JPH08301917A - Method for preparing homogeneous polymerization catalyst - Google Patents

Abstract

PURPOSE: To prepare a homogeneous polymerization catalyst having a high catalytic activity by mixing a transition metal compound with a compound which can react with the metal compound to form an ionic complex or a specified oxygenous compound and aging the obtained mixture. CONSTITUTION: A method for preparing a homogeneous polymerization catalyst comprising a transition metal compound (A) and oxygenous compounds (B) represented by formula I (wherein R<1> to R<5> are each 1-8C alkyl; Y<1> to Y<3> are each a group III element; and a and b are each 0-50, provided that a+b>=1) and/or formula II (wherein R<6> and R<7> are each 1-8C alkyl; Y<4> and Y<5> are each a group III element; and c and d are each 0-50, provided that c+d>=1), which comprises mixing catalyst components A and B together and aging the obtained mixture. According to this method, the catalyst can be brought into the state of the highest possible catalytic activity within a short time. The catalyst prepared by this method is used as a polymerization catalyst for, e.g. an aromatic vinyl compound or an α-olefin and, especially when used in the polymerization of an aromatic vinyl compound, it can give a syndiotactic styrene polymer at good efficiency.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in the method for preparing a homogeneous catalyst for polymerization. More specifically, the polymerization is carried out by mixing each catalyst component and then aging it under appropriate conditions so that the catalyst activity is as high as possible. The present invention relates to a method for preparing a homogeneous catalyst for use.

[0002]

2. Description of the Related Art In recent years, homogeneous catalysts such as metallocene catalysts have high catalytic activity and excellent copolymerizability between olefins, and give polymers having a narrow molecular weight distribution to polymerize α-olefins and styrenes. It is attracting attention as a catalyst. It is also known that when a styrene is polymerized using this catalyst, a styrene polymer having a high syndiotactic structure can be obtained. By the way, in the previous research, since it was carried out only on a laboratory scale, after the homogeneous catalyst was prepared, it was immediately subjected to the polymerization step, and the relationship between the expression of the activity and the improvement thereof by mixing the catalyst components. Was not considered at all.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for preparing a homogeneous catalyst for polymerization, which can make the catalyst activity as high as possible after mixing the catalyst components under such circumstances. It is what

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that the catalyst activity is shortened by mixing each catalyst component and then aging it under appropriate conditions. It has been found that it can reach the highest level in time. The present invention has been completed based on such findings. That is, the present invention, after mixing each catalyst component,
It is intended to provide a method for preparing a homogeneous catalyst for polymerization, which is characterized by aging. Incidentally, the term "aging" in the present invention means an operation of mixing the respective catalyst components, bringing them into contact with each other, and then completing the reaction. By appropriately selecting this aging condition, the prepared homogeneous catalyst It is possible to reach the highest activity in a short time.

The homogeneous catalyst prepared by the method of the present invention is used for polymerization. Examples of the monomer polymerized by using this catalyst include aromatic vinyl compounds and α-olefins. Here, as the aromatic vinyl compound, for example, styrene, p-methylstyrene, m
-Methylstyrene, o-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, p-ethylstyrene, m-ethylstyrene, p-tertiary Alkyl styrenes such as tributyl styrene; polyvinyl benzenes such as p-divinylbenzene, m-divinylbenzene, trivinylbenzene; p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene , Halogenated styrenes such as o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, and alkoxystyrenes such as methoxystyrene, ethoxystyrene, and t-butoxystyrene. Is mentioned.

Examples of α-olefins include ethylene; propylene; butene-1; pentene-1; hexene-1; heptene-1; octene-1; nonene-
1; decene-1; 4-phenylbutene-1; 6-phenylhexene-1; 3-methylbutene-1; 4-methylpentene-1; 3-methylpentene-1; 3-methylhexene-1; 4-methyl Hexene-1; 5-methylhexene-1; 3,3-dimethylpentene-1; 3,4-dimethylpentene-1; 4,4-dimethylpentene-1; α-olefins such as vinylcyclohexane, hexafluoropropene; Tetrafluoroethylene; 2-Fluoropropene; Fluoroethylene; 1,1-Difluoroethylene; 3-Fluoropropene; Trifluoroethylene;
Examples thereof include halogen-substituted α-olefins such as 3,4-dichlorobutene-1. The aromatic vinyl compounds may be used alone or in combination of two or more, and the α-olefins may be used alone or in combination of two or more. Moreover, you may use combining an aromatic vinyl compound and (alpha) -olefins. Further, the aromatic vinyl compound and / or α-olefins may be used in combination with another polymerizable unsaturated compound.

Examples of other polymerizable unsaturated compounds include cyclopentene; cyclohexene; norbornene; 5-methylnorbornene; 5-ethylnorbornene; 5-propylnorbornene; 5,6-dimethylnorbornene; 1-methylnorbornene; 7-methylnorbornene; 5,5,6-trimethylnorbornene; 5-phenylnorbornene; cyclic olefins such as 5-benzylnorbornene; butadiene; isoprene; chain diene compounds such as 1,6-hexadiene; norbornadiene; 5-ethylidenenorbornene 5-vinyl norbornene; cyclic diene compounds such as dicyclopentadiene, and the like. These other polymerizable unsaturated compounds are
Each may be used alone, or two or more kinds may be used in combination. The homogeneous catalyst prepared by the method of the present invention includes (A) transition metal compounds, (B) (a) and (A)
A compound capable of forming an ionic complex by reacting with a transition metal compound as a component or (b) the general formula (I)

[0008]

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(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)

[0010]

[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. ) And an (C) alkyl group-containing metal compound optionally used. 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,
It represents an arylthio group, an amino group (—NR ₂ ), an amide group, a phosphide group, 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. Also, R ^{8 to} R ¹¹
A complex in which any two of them are crosslinked with CH ₂ or Si (CH ₃ ) ₂ is also included. 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). TiR ¹² _e R ¹³ _f R ¹⁴ _g R ¹⁵ _{4- (e + f + g)} ... (V) TiR ¹² _h R ¹³ _i R ¹⁴ _{3- (h + i)} ... (VI) [wherein , 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, an alkylaryl group, an arylalkyl. Group, aryloxy group having 6 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms, amino group having 1 to 50 carbon atoms, amide group, phosphide group, cyclopentadienyl group, substituted cyclopentadienyl group, indenyl Group, substituted indenyl group, fluorenyl group, substituted fluorenyl group, alkylthio group, arylthio group, chelating ligand or 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 6 ~ 20
Aryloxy group (specifically, phenoxy group, etc.), C1-C20 acyloxy group (specifically, acetoxy group, benzoyloxy group, butylcarbonyloxy group, heptadecylcarbonyloxy group, etc.), carbon number 1 to 50 amino groups (specifically, dimethylamino group, diethylamino group, diphenylamino group, bistrimethylsilyl group, etc.), amide groups (specifically, acetamide group, ethylamide group, diphenylamide group, methylphenylamide) Groups, etc.), phosphide groups (specifically, dimethylphosphide groups, diethylphosphide groups, diphenylphosphide groups, etc.), cyclopentadienyl groups, substituted cyclopentadienyl groups (specifically, methylcyclopentadiene groups). Enyl group, 1,2-dimethylcyclopentadienyl group, 1,2,4-to Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3
-Di (trimethylsilyl) cyclopentadienyl group, tert-butylcyclopentadienyl group, 1,3-di (tert-butyl) cyclopentadienyl group, pentamethylcyclopentadienyl group, etc.), indenyl group, Substituted indenyl group (specifically, methylindenyl group, dimethylindenyl group, tetramethylindenyl group, hexamethylindenyl group, 4,5,6,7-tetrahydroindenyl group, 4,5,6,6 7-tetrahydro-1,2,3 trimethylindenyl group, 8-methyltetrahydroindenyl group, etc.), fluorenyl group, substituted fluorenyl group (specifically, methylfluorenyl group, dimethylfluorenyl group, tetramethyl Fluorenyl group,
Octamethylfluorenyl group, octahydrofluorenyl group, 9-methyloctahydrofluorenyl 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, etc.), chelating ligand (specifically, 2,2′-thiobis (4-methyl-6-t-butylphenoxy) group, etc.) or halogen Indicates an atom (specifically chlorine, bromine, iodine, fluorine). These R ¹² ,
R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different.

Further, the titanium compound is represented by the general formula (VII) TiR ¹⁶ XYZ (VII) [wherein R ¹⁶ is cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, fluorenyl group] Group, a substituted fluorenyl group and the like (specifically the same as those described above for R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ ), X, Y and Z each independently represent a hydrogen atom or a carbon number. An alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an aryl group having 6 to 20 carbons, and 6 carbons
To an aryloxy group having 20 to 20 carbon atoms, an arylalkyl group having 6 to 20 carbon atoms, an alkyl or arylamide group having 1 to 40 carbon atoms, or a halogen atom (specifically, the above R
⁽¹² , R ¹³ , R ¹⁴ and R ¹⁵ are the same as those described above). ] There is a compound represented by. Where X, Y
And a compound in which one of Z and R ¹⁶ is crosslinked by CH ₂ , Si (CH ₃ ) ₂ or the like.

Further, as the titanium compound, a compound represented by the general formula (VII
I)

[0016]

[Chemical 7]

[In the formula, R ¹⁷ and R ¹⁸ each represent a halogen atom, an alkoxy group having 1 to 20 carbon atoms, and 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.

Examples of zirconium compounds as transition metal compounds include tetrabenzyl zirconium, zirconium tetraethoxide, zirconium tetrabutoxide, bisindenyl zirconium dichloride, triisopropoxy zirconium chloride, zirconium benzyl dichloride and tributoxy zirconium chloride. There are tetrabenzyl hafnium, hafnium tetraethoxide, hafnium tetrabutoxide, etc. in the hafnium compound, and further in the vanadium compound,
Examples include vanadyl bisacetylacetonate, vanadyltriacetylacetonate, triethoxyvanadyl, and tripropoxyvanadyl. 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, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group and a substituted fluorenyl group, respectively. Is the above R ¹² ,
It is the same as that described for R ¹³ , R ¹⁴ and R ¹⁵ . R ¹⁹ and R ²⁰ may be the same or different,
Further, R ¹⁹ and R ²⁰ are alkylidene groups having 1 to 5 carbon atoms (specifically, methine group, ethylidene group, propylidene group,
Dimethylcarbyl group, etc.) or an alkylsilylene group having 1 to 20 carbon atoms and 1 to 5 silicon atoms (specifically, a dimethylsilylene group, a diethylsilylene group, a dibenzylsilylene group, etc.) Good. on the other hand,
R ²¹ and R ²² are as described above, but more specifically, 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). Group, amyl group, isoamyl group, octyl group, 2-ethylhexyl group, etc.), C6-20
Aryl group (specifically, a phenyl group, a naphthyl group, etc.), an arylalkyl group having 7 to 20 carbon atoms (specifically, a benzyl group, etc.), an alkoxy group having 1 to 20 carbon atoms (specifically, , Methoxy group, ethoxy group, propoxy group, butoxy group, amyloxy group, hexyloxy group,
An octyloxy group, a 2-ethylhexyloxy group, etc.), an aryloxy group having 6 to 20 carbon atoms (specifically, a phenoxy group, etc.), an amino group and a carbon number of 1
~ 20 thioalkoxy groups are shown.

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 which 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 1 to 20 carbon atoms, 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 (C₆H_Five)_Four,^-BF_Four ^-, PF₆ ^-, P (C
₆F_Five)₆ ^-, Al (C₆HF_Four)_Four ^-And the like.
 Also, as the metal cation, Cp₂Fe⁺, (MeC
p)₂Fe⁺, (TBuCp)₂Fe⁺, (Me₂C
p)₂Fe⁺, (Me₃Cp)₂Fe⁺, (Me _FourC
p)₂Fe⁺, (Me_FiveCp)₂Fe⁺, Ag⁺, Na
⁺, Li⁺Etc., and other chaosin
Is pyridinium, 2,4-dinitro-N, N-diethyl
Luanilinium, diphenylammonium, p-nitro
Anilinium, 2,5-dichloroaniline, p-nitro
-N, N-dimethylanilinium, quinolinium, N,
N-dimethylanilinium, N, N-diethylanilini
Nitrogen-containing compounds such as um, triphenylcarbenium
Mum, tri (4-methylphenyl) carbenium, tri
Carbeni such as (4-methoxyphenyl) carbenium
Um compounds, CH₃PH₃ ⁺, C₂H_FivePH₃ ⁺, C₃
H₇PH₃ ⁺, (CH₃)₂PH₂ ⁺, (C₂H_Five)₂
PH₂ ⁺, (C₃H₇)₂PH₂ ⁺, (CH₃)₃PH
⁺, (C₂H_Five)₃PH⁺, (C₃H₇)₃PH⁺,
(CF₃)₃PH⁺, (CH₃)_FourP⁺, (C₂H_Five)
_FourP⁺, (C₃H₇)_FourP⁺Alkyl phosphos such as
N-ion, and C₆H_FivePH₃ ⁺, (C₆H_Five)₂
PH₂ ⁺, (C₆H _Five)₃PH⁺, (C₆H_Five)
_FourP⁺, (C₂H_Five)₂(C₆H_Five) PH⁺, (C
H₃) (C₆H_Five) PH₂ ⁺, (CH₃)₂(C
₆H_Five) PH⁺, (C₂H_Five) ₂(C₆H_Five)₂P⁺What
Which include aryl phosphonium ions
It

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, Acetylferrocenium tetrakis (pentafluorophenyl) borate, Formylferrocenium tetrakis (pentafluorophenyl) borate, Cyanoferrocenium tetrakis (pentafluorophenyl) 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)₃Such as lewis
Acids can also be used. In the present invention, the above
Ionic complex that reacts with the transition metal compound of component (a)
The compound capable of forming
You may use it together.

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

[0028]

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

[0030]

[Chemical 9]

Those having a cyclic structure represented by 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)

[0034]

[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)

[0036]

[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 Specific examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum and the like, and trimethylaluminum is preferable among them. 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 kinds. 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, etc. 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 of the component (C) may be used alone or in combination of two or more.

In the method of the present invention, homogeneous catalysts are prepared by mixing the catalyst components and then aging them. When the catalyst components are mixed and maintained at high temperature, high activity is exhibited in a short time.

This aging condition is appropriately selected depending on the type and amount ratio of each catalyst component in order to express as high a catalytic activity as possible, but the following aging temperature and aging time are usually adopted. That is, the aging temperature is 10 to 30 ° C.
Then, the aging time is selected in the range of 40 to 200 minutes and 25
At ~ 45 ° C, it is selected within a range of 15 to 50 minutes. Also,
At 40 to 60 ° C, it is selected in the range of 5 to 25 minutes and 55 to 55 minutes.
At 75 ° C the aging time is less than 10 minutes.

There are no particular restrictions on the method of mixing the catalyst components, and various techniques can be applied. For example, when preparing a homogeneous catalyst consisting of the above-mentioned components (A), (B) and (C), the components can be mixed by mixing the components (A) and (B) and contacting each other. (C)
A method of adding the components, a method of adding the components (B) to the reaction product obtained by mixing the components (A) and (C) and bringing them into contact with each other,
A method of adding the component (A) to the reaction product obtained by mixing and contacting the component (B) and the component (C), a method of simultaneously mixing the component (A), the component (B) and the component (C), etc. Is used. The mixing and aging of each catalyst component is generally carried out in an inert solvent under an atmosphere of an inert gas such as nitrogen or argon. Examples of the inert solvent include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane and octane. And so on.

The homogeneous catalyst prepared by the method of the present invention comprises:
It is particularly suitable as a catalyst for polymerization of an aromatic vinyl compound, and by homopolymerizing or copolymerizing an aromatic vinyl compound using this homogeneous catalyst, the polymerization chain portion of the aromatic vinyl compound is highly syndiotactic. A styrenic homopolymer or copolymer having a structure can be efficiently obtained.

[0045]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

EXAMPLE 1 1.2 ml of methylaluminoxane (MAO), 3.8 mmol of triisobutylaluminum, 150 μmol of pentamethylcyclopentadienyl titanium trimethoxide and Toluene is mixed at room temperature and premixed catalyst solution 5
After obtaining 0 ml, this solution was placed under a nitrogen atmosphere,
The mixture was aged at 20 ° C. for 60 minutes to prepare a homogeneous catalyst solution.
Next, in a 20 ml container that was dried and purged with nitrogen,
After adding 10 ml of styrene and 5 μmol of triisobutylaluminum and sealing the mixture, the temperature was raised to 70 ° C., 83 μl of the homogeneous catalyst solution was added, and polymerization was carried out for 1 hour. After the reaction was completed, the produced polymer was dried to obtain syndiotactic polystyrene (SPS) 3.6.
1 g was obtained. The SPS activity was 303 kg / gTi. Table 1 shows the aging conditions and the results.

Example 2 The procedure of Example 1 was repeated, except that the premixed catalyst solution was aged in a nitrogen atmosphere at 40 ° C. for 20 minutes. Table 1 shows the aging conditions and the results.

Example 3 The procedure of Example 1 was repeated, except that the premixed catalyst solution was aged in a nitrogen atmosphere at 50 ° C. for 10 minutes. Table 1 shows the aging conditions and the results.

[0049]

[Table 1]

[0050]

According to the method for preparing a homogeneous catalyst of the present invention, the catalyst activity can be made as high as possible in a short time by mixing the respective catalyst components and then aging them under appropriate conditions. The homogeneous catalyst prepared by the method of the present invention is used as a catalyst for polymerization of aromatic vinyl compounds and α-olefins, and in particular, when used in the polymerization of aromatic vinyl compounds, syndiotactic styrene polymer. Can be given efficiently.

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[Procedure amendment]

[Submission date] March 25, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction content]

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 (C₆H_Five)_Four,^-BF_Four ^-, PF₆ ^-, P (C
₆F_Five)₆ ^-, Al (C₆HF_Four)_Four ^-And the like.
 Also, as the metal cation, Cp₂Fe⁺, (MeC
p)₂Fe⁺, (TBuCp)₂Fe⁺, (Me₂C
p)₂Fe⁺, (Me₃Cp)₂Fe⁺, (Me _FourC
p)₂Fe⁺, (Me_FiveCp)₂Fe⁺, Ag⁺, Na
⁺, Li⁺And otherCationAs
Is pyridinium, 2,4-dinitro-N, N-diethyl
Luanilinium, diphenylammonium, p-nitro
Anilinium, 2,5-dichloroaniline, p-nitro
-N, N-dimethylanilinium, quinolinium, N,
N-dimethylanilinium, N, N-diethylanilini
Nitrogen-containing compounds such as um, triphenylcarbenium
Mum, tri (4-methylphenyl) carbenium, tri
Carbeni such as (4-methoxyphenyl) carbenium
Um compounds, CH₃PH₃ ⁺, C₂H_FivePH₃ ⁺, C₃
H₇PH₃ ⁺, (CH₃)₂PH₂ ⁺, (C₂H_Five)₂
PH₂ ⁺, (C₃H₇)₂PH₂ ⁺, (CH₃)₃PH
⁺, (C₂H_Five)₃PH⁺, (C₃H₇)₃PH⁺,
(CF₃)₃PH⁺, (CH₃)_FourP⁺, (C₂H_Five)
_FourP⁺, (C₃H₇)_FourP⁺Alkyl phosphos such as
N-ion, and C₆H_FivePH₃ ⁺, (C₆H_Five)₂
PH₂ ⁺, (C₆H _Five)₃PH⁺, (C₆H_Five)
_FourP⁺, (C₂H_Five)₂(C₆H_Five) PH⁺, (C
H₃) (C₆H_Five) PH₂ ⁺, (CH₃)₂(C
₆H_Five) PH⁺, (C₂H_Five) ₂(C₆H_Five)₂P⁺What
Which include aryl phosphonium ions
It

Claims (3)

[Claims] 1. A transition metal compound (A), and (B)
(A) a compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex, or (b) a compound represented by 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, and Y ^{1 to} Y ³ each represent an element of Group 13 of the periodic table,
They may be the same or different, and a and b each represent a number of 0 to 50, and 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, and they may be the same or different, and Y ⁴ and Y ⁵ each represent an element of Group 13 of the periodic table, They may be the same or different from each other, c
And d each represent a number of 0 to 50, and c + d is 1 or more. ] The homogeneous catalyst for polymerization which consists of an oxygen-containing compound represented by these, Each catalyst component is mixed, Then, it ages, The preparation method of the homogeneous catalyst for polymerization characterized by the above-mentioned. 2. A transition metal compound (A), and (B)
(A) a compound capable of reacting with the transition metal compound of the component (A) to form an ionic complex, or (b) a compound represented by 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, and Y ^{1 to} Y ³ each represent an element of Group 13 of the periodic table,
They may be the same or different, and a and b each represent a number of 0 to 50, and 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, and they may be the same or different, and Y ⁴ and Y ⁵ each represent an element of Group 13 of the periodic table, They may be the same or different from each other, c
And d each represent a number of 0 to 50, and c + d is 1 or more. ] In a homogeneous catalyst for polymerization comprising an oxygen-containing compound represented by the formula (C) and an alkyl group-containing metal compound (C), a method for preparing a homogeneous catalyst for polymerization, characterized in that each catalyst component is mixed and aged. . 3. The method for preparing a homogeneous polymerization catalyst according to claim 1, wherein the homogeneous polymerization catalyst is an aromatic vinyl compound polymerization catalyst.