JP2000143715A - Production of aromatic vinyl compound.alpha-olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic vinyl compound.alpha-olefin copolymer in high productivity by copolymerizing an aromatic vinyl compound with an α-olefin in the presence of a catalyst comprising a specific transition metal imine compound and a specific compound. SOLUTION: This method for producing an aromatic vinyl compound.alpha-olefin copolymer comprises copolymerizing (A) an aromatic vinyl compound with (B) an α-olefin in the presence of (C) a catalyst comprising (i) a transition metal imine compound of the formula [M is a transition metal in the groups 8-11 in the periodic table; R1-R4 are each H, a halogen, a (halogenated) hydrocarbon, an oxygen-containing group or the like; R5, R6 are each a halogen, a (halogenated) hydrocarbon, an oxygen- containing group or the like, provided that R1 and R5, R2 and R6, R1 and R3, R2 and R4, and R3 and R4 may each be bound to each other to form a ring; (n) is the valency of M; X is H, a halogen, a 1-10C (halogenated) hydrocarbon or the like; Y is an atom in the groups 15-16 in the periodic table; Y is an atom in the groups 15-16 in the periodic table] and (ii) one or more kinds of compounds selected from organic metal compounds, organic aluminumoxy compounds and compounds each capable of reacting with the component i to form an ion pair.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aromatic vinyl compound, α
More specifically, the present invention relates to a method for producing an olefin copolymer, and more particularly, to copolymerize an aromatic vinyl compound and an α-olefin by copolymerizing an aromatic vinyl compound and an α-olefin in the presence of a catalyst containing a specific transition metal imine compound. The present invention relates to a method for producing a polymer.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Olefin polymerization catalysts include:
So-called Kaminsky catalysts are well known. This catalyst is characterized by a very high polymerization activity and a polymer having a narrow molecular weight distribution.

As a transition metal compound used for such a Kaminsky catalyst, for example, bis (cyclopentadienyl) zirconium dichloride (JP-A-58-19)
309) and ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride (Japanese Unexamined Patent Publication No.
No. 130314). It is also known that when the transition metal compound used for the polymerization is different, the olefin polymerization activity and the properties of the obtained polyolefin are greatly different.

Further, as a new catalyst for olefin polymerization, for example, Japanese Patent Application Laid-Open No. 8-245713 has proposed an olefin polymerization catalyst comprising a titanium amide compound having a titanium-nitrogen bond and aluminoxane.

Also, Organometallics 1996, 15,562-569
Describes an organometallic complex of Group 4 of the periodic table having a bis (borylamide) ligand represented by [Mes2BNCH2CH2NBMes2] -2, and describes that this complex exhibits a slight ethylene polymerization activity.

[0006] Polyolefins are generally used in various fields such as for molded articles because of their excellent mechanical properties. However, in recent years, the demand for physical properties of polyolefins has been diversified, and polyolefins having various properties have been developed. Is desired. It is also desired to improve productivity.
Under these circumstances, it has been desired to develop a method for producing a polyolefin having high polymerization activity and excellent properties, particularly an aromatic vinyl compound / α-olefin copolymer, using a catalyst containing a transition metal amide compound. I have.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has been made in view of the above-mentioned problems, and is intended to provide an aromatic vinyl compound / α-olefin copolymer with high productivity using a catalyst containing a transition metal amide compound. It is an object of the present invention to provide a production method capable of obtaining the following.

[0008]

[0009]

SUMMARY OF THE INVENTION The aromatic vinyl compound according to the present invention, α-
The method for producing the olefin copolymer includes (A) a transition metal imine compound represented by the following general formula (I) and (B) (B-
1) at least one compound selected from an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound which forms an ion pair by reacting with the transition metal amide compound (A). It is characterized in that an aromatic vinyl compound and an α-olefin are copolymerized in the presence of a catalyst.

[0010]

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In the formula, M represents a transition metal atom belonging to Groups 8 to 11 of the periodic table, and R 1 to R 4 may be the same or different from each other and are a hydrogen atom, a halogen atom, a halogenated hydrocarbon group, a hydrocarbon, Group, heterocyclic compound residue, oxygen-containing group,
Nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups,
A silicon-containing group, a germanium-containing group, a tin-containing group, or the like; R5 and R6 may be the same or different from each other, and may be a halogen atom, a halogenated hydrocarbon group, a hydrocarbon group, a heterocyclic compound residue, Containing group, nitrogen containing group,
Shows such as boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups,
R1 and R5 may be connected to each other to form a ring, R2 and R6 may be connected to each other to form a ring, or R1 and R3 may be connected to each other to form a ring. R2 and R4 may be linked to each other to form a ring, R3 and R4 may be linked to each other to form a ring, n is a valence of M, and X is hydrogen Atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
And represents a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, and the like. When n is 2 or more, a plurality of groups represented by X may be the same or different. Y represents an atom of Group 15 or 16 of the periodic table.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing an aromatic vinyl compound / α-olefin copolymer according to the present invention will be specifically described.

In the production method of the present invention, when copolymerizing an aromatic vinyl compound and an α-olefin, (A) a transition metal imine compound represented by the following general formula (I) and (B) At least one compound selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) a compound which reacts with the transition metal imine compound (A) to form an ion pair Are used.

First, each component forming the olefin polymerization catalyst of the present invention will be described. (A) Transition metal imine compound The transition metal imine compound (A) used in the present invention is a compound represented by the following general formula (I).

[0015]

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In the formula, M represents a transition metal atom belonging to groups 8 to 11 of the periodic table, and may be a transition metal atom belonging to groups 8 and 9 of the periodic table such as iron, ruthenium, osnium, cobalt, rhodium, and iridium. Preferred are iron and cobalt.

R 1 to R 4 may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group,
Nitrogen-containing groups, boron-containing groups, sulfur-containing groups, phosphorus-containing groups,
It indicates a silicon-containing group, a germanium-containing group, a tin-containing group, or the like.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of the hydrocarbon group include those having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. A chain or branched alkyl group; an aryl group having 6 to 20 carbon atoms such as phenyl, naphthyl and anthryl; and a substituent such as the alkyl group having 1 to 20 carbon atoms in these aryl groups is 1 to
5 substituted aryl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; It is not limited to these.

Examples of the halogenated hydrocarbon group include, but are not limited to, the above-mentioned hydrocarbon groups substituted with halogen.

The heterocyclic compound includes a nitrogen-containing heterocyclic ring,
Examples include an oxygen-containing heterocycle and a sulfur-containing heterocycle, but are not limited thereto. Examples of the oxygen-containing group include an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and an acid anhydride, but are not limited thereto. Absent. Examples of the nitrogen-containing group include an amino group, imino group, amide group, imide group, hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, and ammonium Examples thereof include, but are not limited to, salts. Examples of the boron-containing group include a borandiyl group, a borantriyl group, and a diboranyl group, but are not limited thereto. Examples of the sulfur-containing group include a mercapto group, a thioester group, a dithioester group, a thioalkoxy group, a thioaryloxy group, a thioacyl group, a thioether group, a thiocyanate ester group, an isocyanate ester group, a sulfone ester group, a sulfonamide group, and a thioamide group. Examples include, but are not limited to, a carboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, a sulfenyl group, and the like. Examples of the phosphorus-containing group include, but are not limited to, a phosphide group, a phosphoryl group, a thiophosphoryl group, and a phosphato group. Examples of the silicon-containing group include, but are not limited to, a hydrocarbon-substituted silyl group, a silyl ether group of a hydrocarbon-substituted silyl, a silicon-substituted alkyl group, and a silicon-substituted aryl group. Examples of the germanium-containing group include a hydrocarbon-substituted germanium group, a germanium ether group of a hydrocarbon-substituted germane, a germanium-substituted alkyl group, a germanium-substituted aryl group, and the like.
It is not limited to this. As a tin-containing group,
Examples include, but are not limited to, hydrocarbon-substituted stannyl groups, stannyl ether groups of hydrocarbon-substituted tin, tin-substituted alkyl groups, and tin-substituted aryl groups.

R1 and R5, R2 and R6, R1 and R3,
R2 and R4, and R3 and R4 may be connected to each other to form an aromatic ring, an aliphatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom, a sulfur atom, or an oxygen atom, and these rings are Further, it may have a substituent.

N is a number satisfying the valence of M, and specifically 1 to 8, preferably 1 to 5, more preferably 1 to 3.
Is an integer.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group; When n is 2 or more, a plurality of groups represented by X may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and an aryl group. More specifically, methyl, ethyl, propyl, butyl, and hexyl Alkyl groups such as octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
And aryl groups such as propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; and an arylalkoxy group such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing group include a substituent in which oxygen of the above-mentioned oxygen-containing group is substituted by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, and p-toluene sulfonate. Sulfonate groups such as catenate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p -Sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include silyls substituted with monohydrocarbons such as methylsilyl and phenylsilyl; silyls substituted with dihydrocarbons such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl and triphenylsilyl. Trialkyl-substituted silyls such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon such as trimethylsilylphenyl And a substituted aryl group.

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferred.

Y represents an atom of Group 15 or 16 of the periodic table, and specifically, a nitrogen atom, a phosphorus atom, an arsenic atom, an antimony atom, and an oxygen atom. Examples thereof include a sulfur atom, a selenium atom, and a tellurium atom, preferably a nitrogen atom, an oxygen atom or a phosphorus atom, and more preferably a nitrogen atom.

In the present invention, among the imine compounds represented by the formula (I), the transition metal imine compound represented by the general formula (I) is a transition metal imine compound represented by the following general formula (Ia) Is more preferable.

[0032]

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In the formula, M represents a transition metal atom belonging to groups 8 to 11 of the periodic table, and may be a transition metal atom belonging to groups 8 and 9 of the periodic table such as iron, ruthenium, osnium, cobalt, rhodium and iridium. Preferred are iron and cobalt.

R7 to R10 may be the same or different from each other and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, or a hydrocarbon-substituted siloxy group. Group, alkoxy group,
Thioalkoxy group, aryloxy group, thioaryloxy group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, It represents a sulfonyl group, a mercapto group or a hydroxy group. As the halogen atom, fluorine, chlorine,
Bromine and iodine.

Specific examples of the hydrocarbon group include those having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. Chain or branched alkane; linear or branched alkene having 2 to 20 carbon atoms such as vinyl, allyl and isopropenyl; linear or branched alkyne having 2 to 20 carbon atoms such as propargyl; A cyclic hydrocarbon having 3 to 20 carbon atoms such as propanyl, cyclobutanyl, cyclopentanyl, cyclohexyl and adamantyl; an aryl group having 6 to 20 carbon atoms such as phenyl, naphthyl, cyclopentadienyl and indenyl; In addition, the above-mentioned alkyl group having 1 to 20 carbon atoms and 6 to 2 carbon atoms.
It may be a substituted aryl group in which 1 to 5 substituents such as 0 aryl group, alkoxy group, aryloxy group and the like are substituted.

Examples of the halogenated hydrocarbon group include groups in which the above hydrocarbon group is substituted with halogen.

Examples of the heterocyclic compounds include nitrogen-containing aromatic rings such as pyridine, pyrimidine and quinoline, oxygen-containing aromatic rings such as furan and pyran, and sulfur-containing aromatic rings such as thiophene. It may have a group.

Specific examples of the hydrocarbon-substituted silyl group include:
Examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl and the like.

Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Specific examples of the thioalkoxy group include thiomethyl,
Thioethyl and the like. Specifically as the aryloxy group, phenoxy, 2,6-dimethylphenoxy, 2,4,6-
Trimethylphenoxy and the like. Specific examples of the thioaryloxy group include thiophenyl, methylthiophenyl, and thionaphthyl.

Specific examples of the acyl group include a formyl group,
Acyl group, benzoyl group, p-chlorobenzoyl group, p-
And a methoxybenzoyl group. Specific examples of the ester group include acetyloxy, benzoyloxy,
Examples include methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like. Specific examples of the thioester group include thioacetyl, thiobenzoyl,
Thiomethoxycarbonyl, thiophenoxycarbonyl,
And the like.

Specific examples of the amide group include acetamido, N-methylacetamido, N-methylbenzamide and the like. Specific examples of the imide group include acetimide and benzimide. Specific examples of the amino group include dimethylamino, ethylmethylamino, diphenylamino and the like. Specific examples of the imino group include methylimino, ethylimino, propylimino,
Butylimino, phenylimino and the like can be mentioned.

Specific examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Specific examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

R11 may be the same or different from each other, and may be a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, Alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, sulfonyl group, Shows a mercapto group or a hydroxy group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Specific examples of the hydrocarbon group include the aforementioned R7 to
It represents the same group as R10. More specifically, a linear or branched alkane having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, etc. Linear or branched alkene having 2 to 20 carbon atoms such as vinyl, allyl, isopropenyl; linear or branched alkyne having 2 to 20 carbon atoms such as propargyl; cyclopropanyl, cyclobutanyl, cycloalkyl; Cyclic hydrocarbons having 3 to 20 carbon atoms such as pentanyl, cyclohexyl and adamantyl; aryl groups having 6 to 20 carbon atoms such as phenyl, naphthyl, cyclopentadienyl and indenyl groups; Alkyl group having 1 to 20 atoms, 6 to 2 carbon atoms
It may be a substituted aryl group in which 1 to 5 substituents such as 0 aryl group, alkoxy group, aryloxy group and the like are substituted.

Specific examples of the halogenated hydrocarbon group include the same groups as those described above for R7 to R10. More specifically, a group in which the hydrocarbon group is substituted with a halogen is exemplified.

Specific examples of the heterocyclic compound include the same groups as those described above for R7 to R10. More specifically, there are nitrogen-containing aromatic rings such as pyridine, pyrimidine, and quinoline, oxygen-containing aromatic rings such as furan and pyran, and sulfur-containing aromatic rings such as thiophene. You may.

Specific examples of the hydrocarbon-substituted silyl group include:
The same groups as those described above for R7 to R10 are shown. More specifically, examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl and the like.

Specific examples of the hydrocarbon-substituted siloxy group include the same groups as those described above for R7 to R10. More specifically, trimethylsiloxy and the like can be mentioned.

Specific examples of the alkoxy group include the aforementioned R7
And the same groups as R10. More specifically, methoxy,
Ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like.
Specific examples of the thioalkoxy group include the same groups as those described above for R7 to R10. More specifically, thiomethyl, thioethyl and the like can be mentioned. Specific examples of the aryloxy group include the same groups as those described above for R7 to R10. More specifically, phenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like can be mentioned. Specific examples of the thioaryloxy group include the same groups as those described above for R7 to R10. More specifically, thiophenyl, methylthiophenyl, thionaphthyl and the like can be mentioned.

Specific examples of the acyl group include the aforementioned R7 to R1
It represents the same group as 0. More specifically, a formyl group, an acyl group, a benzoyl group, a p-chlorobenzoyl group, a p-methoxybenzoyl group and the like can be mentioned. Specific examples of the ester group include the same groups as those described above for R7 to R10. More specifically, acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like can be mentioned. Specific examples of the thioester group include the same groups as those described above for R7 to R10. More specifically, thioacetyl, thiobenzoyl, thiomethoxycarbonyl, thiophenoxycarbonyl and the like can be mentioned.

Specific examples of the amide group include the aforementioned R7 to R1.
It represents the same group as 0. More specifically, acetamide, N
-Methylacetamide, N-methylbenzamide and the like. Specific examples of the imide group include the aforementioned R7 to R10
And the same groups as above. More specifically, examples include acetimide and benzimide. Specific examples of the amino group include the same groups as those described above for R7 to R10. More specifically, dimethylamino, ethylmethylamino, diphenylamino and the like can be mentioned. Specifically as the imino group,
The same groups as those described above for R7 to R10 are shown. More specifically, methylimino, ethylimino, propylimino, butylimino, phenylimino and the like can be mentioned.

Specific examples of the sulfone ester group include the same groups as those described above for R7 to R10. More specifically, methyl sulfonate, ethyl sulfonate, phenyl sulfonate and the like can be mentioned. Specific examples of the sulfonamide group include the same groups as those described above for R7 to R10. More specifically, phenylsulfonamide, N-methylsulfonamide, N-methyl-p-toluenesulfonamide and the like can be mentioned.

R7 and R9, R8 and R10, R8 and R11, R
Each of 9 and R10 may be linked to each other to form an aromatic ring, an aliphatic ring, or a hydrocarbon ring containing a heteroatom such as a nitrogen atom, a sulfur atom, or an oxygen atom. May be provided.

R12 to R16 may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, or a hydrocarbon-substituted siloxy group. Group, alkoxy group,
Alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group,
It represents a sulfonyl group, a mercapto group or a hydroxy group. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Specific examples of the hydrocarbon group include those having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. Chain or branched alkane; linear or branched alkene having 2 to 20 carbon atoms such as vinyl, allyl and isopropenyl; linear or branched alkyne having 2 to 20 carbon atoms such as propargyl; A cyclic hydrocarbon having 3 to 20 carbon atoms such as propanyl, cyclobutanyl, cyclopentanyl, cyclohexyl and adamantyl; an aryl group having 6 to 20 carbon atoms such as phenyl, naphthyl, cyclopentadienyl and indenyl; In addition, the above-mentioned alkyl group having 1 to 20 carbon atoms and 6 to 2 carbon atoms.
It may be a substituted aryl group in which 1 to 5 substituents such as 0 aryl group, alkoxy group, aryloxy group and the like are substituted.

Examples of the halogenated hydrocarbon group include groups in which the above hydrocarbon group is substituted with halogen.

Examples of the heterocyclic compound include nitrogen-containing aromatic rings such as pyridine, pyrimidine and quinoline, oxygen-containing aromatic rings such as furan and pyran, and sulfur-containing aromatic rings such as thiophene. It may have a group.

Specific examples of the hydrocarbon-substituted silyl group include:
Examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl and the like.

Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Specific examples of the thioalkoxy group include thiomethyl,
Thioethyl and the like. Specifically as the aryloxy group, phenoxy, 2,6-dimethylphenoxy, 2,4,6-
Trimethylphenoxy and the like. Specific examples of the thioaryloxy group include thiophenyl, methylthiophenyl, and thionaphthyl.

Specific examples of the acyl group include a formyl group,
Acyl group, benzoyl group, p-chlorobenzoyl group, p-
And a methoxybenzoyl group. Specific examples of the ester group include acetyloxy, benzoyloxy,
Examples include methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like. Specific examples of the thioester group include thioacetyl, thiobenzoyl,
Thiomethoxycarbonyl, thiophenoxycarbonyl,
And the like.

Specific examples of the amide group include acetamido, N-methylacetamido, N-methylbenzamide and the like. Specific examples of the imide group include acetimide and benzimide. Specific examples of the amino group include dimethylamino, ethylmethylamino, diphenylamino and the like. Specific examples of the imino group include methylimino, ethylimino, propylimino,
Butylimino, phenylimino and the like can be mentioned.

Specific examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Specific examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

At least one of R12 to R16 is a group other than a hydrogen atom, and two or more of the groups represented by R12 to R16 may be linked to each other to form a ring; Preferably, adjacent groups are connected to each other to form an aliphatic ring,
An aromatic ring or a hydrocarbon ring containing a hetero atom such as a nitrogen atom may be formed, and these rings may further have a substituent.

N is a number satisfying the valence of M, and specifically 1 to 8, preferably 1 to 5, more preferably 1 to 3.
Is an integer.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group; When n is 2 or more, a plurality of groups represented by X may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and an aryl group. More specifically, methyl, ethyl, propyl, butyl, and hexyl Alkyl groups such as octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
And aryl groups such as propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; and an arylalkoxy group such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing group include a substituent in which oxygen of the above-mentioned oxygen-containing group is substituted by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, and p-toluene sulfonate. Sulfonate groups such as catenate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p -Sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include silyls substituted with monohydrocarbons such as methylsilyl and phenylsilyl; silyls substituted with dihydrocarbons such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl and triphenylsilyl. Trialkyl-substituted silyls such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon such as trimethylsilylphenyl And a substituted aryl group.

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferred.

Y represents an atom of Group 15 of the periodic table, and specifically includes a nitrogen atom, a phosphorus atom, an arsenic atom, an antimony atom and the like, preferably a nitrogen atom or a phosphorus atom, and more preferably a nitrogen atom. .

In the present invention, among the imine compounds represented by the formula (I), the transition metal imine compound represented by the general formula (I) is a transition metal imine compound represented by the following general formula (Ib) More preferably, it is a compound.

[0075]

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In the formula, M represents a transition metal atom belonging to groups 8 to 11 of the periodic table, and may be a transition metal atom belonging to groups 8 and 9 of the periodic table such as iron, ruthenium, osnium, cobalt, rhodium, and iridium. Preferred are iron and cobalt.

R17 to R20 may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, or a hydrocarbon-substituted siloxy group. Group, alkoxy group,
Thioalkoxy group, aryloxy group, thioaryloxy group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, It represents a sulfonyl group, a mercapto group or a hydroxy group. As the halogen atom, fluorine, chlorine,
Bromine and iodine.

Specific examples of the hydrocarbon group include those having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. Chain or branched alkane; linear or branched alkene having 2 to 20 carbon atoms such as vinyl, allyl and isopropenyl; linear or branched alkyne having 2 to 20 carbon atoms such as propargyl; A cyclic hydrocarbon having 3 to 20 carbon atoms such as propanyl, cyclobutanyl, cyclopentanyl, cyclohexyl and adamantyl; an aryl group having 6 to 20 carbon atoms such as phenyl, naphthyl, cyclopentadienyl and indenyl; In addition, the above-mentioned alkyl group having 1 to 20 carbon atoms and 6 to 2 carbon atoms.
It may be a substituted aryl group in which 1 to 5 substituents such as 0 aryl group, alkoxy group, aryloxy group and the like are substituted.

Examples of the halogenated hydrocarbon group include a group in which the above hydrocarbon group is substituted with halogen.

Examples of the heterocyclic compound include nitrogen-containing aromatic rings such as pyridine, pyrimidine and quinoline, oxygen-containing aromatic rings such as furan and pyran, and sulfur-containing aromatic rings such as thiophene. It may have a group.

Specific examples of the hydrocarbon-substituted silyl group include:
Examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl and the like.

Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Specific examples of the thioalkoxy group include thiomethyl,
Thioethyl and the like. Specifically as the aryloxy group, phenoxy, 2,6-dimethylphenoxy, 2,4,6-
Trimethylphenoxy and the like. Specific examples of the thioaryloxy group include thiophenyl, methylthiophenyl, and thionaphthyl.

Specific examples of the acyl group include a formyl group,
Acyl group, benzoyl group, p-chlorobenzoyl group, p-
And a methoxybenzoyl group. Specific examples of the ester group include acetyloxy, benzoyloxy,
Examples include methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like. Specific examples of the thioester group include thioacetyl, thiobenzoyl,
Thiomethoxycarbonyl, thiophenoxycarbonyl,
And the like.

Specific examples of the amide group include acetamido, N-methylacetamido, N-methylbenzamide and the like. Specific examples of the imide group include acetimide and benzimide. Specific examples of the amino group include dimethylamino, ethylmethylamino, diphenylamino and the like. Specific examples of the imino group include methylimino, ethylimino, propylimino,
Butylimino, phenylimino and the like can be mentioned.

Specific examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Specific examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

R17 and R19, R18 and R20, R19 and R20
May be connected to each other to form an aromatic ring, an aliphatic ring or a hydrocarbon ring containing a hetero atom such as a nitrogen atom, a sulfur atom, or an oxygen atom, and these rings further have a substituent. You may.

R21 to R30 may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, or a hydrocarbon-substituted siloxy group. Group, alkoxy group,
Thioalkoxy group, aryloxy group, thioaryloxy group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group, It represents a sulfonyl group, a mercapto group or a hydroxy group. As the halogen atom, fluorine, chlorine,
Bromine and iodine.

Specific examples of the hydrocarbon group include those having 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. Chain or branched alkane; linear or branched alkene having 2 to 20 carbon atoms such as vinyl, allyl and isopropenyl; linear or branched alkyne having 2 to 20 carbon atoms such as propargyl; A cyclic hydrocarbon having 3 to 20 carbon atoms such as propanyl, cyclobutanyl, cyclopentanyl, cyclohexyl and adamantyl; an aryl group having 6 to 20 carbon atoms such as phenyl, naphthyl, cyclopentadienyl and indenyl; In addition, the above-mentioned alkyl group having 1 to 20 carbon atoms and 6 to 2 carbon atoms.
It may be a substituted aryl group in which 1 to 5 substituents such as 0 aryl group, alkoxy group, aryloxy group and the like are substituted.

Examples of the halogenated hydrocarbon group include groups in which the above hydrocarbon group is substituted with halogen.

Examples of the heterocyclic compound include nitrogen-containing aromatic rings such as pyridine, pyrimidine and quinoline, oxygen-containing aromatic rings such as furan and pyran, and sulfur-containing aromatic rings such as thiophene. It may have a group.

Specific examples of the hydrocarbon-substituted silyl group include:
Examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl and the like.

Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like. Specific examples of the thioalkoxy group include thiomethyl,
Thioethyl and the like. Specifically as the aryloxy group, phenoxy, 2,6-dimethylphenoxy, 2,4,6-
Trimethylphenoxy and the like. Specific examples of the thioaryloxy group include thiophenyl, methylthiophenyl, and thionaphthyl.

Specific examples of the acyl group include a formyl group,
Acyl group, benzoyl group, p-chlorobenzoyl group, p-
And a methoxybenzoyl group. Specific examples of the ester group include acetyloxy, benzoyloxy,
Examples include methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like. Specific examples of the thioester group include thioacetyl, thiobenzoyl,
Thiomethoxycarbonyl, thiophenoxycarbonyl,
And the like.

Specific examples of the amide group include acetamido, N-methylacetamido, N-methylbenzamide and the like. Specific examples of the imide group include acetimide and benzimide. Specific examples of the amino group include dimethylamino, ethylmethylamino, diphenylamino and the like. Specific examples of the imino group include methylimino, ethylimino, propylimino,
Butylimino, phenylimino and the like can be mentioned.

Specific examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Specific examples of the sulfonamide group include phenylsulfonamide, N-methylsulfonamide, and N-methyl-p-toluenesulfonamide.

At least one of R21 to R25 is a group other than a hydrogen atom, and at least one of R26 to R30
One is a group other than a hydrogen atom, and two or more of the groups represented by R21 to R25 may be connected to each other to form a ring; and among the groups represented by R26 to R30, Two or more groups may be connected to each other to form a ring, and preferably, adjacent groups are connected to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. These rings may be formed, and these rings may further have a substituent.

N is a number satisfying the valence of M, and specifically 1 to 8, preferably 1 to 5, more preferably 1 to 3.
Is an integer.

X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, or a silicon-containing group; When n is 2 or more, a plurality of groups represented by X may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an alkenyl group, an arylalkyl group, and an aryl group. More specifically, methyl, ethyl, propyl, butyl, and hexyl Alkyl groups such as octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, norbornyl and adamantyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; Phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
And aryl groups such as propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl.

Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which the aforementioned hydrocarbon group having 1 to 20 carbon atoms is substituted with halogen. Examples of the oxygen-containing group include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; an aryloxy group such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy; and an arylalkoxy group such as phenylmethoxy and phenylethoxy.

Examples of the sulfur-containing group include a substituent in which the oxygen of the oxygen-containing group is substituted by sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. Sulfonate groups such as catenate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p -Sulfinate groups such as toluenesulfinate, trimethylbenzenesulfinate and pentafluorobenzenesulfinate.

Examples of the silicon-containing group include silyls substituted with monohydrocarbons such as methylsilyl and phenylsilyl; silyls substituted with dihydrocarbons such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl and triphenylsilyl. Trialkyl-substituted silyls such as dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl and trinaphthylsilyl; silyl ethers of hydrocarbon-substituted silyls such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; silicon such as trimethylsilylphenyl And a substituted aryl group.

Of these, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group is preferred.

Y represents an atom belonging to Group 15 of the periodic table, and specifically includes a nitrogen atom, a phosphorus atom, an arsenic atom, an antimony atom, etc., preferably a nitrogen atom or a phosphorus atom, and more preferably a nitrogen atom. .

The following formulas (I), (Ia) and (I-
Specific examples of the transition metal imine compound represented by b) are shown below, but it should not be construed that the invention is limited thereto.

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Embedded image In the above examples, Me represents a methyl group, Et represents an ethyl group, nPr represents an n-propyl group, and iPr represents i-
Represents a propyl group, sBu represents a sec-butyl group, tB
u represents a tert-butyl group, nOct represents an n-octyl group,
Ph represents a phenyl group.

In the present invention, a transition metal imine compound in which iron is replaced with cobalt in the above compounds can be used.

These compounds may be used alone or
Two or more kinds may be used in combination. (B-1) Organometallic compound As the (B-1) organometallic compound used in the present invention, specifically, the first and second groups of the periodic table represented by the following formulas (B-1a) to (B-1c) And organometallic compounds belonging to groups 12 and 13 are used.

[0148] (B-1a) In the formula _{R a m Al (OR b)} n Hp Xq ( wherein, R _a and R _b may be the same or different from each other, the number of carbon atoms 1 to 15, preferably Represents a hydrocarbon group of 1 to 4, X represents a halogen atom, and m represents 0 <m
≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q <
The number is 3, and m + n + p + q = 3. The organoaluminum compound represented by).

[0149] (B-1b) In the general formula M ¹ AlR _a 4 (wherein, M ¹ is shown a Li, Na or K, R _a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a Group 1 metal and aluminum represented by the formula:

(B-1c) Formula R _a R _b M ² (wherein R _a and R _b may be the same or different and each have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A hydrocarbon group, and M ² represents Mg, Zn or Cd.) A dialkyl compound of a Group 2 or 12 metal.

Examples of the organoaluminum compound belonging to the above (B-1a) include compounds represented by the following formulas (II) to (V). In the general formula _{R a m Al (OR b)} 3-m (II) ( the formulas, Ra and Rb may be the same or different from each other, from 1 to 15 carbon atoms, preferably 1 to 4 hydrocarbon An organoaluminum compound represented by the general formula _: Ram AlX3-m (III) (where Ra is a number of carbon atoms) 1 to 15, preferably 1 to
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organoaluminum compound represented by the general formula _: Ram AlH3-m (IV) (where Ra has 1 to 15 carbon atoms, preferably 1 to 5 carbon atoms)
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{R a m Al (OR b)} n Xq (V) ( wherein, R _a and R _b may be the same or different, 1 to carbon atoms 15, preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3,
And m + n + q = 3. The organoaluminum compound represented by).

More specifically, as the aluminum compound belonging to (B-1a), a compound represented by the formula (II) is converted to trimethylaluminum, triethylaluminum, tri-n-
Butyl aluminum, tripropyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tri n-alkyl aluminum such as tridecyl aluminum; triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, bird
2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-
Methylpentyl aluminum, tri-4-methylpentyl aluminum, tri-2-methylhexyl aluminum, tri
Tribranched alkyl aluminum such as 3-methylhexyl aluminum and tri 2-ethylhexyl aluminum;
Tricycloalkyl aluminums such as tricyclohexyl aluminum, tricyclooctyl aluminum;
Triaryl aluminum such as triphenyl aluminum and tolyl aluminum; (i-C ₄ H ₉ ) x Aly
(C ₅ H ₁₀ ) z (where x, y, and z are positive numbers, z
≧ 2x. Alkenyl aluminum such as isoprenyl aluminum; alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide; dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide and the like Dialkylaluminum alkoxide; alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; Ra2.5 Al (O
Rb) Alkyl aluminum partially alkoxylated having an average composition represented by 0.5 or the like; diethyl aluminum phenoxide, diethyl aluminum (2,6-dialkyl
-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), Isobutyl aluminum bis (2,6-di-t
Alkyl aluminum aryloxides such as -butyl-4-methylphenoxide); dialkylaluminums such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride as compounds represented by formula (III) Halides; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; ethyl aluminum dichloride, propyl aluminum dichloride;
Partially aluminum halides such as alkylaluminum dihalides such as butylaluminum dibromide; dialkylaluminum hydrides such as compounds represented by formula (IV); diethylaluminum hydride, dibutylaluminum hydride;
Dialkylaluminum hydrides such as diisobutylaluminum hydride; other partially hydrogenated alkylaluminums such as ethylaluminum dihydride and alkylaluminum dihydride such as propylaluminum dihydride; as a compound represented by the formula (V), ethyl Partially alkoxylated and halogenated alkylaluminums such as aluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide and the like can be mentioned.

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

The compounds belonging to the above (B-1b) include:
iAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified.

Still further, (B-1) the organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, and propylmagnesium bromide. , Propyl magnesium chloride, butyl magnesium bromide, butyl magnesium chloride, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like can also be used.

Further, a compound which forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyllithium, or a combination of aluminum halide and alkylmagnesium can also be used.

Of these, organoaluminum compounds are preferred. The above-mentioned (B-1) organometallic compounds are used alone or in combination of two or more.

(B-2) Organoaluminum oxy compound The (B-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. May be a benzene-insoluble organic aluminum oxy compound.

A conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used in preparing the aluminoxane include those described in the above (B-1a).
And the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Solvents used for the preparation of aluminoxanes include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Among them, hydrocarbon solvents such as chlorinated products and brominated products are exemplified. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organoaluminum oxy compound used in the present invention, the Al component soluble in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Yes, insoluble or poorly soluble in benzene.

(B-3) A compound that forms an ion pair by reacting with a transition metal amide compound The compound (B-3) used in the present invention that forms an ion pair by reacting (hereinafter referred to as “ionized ionic compound”) ") Means a compound having an ability to form an ion pair with the transition metal amide compound (A). Examples of the "ionized ionic compound" include JP-A-1-501950, JP-A-1-502036, and JP-A-3-179.
No. 005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, etc., Lewis acids, ionic compounds, borane compounds and carborane compounds, etc. Can be mentioned.

Specifically, as the Lewis acid, BR3
(R is a phenyl group or a fluorine which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group.), For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) ) Boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include a compound represented by the following general formula (VI).

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In the formula, R 31 includes H +, carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R32 to R35 may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilyl; Nium cation, N,
N, N-dialkylanilinium cations such as N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation No.

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

As R14, a carbonium cation, an ammonium cation and the like are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation and an N, N-diethylanilinium cation are particularly preferable.

As the ionic compound, a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt,
Dialkylammonium salts, triarylphosphonium salts and the like can also be mentioned.

Specific examples of the trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron and trimethylammonium tetra (p -Tolyl) boron, trimethylammoniumtetra (o-tolyl) boron, tri (n-butyl) ammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (o, p-dimethylphenyl) boron,
Tri (n-butyl) ammonium tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditri Fluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkyl ammonium salt include, for example, di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
N, N-diethylanilinium pentaphenylcyclopentadienyl complex, and a boron compound represented by the following formula (VII) or (VIII) can also be mentioned.

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

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Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and bis [tri (n-butyl) ammonium ] Undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-
Salts of anions such as butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate Borate) salts of metal borane anions such as nickelate (III).

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Metal carborane anions such as (carboundecaborate) nickelate (IV).

The above (B-3) ionized ionic compounds are used alone or in combination of two or more. In the method for producing an aromatic vinyl compound / α-olefin copolymer according to the present invention, the transition metal amide compounds (A), (B-1), and (B-1)
2) A particulate carrier (C) as described below can be used, if necessary, together with at least one compound (B) selected from an organic aluminum oxy compound and (B-3) an ionized ionic compound.

(C) Particulate Carrier The (C) particulate carrier used as required in the present invention is an inorganic or organic compound having a particle size of 10 to 3
A granular or particulate solid of 00 μm, preferably 20-200 μm, is used. Of these, a porous oxide is preferable as the inorganic compound, specifically, SiO ₂ ,
Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , C
aO-, ZnO, BaO, etc. ThO _2, or a mixture containing them, for example, SiO ₂ -MgO, SiO ₂ -Al ₂
O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO _2-
Examples thereof include Cr ₂ O ₃ and SiO ₂ —TiO ₂ —MgO. Among them, those containing at least one component selected from the group consisting of SiO ₂ and Al ₂ O ₃ as a main component are preferable.

The above inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO
₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (N
O ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O, and other carbonates, sulfates, nitrates, and oxide components may be contained.

The properties of the fine particle carrier (C) vary depending on the kind and the production method, but the carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² / g.
Preferably, it is in the range of 100 to 700 m ² / g, and the pore volume is in the range of 0.3 to 2.5 cm ³ / g. The carrier is optionally at 100 to 1000 ° C,
Preferably, it is used by firing at 150 to 700 ° C.

Further, examples of the particulate carrier (C) that can be used in the present invention include a granular or particulate solid of an organic compound having a particle size in the range of 10 to 300 μm. As these organic compounds, ethylene, propylene, 1-butene, 4-methyl-1-pentene and other (co) polymers mainly composed of α-olefins having 2 to 14 carbon atoms or vinylcyclohexane, A polymer or copolymer formed mainly with styrene can be exemplified.

In the present invention, α-
Specifically as olefin, ethylene, propylene,
1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1- Hexene, 4,4-dimethyl
-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-
Hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-
3 or 2 carbon atoms such as octadecene and 1-eicosene
0, preferably 4 to 8 α-olefins. Particularly preferred are 1-butene, 1-hexene, 4
-Methyl-1-pentene and 1-octene. These α-olefins can be used alone or in combination of two or more.

In the present invention, specific examples of the aromatic pinyl compound supplied to the polymerization reaction include styrene; 0-methylstyrene, m-methylstyrene, P-methylstyrene,
Mono- or polyalkylstyrenes such as 0, P-dimethylstyrene, 0-ethylstyrene, m-ethylstyrene, P-ethylstyrene; methoxystyrene, ethoxystyrene, vinylbenzoic acid, methylvinylbenzoate, vinylpentyl acetate, hydroxy Functional group-containing styrene derivatives such as styrene, 0-chlorostyrene, P-chlorostyrene, and divinylbenzene; 3-phenylpropylene, 4-phenylbutene, α-methylstyrene, and the like. Preferred are styrene and α-methylstyrene. These aromatic vinyl compounds can be used alone or
It can be used in combination of more than one kind.

The content of the aromatic vinyl compound in the copolymer of the α-olefin and the aromatic vinyl compound can be selected from a wide range, but is preferably from 0.5 to 10 mol%. α-
Specific combinations of olefins and aromatic vinyl compounds include ethylene / styrene copolymer, ethylene / propylene / styrene copolymer, ethylene / α-styrene copolymer, ethylene / styrene / α-styrene copolymer, etc. Can be mentioned.

In the method for producing an aromatic vinyl compound / α-olefin copolymer according to the present invention, an aromatic vinyl compound and an α-olefin are copolymerized in the presence of the above-mentioned catalyst. FIG. 1 shows a process for preparing an olefin polymerization catalyst used in the present invention.

In the polymerization, the method of use and the order of addition of each catalyst component are arbitrarily selected, and the following methods are exemplified. (1) Component (A) and at least one component (B) selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) an ionized ionic compound Simply referred to as "component (B)") in any order. (2) A method in which the catalyst in which the component (A) and the component (B) are brought into contact in advance is added to the polymerization reactor. (3) A method in which the catalyst component in which the component (A) and the component (B) are brought into contact in advance and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different. (4) A method in which the catalyst component in which the component (A) is supported on the fine-particle carrier (C) and the component (B) are added to the polymerization vessel in an arbitrary order. (5) A method in which a catalyst in which the component (A) and the component (B) are supported on the fine particle carrier (C) is added to a polymerization reactor. (6) A method in which the catalyst component in which the component (A) and the component (B) are supported on the fine particle carrier (C) and the component (B) are added to the polymerization vessel in an arbitrary order. In this case, the components (B) may be the same or different. (7) A method in which the catalyst component in which the component (B) is supported on the fine particle carrier (C) and the component (A) are added to the polymerization reactor in an arbitrary order. (8) A method in which the catalyst component in which the component (B) is supported on the particulate carrier (C), the component (A), and the component (B) are added to the polymerization reactor in an arbitrary order. In this case, the components (B) may be the same or different.

The solid catalyst component in which the component (A) and the component (B) are supported on the fine particle carrier (C) may be preliminarily polymerized with an olefin. In the present invention, the copolymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method, but preferably a liquid phase polymerization method is employed.

Specific examples of the inert hydrocarbon medium used in the copolymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof; The α-olefin used and / or ethylene itself can be used as a solvent.

Of these inert hydrocarbon media, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred. It is also preferable to use the α-olefin used for polymerization as a solvent.

The concentration of the component (A) in the reaction system in the liquid phase polymerization is usually 10-8 to 10-2 mol / l, preferably 10-7 to 10-3 mol / l. Can be

The component (B-1) is composed of the component (B-1) and the component (A)
The molar ratio with the transition metal atom (M) in [(B-1) / M] is
Usually 0.01 to 5000, preferably 0.05 to 200
It is used in such an amount that it becomes zero. Component (B-2) is replaced by component (B
-2) has a molar ratio [(B-2) / M] of the transition metal atom (M) in the component (A) of usually 10 to 5
000, preferably 20 to 2,000. Component (B-3) has a molar ratio [(B-3) / M] of component (B-3) to transition metal atom (M) in component (A) of usually 1 to 10, preferably 1 to 10. It is used in such an amount as to be 1 to 5.

The polymerization temperature using such a polymerization catalyst is usually -50 to 200 ° C, preferably 0 to 170 ° C.
It is in the range of ° C. The polymerization pressure is usually from normal pressure to 100 kg /
cm2, preferably normal pressure to 50 kg / cm2, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the obtained polymer can be adjusted by adding hydrogen to the polymerization system or changing the polymerization temperature.

The aromatic vinyl compound obtained by the present invention, α
-The olefin copolymer comprises a structural unit (Ui) derived from an α-olefin (i) and an aromatic vinyl compound (i
molar ratio with the structural unit (Uii) derived from (i) [(Ui
) :( Uii)] is from 99: 1 to 1:99, preferably from 98: 2 to 2:98. Further, the intrinsic viscosity [η] of the aromatic vinyl compound / α-olefin copolymer obtained in the present invention measured in a decalin solvent at 135 ° C. is desirably 0.01 dl / g or more.

[0202]

The aromatic vinyl compound according to the present invention, α-
According to the method for producing an olefin copolymer, an aromatic vinyl compound / α-olefin copolymer can be obtained with high polymerization activity. In addition, the obtained aromatic vinyl compound α
-The olefin copolymer has a narrow molecular weight distribution.

[0203]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[0204]

Example 1 20 ml of heptane and then 20 parts of styrene were placed in a 100 ml glass autoclave, which had been sufficiently replaced with nitrogen.
ml and the liquid and gas phases were saturated with ethylene. In addition, methylaluminoxane is converted to aluminum atom
1.25 mmol, and then 0.0005 mmol of a transition metal imine compound (A-1) represented by the following formula (a) was added to initiate polymerization. After polymerization was carried out at 25 ° C. for 1 hour under an atmosphere of ethylene gas at normal pressure, a small amount of methanol was added to terminate the polymerization. The polymerization reaction solution was added to a large excess of a methanol-hydrochloric acid solution to precipitate a polymer. The obtained polymer is
The mixture was extracted with chloroform at room temperature, and the chloroform-soluble portion was extracted with acetone at room temperature. As a result, 0.5 g of an ethylene / styrene copolymer having a styrene content of 1 mol% was obtained as an acetone-insoluble portion.

[0205]

Embedded image

[0206]

Example 2 In the polymerization of Example 1, a titanium compound (A
-1) instead of a titanium compound (A) represented by the following formula (b):
Copolymerization of ethylene and styrene was carried out in the same manner as in Example 1 except that 5 mmol of -2) was used. Extraction of the produced polymer was performed in the same manner as in Example 1. As a result, an ethylene / styrene copolymer having a styrene content of 0.5 mol% 1.1
g was obtained.

[0207]

Embedded image

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a process for preparing an olefin polymerization catalyst used in the present invention.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Terunori Fujita 1-2-1, Waki, Waki-machi, Kuga-gun, Yamaguchi F-term Mitsui Chemicals, Inc. 4J028 AA01A AB00A AC45A AC46A AC47A BA00A BA01B BB00A BB01B BC05B BC08B BC09B BC12B BC15B BC24B BC25B BC27B BC29B CA25C CA26C CA27C CA28C CA29C EA01 EB02 EB04 EB05 EB06 EB07 EB08 EB09 EB10 EB21 EC02 GB01 4J100 AA02P AA03P AA04P AA07B AABABQAAB ABQAAB18

Claims (3)

[Claims] (A) a transition metal imine compound represented by the following general formula (I), (B) an organometallic compound (B-1),
2) an aromatic vinyl oxy compound and (B-3) a catalyst comprising at least one compound selected from a compound which reacts with the transition metal amide compound (A) to form an ion pair; A process for producing an aromatic vinyl compound / α-olefin copolymer, characterized by copolymerizing the compound with an α-olefin; (Wherein, M represents a transition metal atom belonging to Groups 8 to 11 of the periodic table,
R1 to R4 may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a halogenated hydrocarbon group, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group,
Shows such as boron-containing groups, sulfur-containing groups, phosphorus-containing groups, silicon-containing groups, germanium-containing groups or tin-containing groups,
R5 and R6 may be the same or different from each other, and include a halogen atom, a halogenated hydrocarbon group, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, A phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group;
5, R2 and R6, R1 and R3, R2 and R4 and R3 and R4 are
N may represent a valence of M, X may represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. In the case where n is 2 or more, a plurality of groups represented by X may be the same or different from each other. Y represents an atom belonging to Group 15 or 16 of the periodic table. ) 2. The transition metal imine compound represented by the following general formula (I-
The method according to claim 1, which is a compound represented by a). Embedded image (Wherein M, X, Y and n are the same as those described above;
To R10 may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, or an alkoxy group. A thioalkoxy group, an aryloxy group, a thioaryloxy group, an acyl group,
Represents a group selected from an ester group, a thioester group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group, a carboxyl group, a sulfonyl group, a mercapto group and a hydroxy group. ,. R7 and R9, R8 and R10, R8 and R11, R9 and R1
0 may be linked to each other to form an aromatic ring, an aliphatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom, a sulfur atom, or an oxygen atom, and these rings further have a substituent. R12 to R16 may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, or a hydrocarbon. Substituted siloxy group, alkoxy group,
Alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group,
It represents a group selected from a sulfonyl group, a mercapto group and a hydroxy group. ) 3. The transition metal imine compound represented by the following general formula (I-
The method according to claim 1, which is a compound represented by b). Embedded image (Wherein M, X, Y and n are the same as those described above;
To R20 may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, or an alkoxy group. A thioalkoxy group, an aryloxy group, a thioaryloxy group, an acyl group,
Represents a group selected from an ester group, a thioester group, an amide group, an imide group, an amino group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group, a carboxyl group, a sulfonyl group, a mercapto group and a hydroxy group. , R17 and R19, R18 and R20, and R19 and R20 may be linked to each other to form an aromatic ring, an aliphatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom, a sulfur atom, or an oxygen atom. These rings may further have a substituent, and R21 to R30 may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a heterocyclic compound. Residue, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, alkoxy group, thioalkoxy group, aryloxy group, thioaryloxy group, acyl group, ester group, thioether Stele group, amide group, imide group, amino group, imino group, sulfone ester group, sulfonamide group, cyano group, nitro group, carboxyl group,
It represents a group selected from a sulfonyl group, a mercapto group and a hydroxy group. )