JP3487448B2 - Method for producing styrenic polymer - Google Patents

Description

Detailed Description of the Invention

The present invention relates to a method for producing a styrene polymer, and more particularly to a method for efficiently and inexpensively producing a styrene polymer having a high syndiotactic structure.

[0002]

2. Description of the Related Art In recent years, a styrene-based polymer having a syndiotactic structure (hereinafter referred to as SPS) is obtained by polymerizing a styrene-based monomer using a catalyst mainly composed of a transition metal compound, particularly a titanium compound and an alkylaluminoxane.
Sometimes referred to as)) is proposed (Japanese Patent Laid-Open No. 62-187708, etc.). Further, in the production of the styrene-based polymer as described above, in order to efficiently produce a styrene-based polymer having a syndiotactic structure without using an expensive and often used aluminoxane, a plurality of groups are bound to the metal anion. A method of using a coordination complex compound composed of cation and cation has also been proposed (JP-A-4-249503, JP-A-4-249504, etc.).

[0003]

However, when the styrene-based monomer is polymerized using the above catalyst,
The catalytic activity decreases, and the amount of residual metal contained in the resulting styrene-based polymer increases, which causes a decrease in molecular weight or deterioration of color tone. Further, there is a problem that the process becomes complicated because the number of steps is increased due to the need to reduce the amount of these residual metals, and the manufacturing cost is increased. As a result of intensive studies under such circumstances, the present inventors have found that when the styrene-based monomer is brought into contact with the SPS polymerization catalyst to polymerize, the indene-based compound contained in the styrene-based monomer is It was found that it affects the catalytic activity.

[0004]

The present invention has been completed based on the above findings. That is, the present invention is characterized by using a styrene-based monomer having an indene-based compound content of 50 ppm or less when the styrene-based monomer is brought into contact with an SPS polymerization catalyst for polymerization. The present invention provides a method for producing a polymer. Further, a preferred embodiment for carrying out the present invention is SP
As the S polymerization catalyst, (A) transition metal compound, (B)
(A) a compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex, or (b) the general formula (I)

[0005]

[Chemical 5]

(In the formula, R ^{1 to} R ⁵ are each 1 to 1 carbon atoms.
8 alkyl group, which may be the same or different from each other, Y ^{1 to} Y ³ each represent an element of Group 13 of the periodic table, and they may be the same or different from each other, and a and b Are numbers 0 to 50, respectively, and a +
b is 1 or more. ) And / or general formula (II)

[0007]

[Chemical 6]

(In the formula, each of R ⁶ and R ⁷ has 1 carbon atom.
~ 8 alkyl groups, which may be the same or different from each other, and Y ⁴ and Y ⁵ are each 1
3 group elements, which may be the same or different from each other, and c and d each represent a number of 0 to 50,
c + d is 1 or more. ) The oxygen-containing metal compound represented by the formula (1) and the optionally used (C) alkyl group-containing metal compound are used for producing the styrene polymer. The syndiotactic polystyrene (SPS) referred to in the present invention refers to a styrene-based polymer in which the polymerization chain part of the styrene-based monomer has a high syndiotactic structure.

There are no particular restrictions on the SPS polymerization catalyst used in the method of the present invention, and various catalysts can be used, but especially (A) transition metal compounds and (B).
(A) a compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex, or (b) an oxygen-containing compound having a specific structure, and (C) an alkyl group used as necessary. A catalyst composed of a contained metal compound is suitable. Although various compounds can be used as the transition metal compound of the component (A), compounds represented by the general formula (III) or the general formula (IV) are usually used. MR ⁸ _e R ⁹ _f R ¹⁰ _g R ¹¹ _{4- (e + f + g)}・ ・ ・ (III) MR ⁸ _h R ⁹ _i R ¹⁰ _{3- (h + i)}・ ・ ・ (IV) , M represents a metal element of Group 3 to 6 of the periodic table or a lanthanoid series metal element, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹
Are hydrogen atom, alkyl group, alkoxy group, aryl group, alkylaryl group, arylalkyl group, acyloxy group, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, fluorenyl group, substituted fluorenyl group, respectively. Group, alkylthio group,
An arylthio group, an amino group (-NR _2), shows a chelating ligand or a halogen atom. e, f, and g each represent an integer of 0 to 4, and h and j each represent an integer of 0 to 3. It also includes a complex in which any two of R ^{8 to} R ¹¹ are crosslinked with CH ₂ or Si (CH ₃ ) ₂ . As the metal element of Group 3 to 6 of the periodic table or the lanthanoid series metal element represented by M, a Group 4 metal element, particularly titanium, zirconium, hafnium or the like is preferably used.

There are various titanium compounds, for example, at least one compound selected from titanium compounds and titanium chelate compounds represented by the following general formula (V) or general formula (VI). T _i R ¹² _e R ¹³ _f R ¹⁴ _g R ¹⁵ _{4- (e + f + g)} ... (V) T _i R ¹² _h R ¹³ _i R ¹⁴ _{3- (h + i)} ... (VI [In the formula, R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or alkylaryl. Group, arylalkyl group, acyloxy group having 1 to 20 carbon atoms, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, fluorenyl group, substituted fluorenyl group, alkylthio group, arylthio group, amino group (-NR _2), shows a chelating ligand or a halogen atom. e, f, and g each represent an integer of 0 to 4, and h and i each represent an integer of 0 to 3. It also includes a complex in which any two of R ^{12 to} R ¹⁵ are crosslinked with CH ₂ or Si (CH ₃ ) ₂ . ]

R ¹² , R in the above general formula (V) or (VI)
¹³ , R ¹⁴ and R ¹⁵ are each a hydrogen atom and have 1 to 20 carbon atoms.
Alkyl groups (specifically, methyl group, ethyl group, propyl group, butyl group, amyl group, isoamyl group, isobutyl group, octyl group, 2-ethylhexyl group, etc.), alkoxy groups having 1 to 20 carbon atoms (specifically Are methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group,
Hexyloxy group, 2-ethylhexyloxy group, etc.), aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group (specifically, phenyl group, tolyl group, xylyl group, benzyl group, etc.), carbon number 1 ~ 20
Acyloxy group (specifically, heptadecylcarbonyloxy group, etc.), cyclopentadienyl group, substituted cyclopentadienyl group (specifically, methylcyclopentadienyl group, 1,2-dimethylcyclopentadienyl group) , Pentamethylcyclopentadienyl group, 4,5, 6,7-
Tetrahydro-1,2,3 trimethylindenyl group etc.), indenyl group, substituted indenyl group (specifically,
Methylindenyl group, dimethylindenyl group, tetramethylindenyl group, hexamethylindenyl group, etc.),
Fluorenyl group, substituted fluorenyl group (specifically, methylfluorenyl group, dimethylfluorenyl group, tetramethylfluorenyl group, octamethylfluorenyl group, etc.), alkylthio group (specifically, methylthio group , Ethylthio group, butylthio group, amylthio group, isoamylthio group, isobutylthio group, octylthio group, 2-ethylhexylthio group, etc., arylthio group (specifically, phenylthio group, p-methylphenylthio group, p-
Methoxyphenylthio group), amino group (-N
R ₂ ), a chelating ligand (specifically, 2,2′-thiobis (4-methyl-6-t-butylphenyl) group, etc.) or a halogen atom (specifically chlorine, bromine, iodine, Fluorine). These R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different.

Further preferred titanium compounds are represented by the general formula (VII) TiR ¹⁶ XYZ (VII) [wherein R ¹⁶ is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group. , Fluorenyl group, substituted fluorenyl group and the like, X, Y
And Z are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and 6 to 6 carbon atoms.
20 aryl group, C 6-20 aryloxy group, C 6-20 arylalkyl group, C 1-
40 alkyl or arylamide groups or halogen atoms of 40 are shown. ] There is a compound represented by. here,
One of X, Y and Z and R ¹⁶ is CH ₂ , Si (CH ₃ ).
_It also includes compounds cross-linked by ₂ or the like. The substituted cyclopentadienyl group represented by R ¹⁶ in this formula is, for example, a cyclopentadienyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms, specifically a methylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl group; 1,
2,4-trimethylcyclopentadienyl group; 1,2,
3,4-Tetramethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group; 1,3-di (trimethylsilyl) cyclopentadienyl group; tertiary butylcyclopentadienyl group; 1,3-di (tertiary Butyl) cyclopentadienyl group; pentamethylcyclopentadienyl group and the like. Also, X, Y and Z
Are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (specifically, methyl group, ethyl group, propyl group, n-
Butyl group, isobutyl group, amyl group, isoamyl group, octyl group, 2-ethylhexyl group, etc.), carbon number 1 to 1
2 alkoxy groups (specifically, methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, etc.), aryl group having 6 to 20 carbon atoms (specifically, Specifically, a phenyl group, a naphthyl group, etc.), an aryloxy group having 6 to 20 carbon atoms (specifically, a phenoxy group, etc.), an arylalkyl group having 6 to 20 carbon atoms (specifically, a benzyl group, etc.), carbon It represents an alkyl or aryl amide group of 1 to 40 or a halogen atom (specifically chlorine, bromine, iodine or fluorine).

Specific examples of the titanium compound represented by the general formula (VII) include cyclopentadienyltrimethyl titanium; cyclopentadienyl triethyl titanium;
Cyclopentadienyl tripropyl titanium; Cyclopentadienyl tributyl titanium; Methyl cyclopentadienyl trimethyl titanium; 1,2-Dimethyl cyclopentadienyl trimethyl titanium; 1,2,4-Trimethyl cyclopentadienyl trimethyl titanium; 1 , 2, 3, 4
-Tetramethylcyclopentadienyl trimethyl titanium; pentamethyl cyclopentadienyl trimethyl titanium; pentamethyl cyclopentadienyl triethyl titanium; pentamethyl cyclopentadienyl tripropyl titanium; pentamethyl cyclopentadienyl tributyl titanium; cyclopentadi Enylmethyl titanium dichloride;
Cyclopentadienyl ethyl titanium dichloride; pentamethyl cyclopentadienyl methyl titanium dichloride;
Pentamethylcyclopentadienylethyl 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; pentamethylcyclopenta Dienyl titanium tributoxide; pentamethylcyclopentadienyl titanium triphenoxide;
Cyclopentadienyl titanium trichloride; pentamethylcyclopentadienyl titanium trichloride; cyclopentadienyl methoxy titanium dichloride; cyclopentadienyl dimethoxy titanium chloride; pentamethyl cyclopentadienyl methoxy titanium dichloride; cyclopentadienyl tribenzyl Titanium; pentamethylcyclopentadienylmethyldiethoxytitanium; indenyl titanium trichloride; indenyl titanium trimethoxide;
Indenyl titanium triethoxide; indenyl trimethyl titanium; indenyl tribenzyl titanium; (t-butylamido) dimethyl (tetramethyl η ⁵ -cyclopentadienyl) silane titanium dichloride; (t-butylamido) dimethyl (tetramethyl η ⁵ -Cyclopentadienyl) silane titanium dimethyl; (t-butylamido) dimethyl (tetramethyl η ⁵ -cyclopentadienyl) silane titanium dimethoxide; 4,5,6,7-tetrahydroindenyl titanium trimethoxide; 1- Methyl-4,
5,6,7-Tetrahydroindenyl titanium trimethoxide; 2-methyl-4,5,6,7-tetrahydroindenyl titanium trimethoxide; 1,2-dimethyl-4,
5,6,7-Tetrahydroindenyl titanium trimethoxide; 1,3-Dimethyl-4,5,6,7-tetrahydroindenyl titanium trimethoxide; 1,2,3-Trimethyl-4,5,6. 7-Tetrahydroindenyl titanium trimethoxide; 1,2,3,4,5,6,7-heptamethyl-4,5,6,7-tetrahydroindenyl titanium trimethoxide; 1,2,4,5,5 6,7-Hexamethyl-4,5,6,7-tetrahydroindenyl titanium trimethoxide; 1,3,4,5,6,7-hexamethyl-4,5,6,7-tetrahydroindenyl titanium trimethoxy Octahydrofluorenyl titanium trimethoxide; 1,2,3,4-tetrahydrofluorenyl titanium trimethoxide; 9-methyl-1,2,3,4
-Tetrahydrofluorenyl titanium trimethoxide; 9
-Methyl-octahydrofluorenyl titanium trimethoxide and the like. Of these titanium compounds,
A compound containing no halogen atom is preferable, and a titanium compound having one π-electron ligand as described above is particularly preferable. Further, as the titanium compound, the general formula (VIII)

[0014]

[Chemical 7]

[In the formula, R ¹⁷ and R ¹⁸ each represent a halogen atom, an alkoxy group having 1 to 20 carbon atoms, or an acyloxy group, and k represents 2 to 20. ] A condensed titanium compound represented by the following may be used. Further, the titanium compound may be used in the form of a complex with an ester or ether. The trivalent titanium compound represented by the general formula (VI) typically includes titanium trihalides such as titanium trichloride and cyclopentadienyl titanium compounds such as cyclopentadienyl titanium dichloride. The thing obtained by reducing a valent titanium compound is mentioned. These trivalent titanium compounds may be used in the form of a complex with an ester or ether. 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 hafnium. Compounds include tetrabenzyl hafnium, hafnium tetraethoxide, hafnium tetrabutoxide, and the like, and vanadium compounds include vanadyl bisacetylacetonate, vanadyl triacetylacetonate, triethoxy vanadyl, tripropoxy vanadyl, and the like. Among these transition metal compounds, titanium compounds are particularly suitable.

As the transition metal compound which is the other component (A), a transition metal compound having two ligands having conjugated π electrons, for example, a compound represented by the general formula (IX) M ¹ R ¹⁹ R ²⁰ R ²¹ R ²² .. (IX) [In the formula, M ¹ represents titanium, zirconium, or hafnium, and R ¹⁹ and R ²⁰ are cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, fluorenyl group, or A substituted fluorenyl group, R ²¹ and R ²² 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; Indicates. However, R ¹⁹ and R ²⁰ have 1 carbon atom
It may be crosslinked by a hydrocarbon group having 5 to 5 carbon atoms, an alkylsilylene group having 1 to 20 carbon atoms and 1 to 5 silicon atoms, or a germanium-containing hydrocarbon group having 1 to 20 carbon atoms and 1 to 5 germanium atoms. ] There is at least one compound selected from the group consisting of transition metal compounds.

R ¹⁹ and R ²⁰ in the above general formula (IX) are a cyclopentadienyl group and a substituted cyclopentadienyl group (specifically, a methylcyclopentadienyl group; 1,
3-dimethylcyclopentadienyl group; 1,2,4-trimethylcyclopentadienyl group; 1,2,3,4-tetramethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadiene group 1,3-di (trimethylsilyl) cyclopentadienyl group; 1,2,4-tri (trimethylsilyl)
Cyclopentadienyl group; tert-butyl cyclopentadienyl group; 1,3-di (tert-butyl) cyclopentadienyl group; 1,2,4-tri (tert-butyl) cyclopentadienyl group etc.) , Indenyl group, substituted indenyl group (specifically, methylindenyl group; dimethylindenyl group; trimethylindenyl group, etc.), fluorenyl group or substituted fluorenyl group (for example, methylfluorenyl group), R ¹⁹ and R ²⁰ may be the same or different, and R ¹⁹ and R ²⁰ are each an alkylidene group having 1 to 5 carbon atoms (specifically, a methine group,
Crosslinking with ethylidene group, propylidene group, dimethylcarbyl group, etc.) or alkylsilylene group having 1 to 20 carbon atoms and 1 to 5 silicon atoms (specifically, dimethylsilylene group, diethylsilylene group, dibenzylsilylene group, etc.) It may have a structured structure. On the other hand, R ²¹ and R ²² are as described above, but more specifically, they are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (methyl group, ethyl group, propyl group, n-butyl group). , Isobutyl group, amyl group, isoamyl group, octyl group, 2-ethylhexyl group, etc.), aryl group having 6 to 20 carbon atoms (specifically, phenyl group, naphthyl group, etc.), 7 to 2 carbon atoms.
0 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, octyl group) Oxy group,
2-ethylhexyloxy group, etc.), an aryloxy group having 6 to 20 carbon atoms (specifically, a phenoxy group, etc.),
Further, it represents an amino group or a thioalkoxy group having 1 to 20 carbon atoms.

Specific examples of the transition metal compound represented by the general formula (IX) include biscyclopentadienyl titanium dimethyl; biscyclopentadienyl titanium diethyl; biscyclopentadienyl titanium dipropyl;
Bis (cyclopentadienyl) titanium dibutyl; Bis (methylcyclopentadienyl) titanium dimethyl; Bis (tert-butyl cyclopentadienyl) titanium dimethyl; Bis (1,3-dimethylcyclopentadienyl) titanium dimethyl; Bis (1 , 3-Ditertiarybutylcyclopentadienyl) titanium dimethyl; bis (1,2,2
4-trimethylcyclopentadienyl) titanium dimethyl; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dimethyl; bispentamethylcyclopentadienyl titanium dimethyl; bis (trimethylsilylcyclopentadienyl) titanium Dimethyl; bis (1,3
-Di (trimethylsilyl) cyclopentadienyl) titanium dimethyl; bis (1,2,4-tris (trimethylsilyl) cyclopentadienyl) titanium dimethyl; bisindenyl titanium dimethyl; bisfluorenyl titanium dimethyl; methylenebiscyclopenta Dienyl titanium dimethyl; ethylidene biscyclopentadienyl titanium dimethyl; methylene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethyl; ethylidene bis (2,3,4,5-tetramethyl cyclopentadi (Enyl) titanium dimethyl; dimethyl silylene bis (2,3,
4,5-Tetramethylcyclopentadienyl) titanium dimethyl; methylene bis indenyl titanium dimethyl; ethylidene bis indenyl titanium dimethyl; dimethyl silylene bis indenyl titanium dimethyl; methylene bis fluorenyl titanium dimethyl; ethylidene bis fluorenyl titanium Dimethyl; dimethylsilylene bisfluorenyl titanium dimethyl; methylene (tert-butyl cyclopentadienyl) (cyclopentadienyl) titanium dimethyl; methylene (cyclopentadienyl) (indenyl)
Titanium dimethyl; ethylidene (cyclopentadienyl)
(Indenyl) titanium dimethyl; dimethylsilylene (cyclopentadienyl) (indenyl) titanium dimethyl;
Methylene (cyclopentadienyl) (fluorenyl) titanium dimethyl; ethylidene (cyclopentadienyl)
(Fluorenyl) titanium dimethyl; dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dimethyl; methylene (indenyl) (fluorenyl) titanium dimethyl; ethylidene (indenyl) (fluorenyl)
Titanium dimethyl; Dimethylsilylene (indenyl) (fluorenyl) titanium dimethyl; Biscyclopentadienyl titanium dibenzyl; Bis (tert-butyl cyclopentadienyl) 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 Pentamethylcyclopentadienyl titanium dibenzyl; bis (trimethylsilylcyclopentadienyl) titanium dibenzyl; bis (1,3-di- (trimethylsilyl) cyclopentadienyl) titanium dibenzyl; bis (1,2,
4-tris (trimethylsilyl) cyclopentadienyl) titanium dibenzyl; bisindenyl titanium dibenzyl; bisfluorenyl titanium dibenzyl; methylene biscyclopentadienyl titanium dibenzyl; ethylidene biscyclopentadienyl titanium dibenzyl; Methylenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl; ethylidenebis (2,3,4
5-tetramethylcyclopentadienyl) titanium dibenzyl; dimethylsilylene bis (2,3,4,5-tetramethylcyclopentadienyl) titanium dibenzyl; methylenebisindenyl titanium dibenzyl; ethylidene bisindenyl titanium dibenzyl Benzyl; dimethylsilylene bis indenyl titanium dibenzyl; methylene bis fluorenyl titanium dibenzyl; ethylidene bis fluorenyl titanium dibenzyl; dimethyl silylene bis fluorenyl titanium dibenzyl; methylene (cyclopentadienyl) (indenyl) titanium Dibenzyl; ethylidene (cyclopentadienyl) (indenyl) titanium dibenzyl; dimethylsilylene (cyclopentadienyl) (indenyl) titanium dibenzyl; methylene (cyclopentadienyl) (fluorenyl) tita Dibenzyl; ethylidene (cyclopentadienyl) (fluorenyl) titanium dibenzyl; dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dibenzyl; methylene (indenyl) (fluorenyl) titanium dibenzyl; ethylidene (indenyl) (fluorenyl) titanium Dibenzyl; dimethylsilylene (indenyl) (fluorenyl) titanium dibenzyl; biscyclopentadienyl titanium dimethoxide; biscyclopentadienyl titanium diethoxide; biscyclopentadienyl titanium dipropoxide; biscyclopentadienyl titanium Dibutoxide; Biscyclopentadienyl titanium diphenoxide; Bis (methylcyclopentadienyl) titanium dimethoxide; Bis (1,3-dimethylcyclopentadienyl) titanium dime Xide; bis (1,2,4-trimethylcyclopentadienyl) titanium dimethoxide; bis (1,2,3,4-tetramethylcyclopentadienyl) titanium dimethoxide; bispentamethylcyclopentadienyl titanium dimethoxy Bis (trimethylsilylcyclopentadienyl) titanium dimethoxide; bis (1,3-di (trimethylsilyl) cyclopentadienyl) titanium dimethoxide; bis (1,
2,4-Tris (trimethylsilyl) cyclopentadienyl) titanium dimethoxide; bisindenyl titanium dimethoxide; bisfluorenyl titanium dimethoxide; methylene biscyclopentadienyl titanium dimethoxide; ethylidene biscyclopentadienyl titanium dimethoxy Methylenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide; ethylidenebis (2,3,4,5-tetramethylcyclopentadienyl) titanium dimethoxide; dimethylsilylenebis (2 ，
3,4,5-Tetramethylcyclopentadienyl) titanium dimethoxide; methylenebisindenyl titanium dimethoxide; methylenebis (methylindenyl) titanium dimethoxide; ethylidenebisindenyl titanium dimethoxide; dimethylsilylene bisindenyl titanium dimethoxy Methylenebis (methylfluorenyl) titanium dimethoxide; ethylidene bisfluorenyl titanium dimethoxide;
Dimethylsilylene bisfluorenyl titanium dimethoxide; methylene (cyclopentadienyl) (indenyl)
Titanium dimethoxide; ethylidene (cyclopentadienyl) (indenyl) titanium dimethoxide; dimethylsilylene (cyclopentadienyl) (indenyl) titanium dimethoxide; methylene (cyclopentadienyl) (fluorenyl) titanium dimethoxide; ethylidene (cyclo) Pentadienyl) (fluorenyl) titanium dimethoxide;
Dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dimethoxide; methylene (indenyl)
(Fluorenyl) titanium dimethoxide; ethylidene (indenyl) (fluorenyl) titanium dimethoxide; dimethylsilylene (indenyl) (fluorenyl) titanium dimethoxide and the like.

The zirconium compounds include ethylidene biscyclopentadienyl zirconium dimethoxide and dimethylsilylene biscyclopentadienyl zirconium dimethoxide, and the hafnium compounds include ethylidene biscyclopentadienyl hafnium dimethoxide and Examples include dimethylsilylene biscyclopentadienyl hafnium dimethoxide. Among these, titanium compounds are particularly preferable. In addition to these combinations, 2,2'-thiobis (4-methyl-6)
-T-butylphenyl) titanium diisopropoxide;
It may be a bidentate complex such as 2,2′-thiobis (4-methyl-6-t-butylphenyl) titanium dimethoxide. In the present invention, among these transition metal compounds, a titanium compound having at least one ligand having a conjugated π electron is suitable. These transition metal compounds may be used alone or in combination of two or more.

Next, in the polymerization catalyst of the present invention, there are various compounds that can react with the transition metal compound used as the component (B) (a) to form an ionic complex. For example, a coordination complex compound composed of an anion in which a plurality of groups represented by the following general formula (X) or (XI) is bound to a metal and a cation can be preferably used. ([L ¹ -H] ^{p +)} _q ^{([M 2 X 1 X 2 ··· X} r ] _{^{(rs) -) j ··· (}} X) ( [L ^{2] p +)} _q ([M ³ X ¹ X ² ... X ^r ] ^(rs)- ) _j ... (XI) [In formula (X) or (XI), L ² is M ⁴ , R ²³ R ²⁴ described later.
M ⁵ or R ²⁵ ₃ C, L ¹ is a Lewis base, M ² and M ³ are metals selected from Groups 5 to 15 of the periodic table, and M ⁴ is Group 1 and 8 of the periodic table. A metal selected from Group 12; M ⁵ is a metal selected from Groups 8 to 10 of the periodic table; X ^{1 to} X ^r are a hydrogen atom, a dialkylamino group, an alkoxy group, an aryloxy group, and a carbon number of 1 to 20, respectively.
Represents an alkyl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, a substituted alkyl group, an organic metalloid group or a halogen atom. R ²³ and R ²⁴
Represents a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ²⁵ represents an alkyl group. s is an integer of 1 to 7 as the valence of M ² and M ³ , r is an integer of 2 to 8, p is an integer of 1 to 7 as the ionic valence of L ¹ -H and L ² , and q is 1 or more. Integer, j = q × p /
(Rs). ]

Specific examples of M ² and M ³ include B, Al,
Each atom such as Si, P, As, Sb, each atom of M ⁴ , such as Ag, Cu, Na, Li, etc., and each atom of M ⁵ , each atom such as Fe, Co, Ni. . Specific examples of X ^{1 to} X ^r include, for example, a dialkylamino group such as a dimethylamino group and a diethylamino group, an alkoxy group such as a methoxy group, an ethoxy group, and n-.
Butoxy group and the like, phenoxy group as the aryloxy group, 2,6-dimethylphenoxy group, naphthyloxy group and the like, and alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group. Group, n-octyl group, 2-ethylhexyl group, etc., aryl group having 6 to 20 carbon atoms, phenyl group as alkylaryl group or arylalkyl group, p-tolyl group,
Benzyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group, 4-tertiary-
Butylphenyl group, 2,6-dimethylphenyl group, 3,
5-dimethylphenyl group, 2,4-dimethylphenyl group, 1,2-dimethylphenyl group and the like, F, Cl, Br, I as halogen, pentamethylantimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, Examples thereof include diphenylarsine group, dicyclohexylantimony group, diphenylboron group and the like. Specific examples of the substituted cyclopentadienyl group represented by R ²³ and R ²⁴ include a methylcyclopentadienyl group, a butylcyclopentadienyl group, a pentamethylcyclopentadienyl group, and the like.

In the present invention, a plurality of groups are bound to the metal.
The anion specifically includes B (C₆F_Five)_Four ^-, B
(C₆HF_Four)_Four ^-, B (C₆H₂F₃)_Four ^-, B (C₆H
₃F ₂)_Four ^-, B (C₆H_FourF)_Four ^-, B (C₆CF₃ F_Four)
_Four ^-, B (C₆F_Five)_Four ^-BF _Four ^-, PF₆ ^-, P (C₆
F_Five)₆ ^-, Al (C₆HF_Four)_Four ^-And so on. Well
Also, as the metal cation, Cp₂Fe⁺, (MeCp)
₂Fe⁺, (TBuCp)₂Fe⁺, (Me₂Cp)₂
Fe⁺, (Me₃Cp)₂Fe⁺, (Me_FourCp)₂F
e⁺, (Me_FiveCp)₂Fe⁺, Ag⁺, Na⁺, Li
⁺Other examples of chaotine include pyridinium.
N, 2,4-dinitro-N, N-diethylanilini
Um, diphenylammonium, p-nitroaniliniu
, 2,5-dichloroaniline, p-nitro-N, N-
Dimethylanilinium, quinolinium, N, N-dimethyl
Such as luanilinium, N, N-diethylanilinium, etc.
Nitrogen-containing compounds, triphenylcarbenium, tri (4
-Methylphenyl) carbenium, tri (4-methoxy)
Carbenium compounds such as phenyl) carbenium, C
H₃PH₃ ⁺, C₂H_FivePH₃ ⁺, C₃H₇PH₃ ⁺，
(CH₃)₂PH ₂ ⁺, (C₂H_Five)₂PH₂ ⁺, (C
₃H₇)₂PH₂ ⁺, (CH₃)₃PH⁺, (C
₂H_Five)₃PH⁺, (C₃H₇)₃PH⁺, (CF₃)
₃PH⁺, (CH ₃)_FourP⁺, (C₂H_Five)_FourP⁺，
(C₃H₇)_FourP⁺Such as alkylphosphonium
On, and C₆H_FivePH₃ ⁺, (C₆H_Five)₂P
H₂ ⁺, (C₆H_Five)₃PH⁺, (C₆H_Five)_FourP⁺，
(C₂H_Five)₂(C₆H_Five) PH⁺, (CH ₃) (C₆
H_Five) PH₂ ⁺, (CH₃)₂(C₆H_Five) PH⁺，
(C₂H_Five)₂(C₆H_Five)₂P⁺Such as arylfo
Sphonium ion etc. are mentioned.

Among the compounds of the general formulas (X) and (XI),
Specifically, the following can be used particularly preferably. Examples of the compound of the general formula (X) include triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetrakis (pentafluorophenyl) borate, and tetrakis (pentafluorophenyl). ) Tri (n-butyl) ammonium borate, triethylammonium hexafluoroarsenate, pyridinium tetrakis (pentafluorophenyl) borate, pyrrolinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, Methyldiphenylammonium tetrakis (pentafluorophenyl) borate and the like can be mentioned. On the other hand, examples of the compound of the general formula (XI) include ferrocenium tetraphenylborate, dimethylferrocenium tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
Decamethylferrocenium borate, Tetrakis (pentafluorophenyl) borate acetylferrocenium, Tetrakis (pentafluorophenyl) formylferrocenium borate, Tetrakis (pentafluorophenyl) cyanocyanoferrocenium borate, Silver tetraphenylborate, Tetrakis ( Pentafluorophenyl) silver borate, tetraphenyl trityl borate, tetrakis (pentafluorophenyl)
Examples thereof include trityl borate, silver hexafluoroarsenate, silver hexafluoroantimonate, and silver tetrafluoroborate.

Further, the transition metal compound of the component (a)
Examples of compounds that can react to form ionic complexes
For example, B (C₆F_Five)₃, B (C₆HF_Four)₃, B (C₆
H₂F₃)₃, B (C₆H₃F₂)₃, B (C₆H
_FourF)₃, B (C₆CF₃F_Four) ₃, BF₃, PF_Five，
P (C₆F_Five)_Five, Al (C₆HF_Four)₃Also used
be able to. In the present invention, the transition of the above component (a)
Capable of reacting with a metal transfer compound to form an ionic complex
One compound may be used, or two or more compounds may be used in combination.
May be.

On the other hand, as the oxygen-containing compound as the component (b), a compound represented by the general formula (I)

[0026]

[Chemical 8]

Having a chain structure represented by:
Or general formula (II)

[0028]

[Chemical 9]

Those having a cyclic structure represented by the following are used.

In the above general formulas (I) and (II), R
^{1 to} R ⁷ each represent an alkyl group having 1 to 8 carbon atoms,
Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. R ^{1 to} R ⁵ may be the same or different from each other, and R ⁶ and R ⁷ may be the same or different from each other. Y ^{1 to} Y ⁵ each represent an element of Group 13 of the periodic table,
Specific examples thereof include B, Al, Ga, In and Tl. Of these, B and Al are preferable. Y ^{1 to} Y ³
They may be the same or different, and Y ⁴ and Y ⁵
They may be the same or different. Also, a to d
Are numbers 0 to 50, respectively, but (a + b) and (c
+ D) is 1 or more. As a to d, the range of 1 to 20 is preferable, and the range of 1 to 5 is particularly preferable.

As the oxygen-containing compound represented by the general formula (I) or (II), a reaction product of an organoaluminum compound and water can be preferably used. The reaction product of this organoaluminum compound and water is mainly represented by the general formula (XII)

[0032]

[Chemical 10]

(Wherein t represents the degree of polymerization, is a number from 2 to 50, and R ²⁶ represents an alkyl group having 1 to 8 carbon atoms), or a chain alkylaluminoxane represented by the general formula ( XI
II)

[0034]

[Chemical 11]

A cyclic alkylaluminoxane having a repeating unit represented by the formula (R ²⁶ in the formula is the same as above). Of such alkyl aluminoxanes,
Those in which R ²⁶ is a methyl group, that is, methylaluminoxane are preferred. The organoaluminum compound to be reacted with water is usually a trialkylaluminum represented by the general formula (XIV) AlR ²⁶ ₃ (XIV) (wherein R ²⁶ is the same as above), specifically, Examples thereof include trimethylaluminum, triethylaluminum, and triisobutylaluminum, and among them, trimethylaluminum is preferable. The reaction products of these trialkylaluminums and water are generally mainly composed of the chain alkylaluminoxane and cyclic alkylaluminoxane, unreacted trialkylaluminum and various condensation products, and further, molecules in which these are complicatedly associated. It contains various substances and becomes various products depending on the contact conditions of trialkylaluminum and water. The reaction method of the trialkylaluminum and water at this time is not particularly limited, and a known method can be used.

In the present invention, the oxygen-containing compound as the component (b) may be used alone or in combination of two or more. Further, as the component (B), one or more compounds of the component (a) and one or more compounds of the component (b) can be used in combination. In the polymerization catalyst of the present invention, an alkyl group-containing metal compound can be used as the component (C), if necessary, together with the components (A) and (B). Here, there are various alkyl group-containing metal compounds, for example, general formula (XV) R ²⁷ _x Al (OR ²⁸ ) _y Q _3-xy (XV) (wherein R ²⁷ and R ²⁸ each represents an alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and x is 0 <x ≦ 3, preferably 2
Or 3, most preferably 3, and y is 0 ≦ y <3, preferably 0 or 1. ), An alkyl group-containing aluminum compound represented by the general formula (XVI), R ²⁷ ₂ Mg ... (XVI) (in the formula, R ²⁷ is the same as the above), and General formula (XVI
I) R ²⁷ ₂ Zn ... (XVII) (in the formula, R ²⁷ is the same as the above), and the alkyl group-containing zinc compound and the like can be mentioned.

Of these alkyl group-containing compounds, alkyl group-containing aluminum compounds, especially trialkylaluminum and dialkylaluminum compounds are preferred. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, dimethylaluminum chloride, diethylaluminum. Dialkyl aluminum halides such as chloride, di-n-propyl aluminum chloride, diisopropyl aluminum chloride, di-n-butyl aluminum chloride, diisobutyl aluminum chloride, di-t-butyl aluminum chloride, dimethyl aluminum methoxide, dimethyl aluminum ethoxide and the like. Dialkyl aluminum alkoxide, dimethyl aluminum hydride, diethyl aluminum Hydride, such as dialkylaluminum hydride such as diisobutylaluminum hydride and the like. Furthermore, dialkyl magnesium such as dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium and diisopropyl magnesium and dialkyl zinc such as dimethyl zinc, diethyl zinc, di-n-propyl ethyl zinc and diisopropyl zinc can be mentioned.

The alkyl group-containing metal compound as the component (C) may be used alone or in combination of two or more kinds. The method for preparing the polymerization catalyst used in the present invention is not particularly limited, and various methods can be applied. For example,
In the case of preparing a catalyst composed of components (A), (B) and (C), the component (C) is added to the reaction product of the components (A) and (B) to prepare a catalyst, which is then polymerized. To contact the monomer to be polymerized, a method in which the component (B) is added to the reaction product of the component (A) and the component (C) to form a catalyst, and the monomer to be polymerized is contacted to the component, and the components (B) and (C) The component (A) is added to the reaction product with the component as a catalyst, and the monomer to be polymerized is brought into contact with the catalyst, or one component (A), (B), or (C) is added to the monomer to be polymerized. A method of contacting is used. Here, even if the component (C) is mixed with the reaction product of the component (A) and the component (B),
It may be mixed with the monomer to be polymerized or further mixed with both. Further, in the case of preparing a catalyst comprising components (A) and (B), a reaction product of the components (A) and (B) is used as a catalyst, and a monomer to be polymerized is brought into contact therewith, (A) A method of using a mixture of the component and the component (B) as a catalyst, and bringing the monomer to be polymerized into contact therewith,
For example, a method of separately adding the component (A) and the component (B) to the monomer to be polymerized and bringing them into contact with each other is used. Addition or contact of the above-mentioned components (A) and (B) and optionally (C) can be performed not only at the polymerization temperature but also at a temperature of 0 to 100 ° C. is there. The catalyst of the present invention as described above exhibits high activity in the production of a styrenic polymer having a high syndiotactic structure.

To produce a styrenic polymer by the method of the present invention, a catalyst for SPS polymerization, preferably (A) above.
A styrene-based monomer such as styrene and / or a styrene derivative in the presence of a catalyst comprising the component, the component (B) and optionally the component (C), or a styrene-based monomer. The monomer is copolymerized with the olefin and / or diene compound. In the present invention, it is necessary to use a styrene-based monomer having an indene-based compound content of 50 ppm or less.
If the content of the indene compound exceeds 50 ppm, the catalytic activity will decrease. From the viewpoint of catalytic activity, it is particularly preferable that the content of the indene compound is 30 ppm or less. The styrene-based monomer is preferably of the general formula (XVIII)

[0040]

[Chemical 12]

(In the formula, R ²⁹ represents a hydrogen atom, a halogen atom or a hydrocarbon group having 20 or less carbon atoms, and m is 1 to 3).
Indicates an integer. When m is 2 or more, each R ²⁹ may be the same or different. ) Is used. Examples of such materials include styrene, p
-Methylstyrene, m-methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethyl Alkyl styrene such as styrene and p-tert-butyl styrene; polyvinyl benzene such as p-divinylbenzene, m-divinylbenzene and trivinylbenzene; p
-Chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o
-Bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-
Examples thereof include halogenated styrene such as fluorostyrene, methoxystyrene, ethoxystyrene, alkoxystyrene such as t-butoxystyrene, or a mixture of two or more thereof. Further, the indene compound contained in the styrene-based monomer, the general formula (XIX) or (X
X)

[0042]

[Chemical 13]

(In the formula, R ³⁰ is a hydrogen atom or has 2 carbon atoms.
It represents a hydrocarbon group of 0 or less, and n represents an integer of 1 to 3.
When n is 2 or more, each R ³⁰ may be the same or different. ), For example, 1H-indene, 2H-indene, 4-methyl-1H-indene, 5-methyl-1H-indene, 6-methyl-1H-.
Indene, 7-methyl-1H-indene, 4-methyl-
2H-indene, 5-methyl-2H-indene, 6-methyl-2H-indene, 7-methyl-2H-indene,
4,5-dimethyl-1H-indene, 4,6-dimethyl-1H-indene, 4,7-dimethyl-1H-indene, 5,6-dimethyl-1H-indene, 5,7-dimethyl-1H-indene, 6,7-dimethyl-1H-indene, 4,5-dimethyl-2H-indene, 4,6-dimethyl-2H-indene, 4,7-dimethyl-2H-indene, 5,6-dimethyl-2H-indene, 5,7-
Dimethyl-2H-indene, 6,7-dimethyl-2H-
Indene, 4-ethyl-1H-indene, 5-ethyl-
1H-indene, 6-ethyl-1H-indene, 7-ethyl-1H-indene, 4-ethyl-2H-indene,
Examples include 5-ethyl-2H-indene, 6-ethyl-2H-indene, 7-ethyl-2H-indene, and the like, or a mixture of two or more kinds thereof.

The styrenic monomer used in the present invention is purified by distillation or chromatography of the styrenic monomer containing the above-mentioned indene compound, or the styrene monomer production raw material is highly purified (for example, 2- Methyl-
The content of the indene compound is adjusted to 50 ppm or less by a method such as removal of 1-ethylbenzene). On the other hand, examples of the olefin copolymerized with the styrene-based monomer include ethylene; propylene; butene-1; pentene-1; hexene-1; heptene-1; octene-1; nonene-1; decene-1; -Phenylbutene-1; 6-phenylhexene-1; 3-methylbutene-1; 4-methylpentene-1; 3-methylpentene-1; 3-methylhexene-1; 4-methylhexene-
1; 5-methylhexene-1; 3,3-dimethylpentene-1; 3,4-dimethylpentene-1; 4,4-dimethylpentene-1; α-olefins such as vinylcyclohexane, hexafluoropropene; tetrafluoro Ethylene; 2-fluoropropene; fluoroethylene;
1,1-difluoroethylene; 3-fluoropropene;
Trifluoroethylene; halogen-substituted α-olefins such as 3,4-dichlorobutene-1; cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1- Cyclic olefins such as methylnorbornene; 7-methylnorbornene; 5,5,6-trimethylnorbornene; 5-phenylnorbornene; 5-benzylnorbornene and the like. Examples of the diene compound include butadiene; isoprene; chain diene compounds such as 1,6-hexadiene; norbornadiene; 5-ethylidenenorbornene; 5-vinylnorbornene; dicyclopentadiene and other cyclic diene compounds. These olefins and diene compounds may be used alone or in combination of two or more.

In the present invention, the components (A) and (B) and the component (C) which is optionally used may be added to the monomer separately, but the solvent may be added before mixing the catalyst component with the monomer. (For example, aromatic hydrocarbons such as toluene and ethylbenzene or aliphatic hydrocarbons such as hexane and heptane) may be premixed with the components (A) and (B) and optionally the component (C). Alternatively, all or part of the component (C) may be added to the monomer. Polymerization of the styrene-based monomer may be carried out in bulk, or may be carried out in an aliphatic hydrocarbon such as pentane, hexane, heptane, an alicyclic hydrocarbon such as cyclohexane, or an aromatic hydrocarbon solvent such as benzene, toluene, xylene. The polymerization temperature is not particularly limited, but is generally 0 to 120.
C, preferably 20 to 90C. Further, the polymerization reaction may be carried out in the presence of hydrogen in order to control the molecular weight of the obtained styrene polymer.

The styrene polymer thus obtained is one in which the polymerization chain portion of the styrene monomer has a high syndiotactic structure. Here, the syndiotactic structure having a highly polymerized chain portion of the styrene-based monomer is a syndiotactic structure having a high stereochemical structure, that is, a side chain with respect to the main chain formed from carbon-carbon bonds. It means that a phenyl group or a substituted phenyl group has a steric structure in which the phenyl group and the substituted phenyl group are alternately located in the opposite directions, and the tacticity thereof is a nuclear magnetic resonance method using an isotope carbon ( ¹³ C-NM
R method). ^The tacticity measured by the ¹³ C-NMR method can be indicated by the abundance ratio of a plurality of continuous structural units, for example, diad in the case of 2, triad in the case of 3 and pentad in the case of 5. However, the "styrene-based polymer having a highly syndiotactic structure" referred to in the present invention is usually 75% or more, preferably 85% or more in racemic dyad, or 30% or more in racemic pentad, preferably 50%
Polystyrene, poly (alkyl styrene), poly (halogenated styrene), poly (alkoxy styrene), poly (vinyl benzoate) having the above syndiotacticity, and mixtures thereof, or copolymers containing these as the main components Means union. Here, as the poly (alkylstyrene), there are poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiarybutylstyrene), etc., and as the poly (halogenated styrene), Examples include poly (chlorostyrene), poly (bromostyrene), and poly (fluorostyrene). Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Of these, particularly preferable styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tertiarybutylstyrene), poly (p-chlorostyrene), poly ( Examples thereof include m-chlorostyrene), poly (p-fluorostyrene), and a copolymer of styrene and p-methylstyrene.

The styrenic polymer produced by the method of the present invention generally has a weight average molecular weight of 10,000 to 3,000,000.
, Preferably 100,000 to 1,500,000, number average molecular weight of 5,0
It is from 00 to 1,500,000, preferably from 50,000 to 1,000,000, and has high syndioctacity as described above. The styrene-based polymer having a highly syndiotactic structure has a melting point of 160 to 310 ° C., and is significantly superior in heat resistance to a conventional styrene-based polymer having an atactic structure.

[0048]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. Example 1 0.4 ml of a solution of 39.3 ml of toluene (2 mol / l) in triisobutylaluminum and 0.4 mg of dimethylanilinium tetrakis (pentafluorophenyl) borate (DMAB) were placed in a 50 ml container which had been dried and purged with nitrogen. Add, 250 mmol /
A premixed catalyst was prepared by sequentially adding 0.32 ml of pentamethylcyclopentadienyl titanium trimethoxide of 1 liter. The amount of indene in styrene was measured by gas chromatography. 10 ml of styrene having an indene content of 5 ppm was dried, put in a 30 ml container purged with nitrogen, heated to 70 ° C., 250 μl of the above premixed catalyst was added, and polymerization was carried out for 1 hour. After the reaction was completed, the product was dried to obtain 4.11 g of a polymer. This polymer is 1mm thick
The slice was cut into the following pieces and subjected to Soxhlet extraction with methyl ethyl ketone for 6 hours. As a result, the SPS yield was 4.01 g.
(Extraction residual rate 97.6%, SPS activity 162 kg /
gTi).

Comparative Example 1 Polymerization was conducted in the same manner as in Example 1 except that the styrene used had an indene content of 60 ppm.
Obtained 1.56 g. This polymer was cut into thin pieces having a thickness of 1 mm or less, and subjected to Soxhlet extraction with methyl ethyl ketone for 6 hours. As a result, the SPS yield was 1.51 g (extraction residual rate 96.8%, SPS activity 63 kg / g Ti).

Examples 2 to 7 and Comparative Examples 2 to 7 Pentamethylcyclopentadienyl titanium trimethoxide, dimethylanilinium tetrakis (pentafluorophenyl) borate (DMAB), triisobutylaluminum and the indene content of the styrene used. Polymerization was carried out in the same manner as in Example 1 except that each of those was set as shown in Table 1 to obtain a polymer. This polymer was examined for SPS activity and specificity in the same manner as in Example 1.
The results are shown in Table 1 together with the results of Example 1 and Comparative Example 1.

[0051]

[Table 1]

[0052]

[Table 2]

DMAB: Dimethylanilinium tetrakis (pentafluorophenyl) borate FCB: Ferrocenium tetrakis (pentafluorophenyl) borate PAB: Pyridinium tetrakis (pentafluorophenyl) borate PBAB: Parabromophenyldimethylammonium tetrakis (pentafluorophenyl) Borate

Example 8 4.0 ml of a solution of 39.3 ml of toluene (2 mol / liter) in triisobutylaluminum and 460 mg of methylaluminoxane were placed in a 50 ml container which had been dried and purged with nitrogen, and 250 ml / liter was added. 0.32 ml of pentamethylcyclopentadienyl titanium trimethoxide was sequentially added to prepare a premixed catalyst. The amount of indene in styrene was measured by gas chromatography. Indene content is 5p
10 ml of styrene of pm was dried, put in a 30 ml container purged with nitrogen, heated to 70 ° C., 250 μl of the above premixed catalyst was added, and polymerization was carried out for 1 hour. After the reaction was completed, the reaction product was dried to obtain 4.27 g of a polymer. This polymer is 1mm thick
The slice was cut into the following pieces and subjected to Soxhlet extraction with methyl ethyl ketone for 6 hours. As a result, SPS yield is 4.15g
(Extraction residual rate 97.2%, SPS activity 168 kg /
gTi).

Comparative Example 8 Polymerization was conducted in the same manner as in Example 8 except that the styrene used had an indene content of 60 ppm.
Obtained 1.58 g. This polymer was cut into thin pieces having a thickness of 1 mm or less, and subjected to Soxhlet extraction with methyl ethyl ketone for 6 hours. As a result, the SPS yield was 1.56 g (extraction residual rate 98.7%, SPS activity 63 kg / g Ti).

Example 9 39.7 ml of toluene and methylaluminoxane 460 were placed in a 50 ml container which had been dried and purged with nitrogen.
250 mg / liter of pentamethylcyclopentadienyl titanium trimethoxide (0.32 ml) was sequentially added to prepare a premixed catalyst. The amount of indene in styrene was measured by gas chromatography. 10 ml of styrene having an indene content of 5 ppm was placed in a container of 30 ml which was dried and purged with nitrogen, and heated to 70 ° C. to prepare the above premixed catalyst 25.
0 microliter was added and polymerization was performed for 1 hour. After the reaction was completed, the reaction product was dried to obtain 1.39 g of a polymer.
This polymer was cut into thin pieces having a thickness of 1 mm or less, and subjected to Soxhlet extraction with methyl ethyl ketone for 6 hours. As a result, the SPS yield was 1.35 g (extraction residual ratio 97.1).
%, SPS activity 55 kg / g Ti).

Comparative Example 9 Polymerization was carried out in the same manner as in Example 9 except that the styrene used had an indene content of 60 ppm.
0.53 g was obtained. This polymer was cut into thin pieces having a thickness of 1 mm or less, and subjected to Soxhlet extraction with methyl ethyl ketone for 6 hours. As a result, the SPS yield was 0.51 g (extraction residual rate 96.0%, SPS activity 21 kg / g Ti).

[0058]

INDUSTRIAL APPLICABILITY As described in detail above, by using a styrene-based monomer having an indene compound content of 50 ppm or less as in the production method of the present invention, it is possible to obtain a catalyst activity without deterioration. It is possible to reduce the amount of residual metal in the styrene polymer. Further, the manufacturing method of the present invention can reduce the manufacturing cost and simplify the process.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 4/00-4/82 C08F 12/00-12/36 C08F 112/00-112/36 C08F 212 / 00-212/36

Claims (6)

(57) [Claims] 1. A styrene monomer having an indene compound content of 30 ppm or less is used when the styrene monomer is brought into contact with a syndiotactic polystyrene polymerization catalyst for polymerization. A method for producing a styrene polymer. 2. A syndiotactic polystyrene polymerization catalyst, (A) the following general formula (III) or general formula _{^{(IV) MR 8 e R 9}} f R 10 g R 11 4- (e + f + g) · .. ( III ) MR ⁸ _h R ⁹ _i R ¹⁰ _{3- (h + i)} ( IV ) [In the formula, M is titanium, zirconium, or hafnium.
And R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each a hydrogen atom,
Alkyl group, alkoxy group, aryl group, alkyl ant
Group, arylalkyl group, acyloxy group, cyclo
Pentadienyl group, substituted cyclopentadienyl group, indene
Denenyl group, substituted indenyl group, fluorenyl group, substituted phenyl group
Fluorenyl group, alkylthio group, arylthio group, amine
Amino group (-NR _2), chelate ligand or a halogen atom
Indicates. e, f and g each represent an integer of 0 to 4,
h and i each represent an integer of 0 to 3. Also, R ⁸ ~
Any two of R ¹¹ are CH ₂ or Si (CH ₃ ) ₂ etc.
It also includes cross-linked complexes. ] The transition metal compound represented by , and (B) (a) said (A)
A compound capable of forming an ionic complex by reacting with the transition metal compound of the component or (b) the general formula (I): (In the formula, R ^{1 to} R ⁵ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, Y ^{1 to} Y ³ represent aluminum , and they may be the same. They may be different, and a and b are each 0 to
Although the number of 50 is shown, a + b is 1 or more. ) And / or general formula (II) (In the formula, R ⁶ and R ⁷ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, Y ⁴ and Y ⁵ represent aluminum , and they may be the same. They may be different, and c and d are each 0
The number of ˜50 is shown, and c + d is 1 or more. ] An oxygen-containing compound represented by
A method for producing the styrene polymer described. 3. A syndiotactic polystyrene polymerization catalyst, (A) the following general formula (III) or general formula _{^{(IV) MR 8 e R 9}} f R 10 g R 11 4- (e + f + g) · .. ( III ) MR ⁸ _h R ⁹ _i R ¹⁰ _{3- (h + i)} ( IV ) [In the formula, M is titanium, zirconium, or hafnium.
And R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each a hydrogen atom,
Alkyl group, alkoxy group, aryl group, alkyl ant
Group, arylalkyl group, acyloxy group, cyclo
Pentadienyl group, substituted cyclopentadienyl group, indene
Denenyl group, substituted indenyl group, fluorenyl group, substituted phenyl group
Fluorenyl group, alkylthio group, arylthio group, amine
Amino group (-NR _2), chelate ligand or a halogen atom
Indicates. e, f and g each represent an integer of 0 to 4,
h and i each represent an integer of 0 to 3. Also, R ⁸ ~
Any two of R ¹¹ are CH ₂ or Si (CH ₃ ) ₂ etc.
It also includes cross-linked complexes. ] The transition metal compound represented by , and (B) (a) said (A)
A compound capable of forming an ionic complex by reacting with the transition metal compound of the component or (b) the general formula (I): (In the formula, R ^{1 to} R ⁵ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, Y ^{1 to} Y ³ represent aluminum , and they may be the same. They may be different, and a and b are each 0 to
Although the number of 50 is shown, a + b is 1 or more. ) And / or general formula (II) (In the formula, R ⁶ and R ⁷ each represent an alkyl group having 1 to 8 carbon atoms, which may be the same or different, Y ⁴ and Y ⁵ represent aluminum , and they may be the same. They may be different, and c and d are each 0
The number of ˜50 is shown, and c + d is 1 or more. ) An oxygen-containing compound represented by the formula ( C), and (C) the following general formula ( X
_{^{V) R 27 x Al (OR}} 28) y Q 3-xy ··· (XV) ( wherein, R ²⁷ and R ²⁸ having 1 to 8 carbon atoms each, preferably
Or 1 to 4 alkyl group, Q is a hydrogen atom or halo.
Indicates a gen atom. Further, x is 0 <x ≦ 3, preferably 2
Or 3, most preferably 3, y is 0 ≦ y <3, preferably
It is preferably 0 or 1. ) Alkyl group-containing aluminum compound represented by the general formula
An alkyl group-containing magnesium compound represented by ( XVI ) R ²⁷ ₂ Mg ( XVI ) ( wherein R ²⁷ is the same as the above) , and
The general formula _{^{(XVII) R 27 2 Zn ···}} (XVII) ( wherein, R ²⁷ is as defined above.) Al <br/> Kill group containing selected from alkyl groups containing zinc compound represented by the The method for producing a styrene-based polymer according to claim 1, which comprises a metal compound. 4. The method for producing a styrene polymer according to claim 2, wherein the transition metal compound as the component (A) is a titanium compound having at least one ligand having a conjugated π electron. 5. The oxygen-containing compound as the component (B) or (b) is a reaction product of an organoaluminum compound and water.
Or the method for producing a styrene-based polymer described in 3. 6. The method for producing a styrene polymer according to claim 3, wherein the alkyl group-containing metal compound as the component (C) is an alkyl group-containing aluminum compound.