based polymer of the present invention, a high degree of polymerization is carried out by using the above-mentioned styrene-based monomer, transition metal compound, co-catalyst and the like in the following production method. A syndiotactic styrene polymer having a syndiotactic structure and a high molecular weight can be obtained.

<Production Method of Syndiotactic Styrene Resin> In the production method of the present invention, the transition metal compound of the component (A) and at least one cocatalyst selected from the above (a) to (d) are used. And at least one styrene at a temperature of −50 ° C. to 40 ° C. in the presence of a component (B), and a halogenated aromatic hydrocarbon solvent having a dielectric constant in the range of 3.0 to 5.5. The system monomer is polymerized.

In the present invention, the method of adding each catalyst component and monomer when polymerizing a styrene monomer or a styrene monomer and a monomer copolymerizable therewith is not particularly limited. The following methods (I) to (VI) using the transition metal compound of the component (A) and at least one cocatalyst selected from the above (a) to (d) are applicable. . In the following description, the component (A) is a transition metal compound, and the component (B) is the above (a) to (d).
Represents at least one cocatalyst selected from

(I) The component (B) and a monomer component such as a styrene monomer are brought into contact with each other in advance, and then contacted with the component (A) to carry out polymerization. (II) After the component (A) and the component (B) are brought into contact in advance, polymerization is carried out by further bringing the component into contact with a monomer component such as a styrene monomer. (III) After the component (A) and a monomer component such as a styrene monomer are brought into contact in advance, the polymerization is carried out by bringing the component (B) into contact with the component (B). (IV) The components (A) and (B) are mixed and brought into contact with a carrier, the formed supported catalyst is separated, and the supported catalyst is brought into contact with a monomer component such as a styrene-based monomer to perform polymerization. I do.

(V) After the component (A) is brought into contact with the carrier, the component (B) is further brought into contact with the carrier, the produced supported catalyst is separated, and the supported catalyst and the monomer component such as a styrene-based monomer are separated. And the polymerization is carried out. (VI) After the component (B) is brought into contact with the carrier, the component (A) is further brought into contact with the component, the produced supported catalyst is separated, and the supported catalyst is brought into contact with a monomer component such as a styrene monomer. Then, polymerization is performed.

In the catalyst reaction product, the above-mentioned transition metal compound and co-catalyst may be combined in any order. These catalyst components are suitably mixed in an inert atmosphere such as nitrogen or argon. The components are mixed at a suitable temperature, preferably from -50 to 40C, more preferably from -25 to 35C. The catalyst reaction product can be easily obtained only by mixing.

Among the above methods (I) to (VI), (I), (I) and (II) are used in view of improving the initiator efficiency and polymerization activity and further narrowing the molecular weight distribution of the obtained polymer. II) and
The methods (IV) to (VI) are preferred. More preferred are the methods (I) and (II). According to this method, a syndiotactic styrene-based resin having a molecular weight distribution (Mw / Mn) of 15 or less, which is a ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn), can be obtained with high efficiency.

The components (A) and (B) can be used in the form of either a solution or a slurry, respectively, but are preferably in the form of a solution in order to obtain a higher polymerization activity. Solvents used for preparing a solution or slurry are aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane, octane, cyclohexane, and mineral oil; benzene, toluene, aromatic hydrocarbon solvents such as xylene, or chloroform. , Methylene chloride, halogenated aliphatic hydrocarbon solvents such as dichloroethane, 2-fluorotoluene, 2-chlorotoluene, fluorobenzene, 2,6-dichlorotoluene, 1,2,
Halogenated hydrocarbon solvents such as 4-trichlorobenzene and chlorobenzene. Preferred solvents are halogenated aromatic hydrocarbons such as 2-fluorotoluene, 2-chlorotoluene, fluorobenzene and the like. Particularly preferably, the dielectric constant used as the polymerization solvent in the production method of the present invention is 3.0.
~ 5.5 halogenated aromatic hydrocarbon solvents. Specific examples include 2-fluorotoluene, 2-chlorotoluene, fluorobenzene, and 2,6-dichlorotoluene. Further, two or more kinds of solvents may be used as a mixture.

The polymerization temperature condition is usually -5 from the viewpoint of producing a high syndiotactic styrene polymer having a high syndiotactic structure and a high molecular weight, which are features of the present invention.
It is necessary to carry out within a range of 0 to 40 ° C. Preferably −40 to 40 ° C., more preferably −25 to 35 ° C.
At a temperature of If the polymerization temperature is lower than −50 ° C., the syndiotacticity is lowered, which is not preferable. If the polymerization temperature is higher than 40 ° C., the molecular weight is lowered, which is not preferable. Typical polymerization times are 30 seconds to 36 hours, preferably 1 minute to 20 hours, more preferably 5 minutes to 10 hours. The optimal time required to produce the desired polymer will vary with the temperature, solvent and other polymerization conditions used.

The polymerization can be carried out at sub-atmospheric pressures as well as at super-atmospheric pressures. It is also carried out at reduced pressure until the lowest component of the polymerization mixture evaporates. However, it is preferred to use a pressure near atmospheric pressure.

In the production method of the present invention, the solvent used for the polymerization is preferably a dielectric solvent from the viewpoint of producing a high syndiotactic styrene polymer having a high syndiotactic structure and a high molecular weight, which are features of the present invention. It is essential to use halogenated aromatic hydrocarbon solvents and mixtures thereof whose ratio is in the range of 3.0 to 5.5. Specific examples include 2-fluorotoluene, 2-chlorotoluene, fluorobenzene, 2,6-dichlorotoluene, and 1,2,4-trichlorobenzene. Among these halogenated aromatic hydrocarbons, 2-fluorotoluene, 2-chlorotoluene and fluorobenzene are preferred from the viewpoint that they have a low melting point and can be produced under a wide range of polymerization temperature conditions. Here, the permittivity is calculated using the CRC Handbook of Chemistry and Physic
Values described in s (76th EDITION) can be used. The method for measuring the dielectric constant of the solvent is not particularly limited, and it can be measured by a method usually used for measuring the dielectric constant of a liquid. As a method for measuring the permittivity, a capacitance change method comprising a measuring method such as a heterodyne beat method or a resonance method, or a bridge method is known (reference materials: Y. Morino, Ichiro Miyagawa, "Chemical Field", No. 8) Vol., P1 (1953)).

When the dielectric constant of the solvent is smaller than 3.0,
This is not preferable because the number of side reactions during polymerization increases and the molecular weight decreases. On the other hand, if the dielectric constant of the solvent is larger than 5.5, the polymerization activity is remarkably reduced, which causes a problem that it becomes difficult to obtain a high molecular weight syndiotactic styrene-based polymer, which is not preferable. The polymerization solvent is used in an appropriate amount to provide a monomer concentration of 0.1 to 98% by weight. Particularly preferably, it is 0.
The use of a suitable amount of solvent to give a monomer concentration of 3 to 70% by weight. If the monomer concentration is lower than 0.1% by weight, the polymerization rate is lowered, so that the productivity of the polymer is lowered and the cost of recovering the polymer from the polymerization reaction product is undesirably increased. On the other hand, if the monomer concentration is higher than 99% by weight, the viscosity of the polymerization reaction product becomes significantly higher as the polymerization conversion rate becomes higher, so that there is a disadvantage that the construction cost of the production equipment becomes higher.

Also, anisole, diphenyl ether,
A polymerization reaction may be carried out by adding a small amount of a polar compound such as an ether such as ethyl ether, diglyme, tetrahydrofuran or dioxane, or an amine such as triethylamine or tetramethylethylenediamine as long as the effects of the present invention are not impaired.

The termination of the polymerization reaction is usually carried out by adding a polymerization terminator to the polymerization system when a predetermined conversion is reached. As the polymerization terminator, for example, alcohols such as methanol, ethanol, propanol, butanol and isobutanol are used, and they may contain an acid such as hydrochloric acid. After termination of the polymerization reaction, the method of recovering the polymer is not particularly limited, for example,
A steam stripping method, precipitation with a poor solvent, or the like may be used.

In order to adjust the molecular weight of the polymer, a chain transfer agent may be added within a range that does not impair the effects of the present invention. As the chain transfer agent, allenes such as 1,2-butadiene, cyclic dienes such as cyclooctadiene, and hydrogen are preferably used.

[0097]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto. First,
Each evaluation and measurement method used in the examples of the present invention will be described. 1) Catalytic activity 1 mmol of catalytic metal was represented by the amount of polymer produced (gram) per hour. 2) Molecular weight and molecular weight distribution of polymer The measurement was performed using SSC-7100 type gel permeation chromatography manufactured by Senshu Kagaku with a differential refractometer attached as a detector. 3)% syndiotacticity It was determined by measuring pentads (racemic pentads) by ¹³ C-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. 4) Methyl ethyl ketone extraction residual amount (MIP) The polymer was extracted with methyl ethyl ketone for 5 hours using a Soxhlet extractor, and the extraction residue was dried at 50 ° C and 5 ° C using a vacuum dryer.
After drying for a time, the obtained polymer was determined by weighing.

Example 1 A polymerization reaction was carried out in a nitrogen atmosphere using a three-neck glass flask having an inner volume of 100 ml, which was dried and purged with nitrogen. 2-
24.3 ml of fluorotoluene (dielectric constant: 4.23) and 5.0 mmol (in terms of Al) of demethylated solid methylaluminoxane were charged and the temperature was kept at 23 ° C. Here styrene 2.5
After aging for 10 minutes, cyclopentadienyl titanitanium trichloride (CpTiCl3) 0.0025
of 2-fluorotoluene solution at 23 ° C.
The polymerization reaction was performed for 10 minutes. The polymerization reaction was stopped by adding a small amount of methanol, and the polymerization solution was poured into a large amount of acidic methanol to precipitate a polymer. Washing the obtained polymer,
After filtration, drying and weighing, the polymer yield was 0.114 g (yield was
4.7%).

The polymerization activity was 274 (g of PS) / (mmol Ti) *
hr). Next, when this polymer was extracted with methyl ethyl ketone for 5 hours using a Soxhlet extractor,
94% of extraction residue (MIP) was obtained. The weight average molecular weight (Mw) of the obtained polymer was 308000, and the number average molecular weight (Mn) was 157.
000, molecular weight distribution (Mw / Mn) was 2.0. Also,
^The syndiotacticity determined by ¹³ C-NMR measurement was 95% or more for racemic pentad. Table 1 shows the results.

Comparative Examples 1 to 3 The same operation as in Example 1 was performed except that the polymerization solvent was changed. Table 1 shows the results.

[0101]

[Table 1]

Examples 2 to 4 The same operation as in Example 1 was performed except that the polymerization solvent was changed. Table 2 shows the results.

[0103]

[Table 2]

Example 5 The same operation as in Example 1 was performed except that the polymerization solvent was changed. Table 3 shows the results.

Example 6 The same operation as in Example 5 was performed except that the amount of methylalumoxane added was changed. Table 3 shows the results.

Comparative Example 4 The same operation as in Example 5 was performed except that the polymerization temperature was changed. Table 3 shows the results.

Comparative Example 5 The same operation as in Example 5 was performed, except that the polymerization temperature and the polymerization solvent were changed. Table 3 shows the results.

[0108]

[Table 3]

Example 7 The same operation as in Example 1 was performed, except that indenyl tita titanium trichloride (IndTiCl 3) was used as the transition metal compound (A). Table 4 shows the results.

Examples 8 to 12 The same operation as in Example 7 was performed except that the type and amount of the transition metal compound (A), the amount of the promoter (B), the type and amount of the monomer, and the polymerization temperature were changed. went. Table 4 shows the results
And Table 5 below.

[0111]

[Table 4]

[0112]

[Table 5]

[0113]

According to the production method of the present invention, a high-molecular-weight syndiotactic styrene-based polymer having a high degree of syndiotacticity can be produced with high efficiency. The resulting styrenic polymer having syndiotacticity has excellent practical heat resistance and various physical properties such as chemical resistance, and is used in a wide range of fields such as home appliances and OA equipment. It is extremely useful as a plastic material to be used.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masahide Murata 2-3-15-504, Suido, Bunkyo-ku, Tokyo (72) Inventor Toshio Kase 5-2-2302, Matsushiro, Tsukuba, Ibaraki Prefecture (72) Inventor Hiroyuki Ozaki 4-6-202 Onogawa Tsukuba, Ibaraki Prefecture (72) Inventor Yoshifumi Fukui 4-63-507 Ninomiya 4-chome, Tsukuba City, Ibaraki Prefecture (72) Hideaki Hagiwara 2-Akubo, Tsukuba City, Ibaraki Prefecture 6-14 Sakurai Heights 203 (72) Inventor Jin Jiju 2-2-7 Kodateno, Kanazawa-shi, Ishikawa Prefecture (72) Inventor Satoshi Miyazawa 1-1-1 Higashi, Tsukuba-shi, Ibaraki Pref. Inventor Kenji Tsuchihara 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Advanced Industrial Science and Technology (72) Inventor Yasumi Suzuki 1-1-1, Higashi, Tsukuba, Ibaraki Institute of Materials Science and Technology (72) Inventor Michihiko Asai 1-1-1, Higashi, Tsukuba, Ibaraki Pref.Institute of Materials Science and Technology, Institute of Industrial Science (72) Kazuo Soga 1-1-1, Higashi, Tsukuba, Ibaraki F-term in Materials Engineering and Industrial Technology Research Institute (reference)

Claims (2)

[Claims] 1. A process for polymerizing styrene monomer using a catalyst in the presence of a solvent, the catalyst component, (A) the following general formula (1) and / or formula (2) MR ¹ _a R _{^{2 b R 3 c X 1 4-}} (a + b + c) (1) MR 1 d R 2 e X 1 3- (d + e) (2) ( wherein, R ^1, R ^2, and R ³ Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, an acyloxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, A thioalkoxy group having 1 to 20 carbon atoms, 6 to 6 carbon atoms
20 thioaryloxy groups, cyclopentadienyl groups,
It represents a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, or a substituted fluorenyl group. M is titanium (Ti), zirconium (Zr)
Alternatively, a transition metal selected from the group consisting of hafnium (Hf) and X ¹ represents a halogen atom. These R ¹ , R ² and R ³ may be the same or different. A, b, and c each represent an integer of 0 to 4,
D and e each represent an integer of 0 to 3. ), (B) the following (a) to (d) (a) an organoaluminum oxy compound, and (b) an ionic compound capable of producing a cationic transition metal compound by reacting with the transition metal compound. At least one selected from a compound, (c) a Lewis acid compound capable of producing a cationic transition metal compound by reacting with the transition metal compound, and (d) an organometallic compound of a metal belonging to Group 1, 2 or 13 of the periodic table. It contains a reaction product with a kind of cocatalyst as a main catalyst component, and the solvent is a halogenated aromatic hydrocarbon having a dielectric constant in the range of 3.0 to 5.5, and -50 ℃ -4
A method for producing a syndiotactic styrene-based polymer, comprising polymerizing at least one styrene-based monomer represented by the following general formula (3) at a temperature of 0 ° C. Embedded image (Wherein, R is a hydrogen atom, a halogen atom, a carbon number of 1 to 30)
Or a substituent containing at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, a silicon atom and a tin atom, and m represents an integer of 0 to 5. However, when m is plural, each R may be the same or different. ) 2. The main component of the catalyst component is represented by the following general formula (4):
The method for producing a syndiotactic styrene-based polymer according to claim 1, wherein the reaction product is a reaction product of a transition metal compound represented by the formula (1) and a cocatalyst comprising an aluminoxane. TiR ⁴ XYZ (4) (wherein, R ⁴ represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group, etc., and X, Y and Z each independently represent a hydrogen atom , An alkyl group having 1 to 12 carbon atoms,
12 alkoxy groups, thioalkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, thioaryloxy group having 6 to 20 carbon atoms, 6 to 20 carbon atoms Represents an arylalkyl group or a halogen atom. )