JP2000313711A - Catalyst for polymerizing olefin and polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin polymerization catalyst having a high polymerization activity, sparingly producing fine powder in polymerization and useful for producing a polyolefin excellent in particle characteristics by supporting both a specific transition metal compound and an organic aluminum oxy compound with a specific organic polymer carrier. SOLUTION: This catalyst is prepared by supporting with (A) an organic polymer carrier (e.g. maleic anhydride-grafted polypropylene) containing a group having a carbonyl group of formula I (wherein Q is H, a halogen or the like) (B) a transition metal compound of formula II [wherein M is a transition metal atom belonging to group 3-11; (m) is 1-6; R1 to R6 are each H, a hydrocarbon or the like; (n) is a number meeting the valence of M; A is 0, S or the like and; X is H, a halogen or the like], e.g. a compound of formula III, preferably in an amount of 10-5 to 3×10-4 mol in terms of the transition metal atom based on 1 g of the ingredient A and (C) an organic aluminum oxy compound (e.g. methylaluminoxane) preferably in an amount of 2×10-3 to 5×10-2 mol in terms of aluminum atom based on 1 g of the ingredient A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for olefin polymerization and a method for olefin polymerization using the catalyst. More specifically, the present invention relates to a method for dispersing salicylaldimine on a carrier comprising an organic polymer having a carbonyl group. TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization in which a transition metal compound having a ligand and an organoaluminum oxy compound are supported, and a method for polymerizing olefin using the catalyst.

[0002]

BACKGROUND OF THE INVENTION In recent years, transition metal compounds (homogeneous catalysts) soluble in inert organic solvents have attracted attention as olefin polymerization catalysts, and among these, metallocene compounds are particularly famous.

An olefin polymerization method using the metallocene compound and an organic aluminum oxy compound as a co-catalyst includes a slurry polymerization method for polymerizing olefins in an inert hydrocarbon, a bulk polymerization method for polymerization in a liquefied olefin monomer, A gas phase polymerization method in which polymerization is performed in a gaseous olefin monomer may be mentioned, but in any case, an organic aluminum oxy compound or a polymer generated during the polymerization may adhere to the inner wall of the reactor and cause a decrease in heat removal ability. In some cases, lumps are formed in the reactor, which may hinder stable operation of the polyolefin production facility. Further, there is a problem that the produced polymer has a very small particle size, a low bulk density of the polymer, and significantly lowers productivity.

JP-A-60-35006, JP-A-61-1
08610, JP-A-61-296008, JP-A-6-296
3-66206 and JP-A-2-173104 disclose the above problem when an organoaluminum oxy compound is supported on an inorganic oxide such as silica gel or alumina and further contacted with a metallocene compound. It is stated that it can be solved.

[0005] However, polyolefins synthesized using a catalyst in which a metallocene compound and / or an organoaluminum oxy compound are supported on an inorganic oxide such as silica gel or alumina are relatively rare, such as silica gel or alumina used as a carrier in a product. Hard inorganic substances remain, which cause fish eyes as foreign matter in the product, lowering the value of the product and clogging the filter installed in the molding machine, melt kneading machine or granulator, A problem arises in that stable operation is difficult to achieve.

[0006] To solve this problem, Japanese Patent Laid-Open No. 9-3 is disclosed.
No. 09911, an olefin can be polymerized with high activity by using a carrier composed of an organic polymer compound having a carbonyl group instead of an inorganic carrier, and a polymer having high stereoregularity can be obtained. There is no adhesion of polymer and organic aluminum oxy compound generated inside to the inner wall of the reactor, no contamination, high bulk density of polymer, extremely low fisheye, high productivity, high quality product Can be produced.

[0007] Recently, as a new olefin polymerization catalyst, a catalyst comprising a transition metal compound having a salicylaldimine ligand and an organometallic compound is described in EP-A-874,005. It is described as exhibiting activity. However, when an olefin (co) polymer is produced using an olefin polymerization catalyst comprising this transition metal compound, an organoaluminum oxy compound and a particulate carrier, a higher polymerization activity has been desired from an industrial viewpoint. .

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and provides a catalyst for olefin polymerization which exhibits high polymerization activity, has a small amount of fine powder generated during polymerization, and has excellent particle properties. It is intended to provide. Another object of the present invention is to provide a method for polymerizing an olefin using a catalyst having such good properties.

[0009]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises:
(A) a carrier comprising an organic polymer having a carbonyl group represented by the following general formula (I): (B) a transition metal compound represented by the following general formula (II); An oxy compound is supported.

[0010]

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(Wherein Q represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group,
It represents an aryloxy group, an oxycarbonyl group, an amino group, an aminocarbonyl group, a hydrazino group or an oxyanion. )

[0012]

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(Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of 1 to 6, and R ^{1 to} R
⁶ may be the same or different from each other, and represent a hydrogen atom,
Halogen atom, hydrocarbon group, heterocyclic compound residue, oxygen-containing group, nitrogen-containing group, boron-containing group, sulfur-containing group,
A phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, two or more of which may be connected to each other to form a ring, and when m is 2 or more, R ¹ Among each other, between R ^2, between R ^3, between R ^4, between R ⁵ ,
R ⁶ may be the same or different from each other, and when m is 2 or more, at least one group among groups represented by R ^{1 to} R ⁶ belonging to one ligand; At least one of the groups represented by R ^{1 to} R ⁶ belonging to another ligand may be linked, n is a number satisfying the valency of M, and A is- O -, - S -, - N (R 7) - or -S
and R ⁷ has the same meaning as R ^{1 to} R ⁶ above, and X
Is a hydrogen atom, a halogen atom, 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, an aluminum-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and when n is 2 or more, Xs may be the same or different from each other; A plurality of groups represented by X may be bonded to each other to form a ring. The catalyst for olefin polymerization according to the present invention comprises (A) a carrier comprising an organic polymer having a carbonyl group represented by the above general formula (I) and (B) a carrier represented by the above general formula (II). A solid catalyst (component) on which a transition metal compound to be supported and (C) an organoaluminum oxy compound are supported;
And (D) an organometallic compound.

The olefin polymerization method according to the present invention is characterized in that olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst and the olefin polymerization method of the present invention will be specifically described below.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

The olefin polymerization catalyst according to the present invention comprises:
(A) A carrier comprising an organic polymer containing a carbonyl-containing group represented by the following general formula (I) (hereinafter sometimes referred to as “carbonyl-containing organic polymer carrier”):
(B) a transition metal compound represented by the following general formula (II):
(C) An organic aluminum oxy compound is supported.

First, each catalyst component forming the olefin polymerization catalyst of the present invention will be described. (A) Carbonyl-containing organic polymer carrier (A)
Is a carrier comprising an organic polymer containing a group having a carbonyl represented by the following general formula (I).

[0019]

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(Wherein Q is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group,
It represents an aryloxy group, an oxycarbonyl group, an amino group, an aminocarbonyl group, a hydrazino group or a xyanion. Although the properties of such carbonyl-containing organic polymer carriers vary depending on the type and manufacturing method, the carbonyl-containing organic polymer carriers preferably used in the present invention have a particle size of usually 10 to 300 μm, particularly 20 to 200 μm. Is preferred.

Examples of the organic polymer compound having a carbonyl group represented by the above general formula (I) include (1) an organic polymer compound obtained by (co) polymerizing a monomer having a carbonyl group. Compound (2) Organic polymer compound obtained by grafting or graft (co) polymerizing an unsaturated compound containing a carbonyl group on an organic polymer compound having no functional group (3) Compound containing a carbonyl group And an organic polymer compound obtained by modification with a precursor compound having a carbonyl group.

These will be described in detail.
The organic polymer compound obtained by (co) polymerizing the monomer having a carbonyl group of (1) is selected from monomers having a carbonyl group.
A homopolymer of two kinds of monomers, a copolymer of two or more monomers selected from monomers containing a carbonyl group, and at least one monomer selected from monomers containing a carbonyl group; And a copolymer with a monomer containing no group.

Examples of the monomer containing a group having a carbonyl group include acrylic acids such as methacrylic acid and acrylic acid; acrylic acid esters such as methyl methacrylate and methyl acrylate; and acrylamide such as methacrylamide, acrylamide and crotonamide. Vinyls such as vinyl acetate, methyl vinyl ketone, acryloyl chloride and acrylaldehyde; lactones such as β-propiolactone; lactams such as ε-caprolactam; tetramethylene diisocyanate, hexamethylene diisocyanate and octamethylene diisocyanate Isocyanates; N- such as β-benzylaspartic anhydride and 4-benzyloxazolide-2,5-dione
Carboxyamino acid anhydrides, ε-aminocaproic acid,
aminocarboxylic acids such as ω-aminoundecanoic acid; carboxylic anhydrides such as maleic anhydride, itaconic anhydride, phthalic anhydride, and pyromellitic anhydride; amines such as hexamethylenediamine, nonamethylenediamine, and phenylenediamine; Dicarboxylic acids such as adipic acid, maleic acid and itaconic acid; haloformyls such as adipic dichloride and phthalic dichloride; esters such as dimethyl terephthalate; ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, bisphenol A and the like Alcohols and the like.

Examples of the monomer having no carbonyl-containing group include α-olefins, styrenes, epoxies, and ethers. The polymerization method for synthesizing an organic polymer compound containing a carbonyl group from the above monomers is not particularly limited, and may be, for example, radical polymerization, cationic polymerization, anionic polymerization, transition metal catalyzed polymerization, ring-opening polymerization, polyaddition, or addition condensation. Alternatively, any of polycondensation may be used.

The organic polymer compound obtained by grafting or graft-polymerizing an unsaturated compound having a carbonyl group onto the organic polymer compound having no functional group (2) is, for example, a compound having the following functional group: Organic polymer compounds obtained by grafting or graft-polymerizing an unsaturated compound containing a carbonyl-containing group as described below by a radical reaction.

Examples of the polymer compound having no functional group include polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, ethylene-butene copolymer, ethylene-propylene-butene copolymer, polyisobutene, polypentene, poly-4-methylpentene, polynorbornene, Polybutadiene, polyisoprene, polystyrene, poly-α-methylstyrene, polyethylene oxide, polypropylene oxide, polytetrahydrofuran, polysiloxane and the like, among them polyethylene, polypropylene, ethylene-propylene copolymer, polybutene, ethylene-butene copolymer,
Preferred are ethylene / propylene / butene copolymer, polyisobutene, polypentene, poly-4-methylpentene, polynorbornene, polybutadiene, polyisoprene, polystyrene, poly α-methylstyrene, and the like.

Examples of unsaturated compounds containing a carbonyl group include acrylic acids such as methacrylic acid and acrylic acid; acrylic acids such as methyl methacrylate, 3-methacryloxypropyltrimethoxysilane and methyl acrylate Esters; acrylamides such as methacrylamide, acrylamide, and crotonamide; vinyls such as vinyl acetate, methyl vinyl ketone, acryloyl chloride, and acrylaldehyde; carboxylic anhydrides such as maleic anhydride and itaconic anhydride; And dicarboxylic acids such as itaconic acid.

Examples of the organic high molecular compound obtained by modification with the compound having a carbonyl group or the precursor compound of the carbonyl group of (3) include polyvinyl alcohol, polyvinyl chloride, polyvinyl pyridine, nitro Polystyrene, polyacrylonitrile,
Organic polymer compounds obtained by partially modifying or modifying an organic polymer compound such as cellulose by a reaction such as an esterification reaction, an oxidation reaction, a reduction reaction, an acylation reaction; polystyrene, poly α-methylstyrene, etc. And haloformyls such as acetyl chloride, adipic dichloride, and phthalic dichloride, and organic high molecular compounds partially modified or modified with acetic anhydride by Friedel-Crafts reaction.

The method for synthesizing the organic polymer compound containing a carbonyl-containing group represented by the above general formula (I) is not particularly limited, and includes a reaction in an organic or aqueous medium, a gas phase reaction, It may be synthesized in any reaction form such as a solid reaction, a bulk reaction without solvent, or a reaction under melt kneading. The content of the group having a carbonyl represented by the general formula (I) in the organic polymer compound is 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, preferably 1 × 10 ⁻² mol per 1 g of the polymer compound. It is from × 10 ^-5 to 1 × 10 ^-3 mol.

The carbonyl-containing organic polymer carrier preferably used in the present invention is obtained by grafting or graft-polymerizing an unsaturated compound having a carbonyl-containing group to a polyolefin. More specifically, polyethylene, polypropylene, polybutene, polyisobutene, polypentene, poly 4-methylpentene, polynorbornene, polybutadiene, polyisoprene, polystyrene, polyolefins such as poly α-methylstyrene,
Organic polymer grafted with maleic anhydride, itaconic anhydride, methacrylic acid, acrylic acid, methyl methacrylate, 3-methacryloxypropyltrimethoxysilane, methyl acrylate, etc., or after grafting, further functionalized on organic polymer Esterification of the group,
Organic polymers that have been at least partially modified or modified by reactions such as amidation, haloformylation, acylation, and the like.

Such a carbonyl-containing organic polymer carrier is hardly soluble or insoluble at room temperature in an inert organic solvent used for supporting a catalyst component and an inert hydrocarbon solvent used for polymerization. It is.

(B) Transition Metal Compound The transition metal compound used in the present invention has the following general formula (I)
I).

[0033]

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(Note that N ... M generally indicates coordination, but in the present invention, it may or may not be coordinated.) In the general formula (II), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), preferably a metal atom of Groups 3 to 9 (Group 3 also includes lanthanoids), more preferably Is a metal atom of groups 3 to 5 and 9 and particularly preferably a metal atom of group 4 or 5. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum,
Cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium and the like, preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, and more preferably,
Titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum and the like are particularly preferable, and titanium, zirconium and hafnium are particularly preferable.

M is an integer of 1 to 6, preferably 1 to 4,
Particularly preferably, 2 or 3 is shown. R ^{1 to} R ⁶ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, 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, two or more of which may be connected to each other to form a ring .

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specifically, the hydrocarbon group has 1 to 1 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, tert-amyl, and n-hexyl. 30, preferably 1 to 20 linear or branched alkyl groups; linear or branched alkenyl groups having 2 to 30, preferably 2 to 20 carbon atoms, such as vinyl, allyl and isopropenyl; A straight-chain or branched alkynyl group having 2 to 30, preferably 2 to 20 carbon atoms such as ethynyl and propargyl; and 3 to 30 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl, preferably 3-20 cyclic saturated hydrocarbon groups; alkyls such as 2-methylcyclopentyl, 2-methylcyclohexyl and 2,5-dimethylcyclohexyl; C5-30 cyclic unsaturated hydrocarbon groups such as cyclopentadienyl, indenyl and fluorenyl; carbon atoms such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthryl Is 6 to 30, preferably 6 to 2
An aryl group of 0; an alkyl-substituted aryl group such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl and di-t-butylphenyl;

In the above-mentioned hydrocarbon group, a hydrogen atom may be substituted with a halogen atom, for example, trifluoromethyl,
Examples thereof include halogenated hydrocarbon groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as pentafluorophenyl and chlorophenyl.

The hydrocarbon group may be substituted with another hydrocarbon group, for example, a cycloalkyl-substituted alkyl group such as cyclopropylmethyl, cyclohexylmethyl and cyclopentylmethyl; an aryl group such as benzyl and cumyl. And a substituted alkyl group.

Further, the hydrocarbon group may be a heterocyclic compound residue; 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 a carboxylic anhydride. Oxygen-containing groups such as groups; amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, amino groups A boron-containing group such as a boranediyl group, a borantoriyl group, a diboranyl group, etc .; a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group;
A sulfur-containing group such as a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfone ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group; It may have a phosphorus-containing group such as a phosphoryl group, a thiophosphoryl group, or a phosphato group, or a silicon-containing group, a germanium-containing group, or a tin-containing group as described later.

Of these, methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl, tert-butyl, neopentyl, tert-amyl, n-
C1-C30, preferably 1-2, carbon atoms such as hexyl
0 linear or branched alkyl group; 6 to 30, preferably 6 carbon atoms such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl and anthracenyl.
A halogen atom, an alkyl group or an alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, an aryl group or an aryloxy having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms. A substituted aryl group in which 1 to 5 substituents such as a group are substituted is preferable.

Examples of the heterocyclic compound residues include nitrogen-containing compounds such as pyrrole, pyridine, pyrimidine, quinoline, and triazine; oxygen-containing compounds such as furan and pyran;
Residues such as sulfur-containing compounds such as thiophene, and these heterocyclic compound residues have 1 to 30 carbon atoms,
Preferably, a group further substituted with a substituent such as an alkyl group or an alkoxy group of 1 to 20 or the like is exemplified.

Oxygen-containing groups, nitrogen-containing groups, boron-containing groups,
Examples of the sulfur-containing group and the phosphorus-containing group include the same as those exemplified above. Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group.Specifically, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenyl Examples include phenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl, and the like. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Examples of the germanium-containing group and the tin-containing group include those in which silicon in the silicon-containing group is replaced with germanium and tin. Next, the examples of R ^{1 to} R ⁶ described above will be described more specifically.

Of the oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like, and aryloxy groups include phenoxy and 2,6-dimethylphenoxy. , 2,4,6-trimethylphenoxy and the like; acyl groups include formyl group, acetyl group, benzoyl group, p-chlorobenzoyl group, p-methoxybensoyl group and the like; and ester groups include acetyloxy and benzoyl groups. Preferred examples include oxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl and the like.

Among the nitrogen-containing groups, amide groups include acetamido, N-methylacetamido, N-methylbenzamide, etc., amino groups include dimethylamino, ethylmethylamino, diphenylamino, etc., and imide groups include: Preferred examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

Among the sulfur-containing groups, alkylthio groups include methylthio, ethylthio and the like, arylthio groups include phenylthio, methylphenylthio, and nartylthio, and thioester groups include acetylthio, benzoylthio, methylthiocarbonyl and phenylthio. Carbonyl and the like, as a sulfone ester group,
Preferable examples include methyl sulfonate, ethyl sulfonate, and phenyl sulfonate. Examples of the sulfonamide group include phenyl sulfonamide, N-methyl sulfonamide, and N-methyl-p-toluene sulfonamide.

Preferably, R ⁶ is a substituent other than hydrogen. That is, R ⁶ is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a boron-containing group, a sulfur-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. In particular, R ⁶ is a halogen atom, a hydrocarbon group, a heterocyclic compound residue, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, an acyl group, an ester group, a thioester. Group, an amide group, an amino group, an imide group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group, and more preferably a halogen atom, a hydrocarbon group, or a hydrocarbon-substituted silyl group. Preferably, there is.

Preferred hydrocarbon groups for R ⁶ include:
1 carbon atom such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, tert-amyl, n-hexyl
A linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 20; a cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. An aryl group having 6 to 30, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenylyl, and triphenylyl; and an alkyl group having 1 to 30, preferably 1 to 20 carbon atoms in these groups. Group or alkoxy group, having 1 to 30 carbon atoms, preferably 1 to
20 halogenated alkyl groups having 6 to 30 carbon atoms,
Preferable examples include groups further substituted with 6 to 20 substituents such as an aryl group or an aryloxy group, a halogen, a cyano group, a nitro group and a hydroxy group.

Preferred hydrocarbon-substituted silyl groups for R ⁶ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,
Dimethylphenylsilyl, dimethyl-t-butylsilyl,
Dimethyl (pentafluorophenyl) silyl and the like. Particularly preferred are trimethylsilyl, triethylphenyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

In the present invention, R ⁶ is preferably a branched alkyl group having 3 to 30, preferably 3 to 20 carbon atoms, such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl and tert-amyl. And the hydrogen atoms of these groups have 6 to 30 carbon atoms, preferably 6 to 30 carbon atoms.
A group selected from a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as a group substituted with an aryl group of 20 (such as a cumyl group), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. It is preferably an aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, fluorenyl, anthryl, and phenanthryl, or a hydrocarbon-substituted silyl group.

R ^{1 to} R ⁶ represent two or more of these groups, preferably adjacent groups, which 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. And these rings may further have a substituent.

When m is 2 or more, R ^{1 s} , R ^{2 s} , R ^{3 s} , R ^{4 s} , R ^{5 s} , and R ^{6 s} may be the same or different from each other. in the case of 2 or more, at least one group of the groups represented by R ¹ to R ⁶ belonging to one of the ligands, R ¹ ~ belonging to other ligands
At least one of the groups represented by R ⁶ may be linked.

N is a number that satisfies the valency of M, and is specifically 0 to 5, preferably 1 to 4, more preferably 1 to 3.
Is an integer. A represents -O-, -S-, -N (R ⁷ )-or-
It represents Se-, and is preferably -O-. Examples of R ⁷ include the same groups and atoms as those described above for R ^{1 to} R ⁶ .

X represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group,
It indicates a boron-containing group, a sulfur-containing group, a phosphorus-containing group, an aluminum-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. When n is 2 or more, they may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. As the hydrocarbon group, the aforementioned R
^{The same} ones as exemplified for ^{1 to} R ⁶ can be mentioned.

Specifically, methyl, ethyl, propyl,
Alkyl groups having 1 to 30 carbon atoms such as butyl, hexyl, octyl, nonyl, dodecyl and eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl and adamantyl;
Alkenyl groups having 2 to 30 carbon atoms such as vinyl, propenyl and cyclohexenyl; arylalkyl groups having 7 to 30 carbon atoms such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, Examples include, but are not limited to, aryl groups having 6 to 30 carbon atoms, such as ethylphenyl, propylphenyl, biphenyl, naphthyl, methylnaphthyl, anthryl, and phenanthryl. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms has been replaced with halogen. Among them, those having 1 to 20 carbon atoms are preferable.

As the heterocyclic compound residue, R ¹
It includes the same as those exemplified in to R ^6. Examples of the oxygen-containing group include the same ones as those described above for R ^{1 to} R ^6. Specific examples include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy, and butoxy; phenoxy, methylphenoxy, and dimethyl. Examples include, but are not limited to, aryloxy groups such as phenoxy and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; and carbonyl groups.

Specific examples of the nitrogen-containing group include the aforementioned R ¹ to
The same ones as those exemplified for R ⁶ can be mentioned, and specifically, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino , Ditolylamino, dinaphthylamino, an arylamino group such as methylphenylamino or an alkylarylamino group.
It is not limited to these.

Specific examples of the boron-containing group include BR
₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like.). Examples of the sulfur-containing group include the same ones as those exemplified above in R ^{1 to} R ⁶ , and specifically, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, sulfonate groups such as p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate, pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzyl Examples include, but are not limited to, sulfinate groups such as sulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate; alkylthio groups; arylthio groups.

Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine and tricyclohexylphosphine; triarylphosphine groups such as triphenylphosphine and tolylphosphine; methylphosphite, ethylphosphite and the like. Examples include, but are not limited to, phosphite groups such as phenyl phosphite (phosphide groups); phosphonic acid groups; and phosphinic acid groups.

Specific examples of the halogen-containing group include P
F₆, BF_FourFluorine-containing groups such as ClO _Four, SbCl₆What
Which chlorine-containing groups, IO_FourAnd iodine-containing groups such as
However, the present invention is not limited to these.

Specific examples of the aluminum-containing group include A
lR ₄ (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like), but is not limited thereto.

Specific examples of the silicon-containing group include the aforementioned R ¹
To R ⁶ , and specifically include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, and tolylsilyl. A hydrocarbon-substituted silyl group such as trinaphthylsilyl; a hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include the same groups as those exemplified in the above R ^{1 to} R ⁶ , and specific examples include a group in which silicon of the silicon-containing group is replaced with germanium. .

Specific examples of the tin-containing group include the aforementioned R ¹ to
The same groups as those exemplified for R ⁶ can be mentioned, and more specifically, a group in which silicon of the silicon-containing group is substituted with tin is mentioned.

When n is 2 or more, Xs may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring. Hereinafter, specific examples of the transition metal compound represented by the general formula (II) are shown, but the invention is not limited thereto.

In the following specific examples, M is a transition metal element, and is individually Sc (III), Ti (III), Ti (I
V), Zr (III), Zr (IV), Hf (IV), V (IV), Nb
(V), Ta (V), Co (II), Co (III), Rh (II), Rh
(III) and Rh (IV), but are not limited thereto. Among them, Ti (IV), Zr (IV), Hf (I
V) is preferred.

X represents a halogen such as Cl or Br, or an alkyl group such as methyl, but is not limited thereto. When there are a plurality of Xs, they may be the same or different.

N is determined by the valence of the metal M. For example, if two monoanion species are bound to a metal,
N = 0 for a divalent metal, n = 1 for a trivalent metal, n = 2 for a tetravalent metal, and n = 3 for a pentavalent metal. For example, if the metal is T
In the case of i (IV), n = 2, and in the case of Zr (IV), n = 2
In the case of Hf (IV), n = 2.

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More specifically, the following can be mentioned.

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In the above examples, Me is a methyl group, Et
Represents an ethyl group, iPr represents an i-propyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group. The transition metal compound (B) represented by the general formula (II) includes a transition metal compound represented by the following general formula (II-b).

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In the formula, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and specific examples thereof include the same transition metal atoms as M in the above general formula (II). R ^{1 to} R ¹⁰ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, 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, and specifically, the same as R ^{1 to} R ⁶ in the above general formula (II) Atoms or groups. Further, two or more of R ^{1 to} R ¹⁰ may be connected to each other to form a ring.

R ⁶ or R ¹⁰ is at least one, especially both, a halogen atom, 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.

N is a number satisfying the valence of M. A and A ′ may be the same or different from each other, and —O—,
-S-, -N (R ⁷ )-or -Se-, both of which are -O-
It is preferred that As R ⁷ , the above R ^{1 to} R ⁶
And the same groups or atoms as mentioned above.

X represents a hydrogen atom, a halogen atom, 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, an aluminum-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and specifically the same as X in the above general formula (II) Atoms or groups.

When n is 2 or more, Xs may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other to form a ring. X is particularly preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a sulfonate group. When n is 2 or more,
The ring formed by linking two or more Xs to each other may be an aromatic ring or an aliphatic ring.

Y is oxygen, sulfur, carbon, nitrogen, phosphorus,
It represents a divalent linking group containing at least one element selected from the group consisting of silicon, selenium, tin and boron.
These bonding groups Y preferably have a main chain of 3 or more atoms,
More preferably 4 or more and 20 or less, particularly preferably 4
It has a structure composed of not less than 10 pieces and not more than 10 pieces. In addition, these bonding groups may have a substituent.

As the divalent linking group (Y), specifically,
Chalcogen atoms such as O-, -S-, -Se-; -NH-,-
N (CH_Three)-, -PH-, -P (CH_Three)-Such as nitrogen or
Phosphorus atom-containing group; -SiH_Two-, -Si (CH_Three)_Two-Such as
Iodine atom-containing group; -SnH_Two-, -Sn (CH_Three)_Two-Such as
Atom-containing group; -BH-, -B (CH_Three)-, -BF-
Examples include a group containing a urine atom. As a hydrocarbon group
Although there is no particular limitation,-(CH _Two)_Four-,-(CH_Two)_Five-,-(CH_Two)₆-
 Saturated hydrocarbon groups having 3 to 20 carbon atoms, such as
Cyclic saturation such as rohexylidene and cyclohexylene
Hydrocarbon group; a part of these saturated hydrocarbon groups is 1 to 10
Hydrocarbon groups, fluorine, chlorine, bromine and other halogens,
Oxygen, sulfur, nitrogen, phosphorus, silicon, selenium, tin, e
Groups substituted by heteroatoms such as urine; benzene, naph
Rings having 6 to 20 carbon atoms such as taren and anthracene
Hydrocarbon residues; pyridine, quinoline, thiophene,
3-20 carbon atoms including heteroatoms such as furan
And the residue of a cyclic compound.

Hereinafter, specific examples of the transition metal compound represented by the general formula (II-b) are shown, but the invention is not limited thereto.

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In the above examples, Me is a methyl group, Et
Represents an ethyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group. In the present invention, in the above compound,
A transition metal compound in which titanium metal is replaced with a metal other than titanium, such as zirconium or hafnium, can also be used.

(C) Organoaluminum oxy compound The organoaluminum oxy compound used in the present invention is:
A conventionally known aluminoxane may be used, or a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-2-78687. 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 adsorbed water or salts containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate,
An organic aluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension such as aluminum sulfate hydrate, nickel sulfate hydrate or cerous chloride hydrate, and adsorbed water or water of crystallization is added to the organic aluminum. A method of reacting with a 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 organoaluminum compounds. Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

The above-mentioned organoaluminum compound is
One type is used alone, or two or more types are used in combination. Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; pentane, hexane, heptane, octane,
Aliphatic hydrocarbons such as decane, dodecane, hexadecane and octadecane; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil or the above aromatic hydrocarbons; Hydrocarbon solvents such as aliphatic hydrocarbons and halides of alicyclic hydrocarbons (eg, 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.

The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component soluble in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Certain, ie, those that are insoluble or poorly soluble in benzene, are preferred.

As the organic aluminum oxy compound used in the present invention, an organic aluminum oxy compound containing boron represented by the following general formula (III) can also be mentioned.

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In the formula, R ¹¹ represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹² may be the same or different and each has a hydrogen atom, a halogen atom, and 1 to 10 carbon atoms.
Represents a hydrocarbon group.

The boron-containing organoaluminum oxy compound represented by the above general formula (III) is represented by the following general formula (I)
The alkylboronic acid represented by V) and the organoaluminum compound are subjected to -8 in an inert solvent under an inert gas atmosphere.
It can be produced by reacting at a temperature of 0 ° C. to room temperature for 1 minute to 24 hours.

R ¹¹ -B- (OH) ₂ ... (IV) (wherein, R ¹¹ represents the same group as described above.) As specific examples of the alkylboronic acid represented by the general formula (IV), Are methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, Fluorophenylboronic acid, 3,5-
Bis (trifluoromethyl) phenylboronic acid and the like can be mentioned. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

The above-mentioned organoaluminum oxy compounds are used alone or in combination of two or more. (D) Organometallic Compound As the organometallic compound used in the present invention, specifically, organometallic compounds of Groups 1 and 2 and Groups 12 and 13 of the periodic table as described below are used. (Da) general formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different, from 1 to 15 carbon atoms, preferably 1 to 4 represents a hydrocarbon group, 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
<3 and m + n + p + q = 3. The organoaluminum compound represented by). (Db) general formula M ² AlR ^a ₄ (wherein, M ² is Li, indicates Na or K, R ^a is the number of carbon atoms 1 to 15, preferably a 1-4 hydrocarbon group.) In A complex alkylated product of aluminum and Group 1 metal of the periodic table. (Dc) Formula R ^a R ^b M ³ (where R ^a and R ^b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms. , M ³ is Mg, Zn, or Cd.) A dialkyl compound of a metal belonging to Group 2 or 12 of the periodic table.

As the organoaluminum compound belonging to (Da), the following compounds can be exemplified. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organic aluminum compound represented by the formula: R ^a _m AlH _3-m (where R ^a has 1 to 15 carbon atoms, preferably 1 to
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 X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, It preferably represents 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 organoaluminum compound belonging to (Da), trimethylaluminum, triethylaluminum, trin-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum,
Tri-n-alkyl aluminums such as tridecyl aluminum; triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri ter
t-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3- Tri-branched alkyl aluminum such as methylhexyl aluminum and tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; diisobutyl aluminum hydride and the like Dialkyl aluminum hydride; (i-C ₄ H ₉ ) _x A
l _y (C ₅ H ₁₀ ) _z (where x, y, and z are positive numbers, z
≧ 2x. ) And the like; trialkenyl aluminum such as triisoprenyl aluminum; alkyl aluminum alkoxide such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide and isobutyl aluminum isopropoxide; dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide dialkylaluminum alkoxides such as; ethylaluminum sesquichloride ethoxide, alkyl aluminum sesqui alkoxides such as butyl sesquichloride butoxide; R ^a _2.5
Al (OR ^b) partially alkylaluminum is alkoxylated with an average composition represented by like _0.5; diethylaluminum phenoxide, diethylaluminum (2,
6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-)
Dialkylaluminum aryloxides such as methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide Alkylaluminum halides; diethylaluminum hydride Dialkylaluminum hydrides such as dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as ethylaluminum dihydride, alkylaluminum dihydrides such as propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum Partially alkoxylated and halogenated alkyl aluminums such as ethoxy bromide can be mentioned.

Compounds similar to (Da) can also be used, and examples thereof include organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, as such a compound,
(C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Compounds belonging to the above (Db) include L
iAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . In addition, (D) organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium 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 alkyl lithium or a combination of aluminum halide and alkyl magnesium can be used.

Among the organometallic compounds (D), organoaluminum compounds are preferred. The (D) organometallic compound as described above is used alone or in combination of two or more.

Preparation Method The olefin polymerization catalyst according to the present invention comprises the carbonyl-containing organic polymer carrier (A) carrying the transition metal compound (B) and the organic aluminum oxy compound (C). .

Such an olefin polymerization catalyst (solid catalyst (component)) is prepared, for example, by mixing a carbonyl-containing organic polymer carrier (A), a transition metal compound (B) and an organic aluminum oxy compound (C) in an inert organic solvent. Alternatively, it can be prepared by mixing and contacting in the absence of a solvent. The mixing order at this time is arbitrarily selected, but preferably, the carbonyl-containing organic polymer carrier (A) and the organic aluminum oxy compound (C) are mixed and contacted in an inert organic solvent to form an organic aluminum oxy compound ( C) preparing a solid component supported on the carbonyl-containing organic polymer carrier (A), isolating and washing the solid component, and bringing the solid component into contact with the transition metal compound (B); And a mixture of the transition metal compound (B) and the organic aluminum oxy compound (C) and the carbonyl-containing organic polymer carrier (A) in an inert organic solvent.

Further, an organic aluminum compound (C) is prepared from an organic polymer compound having a carbonyl group represented by the general formula (I) (the shape is not limited) and the organic aluminum oxy compound (C). Can be also prepared by preparing a solid component supported on the carbonyl-containing organic polymer carrier (A), and then supporting the transition metal compound (B) on the solid component.

In any of the above methods, the organic metal compound (D) can be further added when the components are mixed and brought into contact. Examples of the inert organic solvent used for preparing the solid catalyst (component) include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers, halogenated hydrocarbons, and the like. Aliphatic hydrocarbons having from 20 to 20 carbon atoms, alicyclic hydrocarbons having from 3 to 20 carbon atoms, aromatic hydrocarbon compounds having from 6 to 20 carbon atoms, ethers having from 2 to 20 carbon atoms, and having from 1 to 2 carbon atoms
And 0 halogenated hydrocarbons. More specifically, examples of the aliphatic hydrocarbon include propane, butane, isobutane, pentane, neopentane, hexane, heptane, octane, decane, dodecane, kerosene, and the like.As the alicyclic hydrocarbon, cyclopentane, cyclohexane , Methylcyclopentane, decalin and the like,
Examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like, examples of the ether include diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane and dioxane, and examples of the halogenated hydrocarbon include ethylene chloride and chlorobenzene. , Dichloromethane, chloroform and the like. Further, the inert organic solvent may be a mixture thereof.

When mixing the above components, a transition metal
Compound (B) is a carbonyl-containing organic polymer carrier (A)
Usually 10 per gram^-8~ 5 × 10^-3, Preferably 5 ×
10 ^-6~ 5 × 10^-FourMole, more preferably 10^-Five~ 2x
10^-FourUsed in a molar amount and the concentration of the transition metal compound (B).
The degree is usually 10^-Four~ 2 × 10^-2Mol / l (dissolved
Medium), preferably 2 × 10^-Four-10^-2Mol / liter
(Solvent). Organic aluminum oxy compounds
(C) is converted to the number of moles of aluminum contained.
Thus, per 1 g of the carbonyl-containing organic polymer carrier (A),
Usually 10^-FiveMol to 0.1 mol, preferably 5 × 10^-Four~
5 × 10^-2Used in molar amounts
Aluminum atom (Al) in compound (C) and transition
Atomic ratio with transition metal atom (M) in metal compound (B)
(Al / M) is usually 10 to 2000, preferably 10
１０００1000, more preferably 20-500.

The mixing temperature for mixing the above components is usually -80 to 200 ° C, preferably -20 to 120 ° C, and the contact time is 1 to 1500 minutes, preferably 5 to 60 minutes.
0 minutes. Further, the mixing temperature may be changed during the mixing contact.

In the solid component in which the organoaluminum oxy compound (C) is supported on the carbonyl-containing organic polymer carrier (A), the organoaluminum oxy compound (C) is an organic polymer which forms the carbonyl-containing organic polymer carrier (A). It is held on the carrier by a chemical bond with the molecular compound. Therefore, in the catalyst for olefin polymerization prepared in the above contact sequence, the transition metal compound (B) is supported on the carbonyl-containing organic polymer carrier (A) via the organoaluminum oxy compound (C), Metal compound (B)
Is chemically bonded to a carbonyl-containing group of an organic polymer forming the carbonyl-containing organic polymer carrier (A),
Alternatively, it is presumed that the carbonyl-containing organic polymer carrier (A) is not directly supported on the organic polymer by impregnation.

The method for preparing the solid component in which the organoaluminum oxy compound (C) is supported on the carbonyl-containing organic polymer carrier (A) includes the following steps: (1) A method in which the above-mentioned general formula (I) is added to a heated inert organic solvent. A method comprising dissolving an organic polymer having a carbonyl group represented by the formula and contacting with an organic aluminum oxy compound. (2) A method of contacting an organic aluminum oxy compound (C) with a carbonyl-containing organic polymer carrier (A) suspended in an inert organic solvent. (3) A method in which an organic aluminum oxy compound (C) is brought into contact with a carbonyl-containing organic polymer carrier (A) without a solvent.

The inert organic solvent used in the methods (1) and (2) includes the same inert organic solvents as described above. In the above method (1), an organic polymer compound containing a carbonyl-containing group represented by the general formula (I) is mixed with an inert organic solvent, and the mixture is mixed at 40 ° C to 2 ° C.
The solution obtained by heating and dissolving in a temperature range of 50 ° C, preferably 60 ° C to 200 ° C, and the organoaluminum oxy compound (C) are mixed and contacted for a contact time of 10 minutes to 24 hours. At this time, an inert organic solvent and a temperature at which the organic polymer compound having a carbonyl group represented by the general formula (I) is dissolved are employed.

Further, by treating the solution subjected to the contact treatment as follows, for example, the organoaluminum oxy compound (C) is converted into the carbonyl-containing organic polymer carrier (A).
And a solid component can be obtained in powder form. Solid components are precipitated by cooling the solution. A solid component is precipitated by adding a poor solvent to the solution. The solution is sprayed onto a poor solvent via a nozzle to precipitate a solid component. The solution is sprayed with a spray drier into an atmosphere in which the solvent evaporates, and powdered. The solvent is removed from the solution to dryness, and the obtained solid is pulverized by a vibration mill, a ball mill, or the like. The operation temperatures of the above-mentioned are lower than the melting point temperature of the organic polymer compound.

In the method (2), the carbonyl-containing organic polymer carrier (A) is suspended in an inert organic solvent.
The organic aluminum oxy compound (C) is mixed and contacted with the organoaluminum oxy compound (C) for a contact time of 10 minutes to 24 hours in a contact temperature range of from 200C to 200C, preferably from -20C to 150C. At this time, an inert organic solvent and a temperature that do not dissolve the carbonyl-containing organic polymer carrier (A) are employed.

Further, a poor solvent may be added to the suspension subjected to the contact treatment. Alternatively, the solvent may be removed from the suspension, and the suspension may be further pulverized by a vibration mill, a ball mill, or the like.
The method (3) is the simplest method, and uses a mixer or a mill such as a mixer or a mill, and the carbonyl-containing organic polymer carrier (A) and the organic compound substantially in the absence of a solvent. Aluminum oxy compound (C)
Mixing and contacting are carried out in a temperature range of 80 ° C to 200 ° C, preferably -20 ° C to 150 ° C for a contact time of 30 minutes to 24 hours. Further, the obtained powder may be suspended in a poor solvent.

The contact amount between the organic polymer compound having a carbonyl group or the carbonyl-containing organic polymer carrier (A) and the organic aluminum oxy compound (C) in the above methods (1) to (3). Is 1 × 1 as the number of moles of aluminum contained in the organic aluminum oxy compound (C) per 1 g of the organic polymer compound or the carbonyl-containing organic polymer carrier (A).
It is 0 ^{-5 to} 0.1 mol, preferably 1 × 10 ^{-4 to} 0.01 mol.

The solid component in which the organoaluminum oxy compound (C) obtained by the above methods (1) to (3) is carried on the carbonyl-containing organic polymer carrier (A) is washed with an inert organic solvent, The removal of the organoaluminum oxy compound (C) not retained on the carrier (A) by chemical bonding with the organic polymer compound forming the carbonyl-containing organic polymer carrier (A) can be achieved by the organic aluminum compound (C). This is preferable from the viewpoint of preventing the adhesion of (3) to the reactor inner wall.

As a washing method, the solid component is suspended in an inert organic solvent, or the solid component is rinsed with an inert organic solvent, and then filtered, decanted or centrifuged to remove the solid component. And the like. The inert organic solvent used here is an organic aluminum oxy compound that is not held on the carbonyl-containing organic polymer carrier (A) by a chemical bond with the organic polymer compound that forms the carbonyl-containing organic polymer carrier (A). The solvent is preferably a solvent that dissolves (C) and insoluble in the carbonyl-containing organic polymer carrier (A). The amount of the washing solvent and the number of washings are not particularly limited. The washing temperature is lower than the melting point of the organic polymer compound forming the carbonyl-containing organic polymer carrier (A).

In the olefin polymerization catalyst thus obtained, the transition metal compound (B) was added to the carbonyl-containing organic polymer carrier (A) in an amount of about 5 g in terms of transition metal atom per 1 g.
× 10 ^-6 to 10 ^-3 mol, preferably 10 ^{-5 to} 3 × 10 ^-4
The organic aluminum oxy compound (C) is supported in an amount of about 10 ^-3 to 10 ^-1 mol, preferably 2 × 10 ^{-3 to} 5 × 10 ^-2 mol in terms of aluminum atom. It is desirable.

The olefin polymerization catalyst according to the present invention may be a prepolymerization catalyst in which an olefin is prepolymerized on the solid catalyst component. FIG. 1 shows a process for preparing the olefin polymerization catalyst according to the present invention.

Polymerization Method In the olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst as described above.

In the present invention, the polymerization can be carried out by any of liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane Alicyclic hydrocarbons such as benzene, toluene, xylene, etc .; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof, and the olefin itself is used as a solvent. You can also.

When olefin polymerization is carried out using the olefin polymerization catalyst as described above, the olefin polymerization catalyst is used as the amount of the transition metal compound (B) supported on the catalyst per 1 liter of reaction volume. , Usually 10
It is used in such an amount as to give ^-12 to 10 ^-2 mol, preferably 10 ^-8 to 10 ^-3 mol.

At this time, an organometallic compound (D) can be used if necessary. In this case, the amount of the organometallic compound (D) depends on the amount of the transition metal 1 in the transition metal compound (B).
2000 mol or less, preferably 50 to 10 per mol
Preferably, the amount is 00 mole. Instead of the organometallic compound (D), apart from the one supported on a carrier,
An organic aluminum oxy compound (C) may be added.

The polymerization temperature is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C. when performing the slurry polymerization method, and is usually in the range of 0 to 90 ° C. when performing the liquid phase polymerization method. The temperature is desirably in the range of 0 to 250C, preferably 20 to 200C. When carrying out the gas phase polymerization method, the temperature is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C. The polymerization pressure is usually from normal pressure to 1
00 kg / cm ² , preferably normal pressure to 50 kg / cm ²
The polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by adding hydrogen to the polymerization system or changing the polymerization temperature. Furthermore, it can be adjusted by the difference of the organometallic compound (D) used.

Examples of the olefin that can be polymerized with such an olefin polymerization catalyst include linear or branched α-olefins having 2 to 30, preferably 2 to 20 carbon atoms, for example, ethylene, propylene, and the like. 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene; a cyclic olefin having 3 to 30, preferably 3 to 20 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2 -Methyl 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; polar monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, Itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene
Α, β-unsaturated carboxylic acids such as -2,3-dicarboxylic anhydride and metal salts thereof such as sodium salt, potassium salt, lithium salt, zinc salt, magnesium salt, calcium salt; methyl acrylate, acrylic Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate
Α, β such as butyl, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate -Unsaturated carboxylic esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate; glycidyl acrylate, glycidyl methacrylate, and itaconic acid Unsaturated glycidyl such as monoglycidyl ester; and halogen-containing monomers such as vinyl chloride and chloroprene. Further, vinylcyclohexane, diene, polyene, or the like can be used.

As the diene or polyene, a cyclic or chain compound having 4 to 30, preferably 4 to 20 carbon atoms and having at least two double bonds is used.
Specifically, butadiene, isoprene, 4-methyl-1,3-
Pentadiene, 1,3-pentadiene, 1,4-pentadiene,
1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene , Vinyl norbornene, dicyclopentadiene; 7-methyl-1,6-octadiene, 4-ethylidene-
8-methyl-1,7-nonadiene, 5,9-dimethyl-1,4,8-decatriene; further aromatic vinyl compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-
Mono- or polyalkylstyrenes such as ethylstyrene and p-ethylstyrene; methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, etc. And 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene and the like.

These olefins can be used alone or
It can be used in combination of more than one kind.

[0140]

Industrial Applicability The olefin polymerization catalyst and the polymerization method according to the present invention can produce a polyolefin having high polymerization activity, a small amount of fine powder generated during polymerization, and excellent particle properties.

[0141]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In this example, the intrinsic viscosity ([η])
Was measured in decalin at 135 ° C.

[0142]

Example 1 [Preparation of solid component (a)] In a 500 ml four-necked flask sufficiently purged with nitrogen, 1 g of maleic anhydride-grafted polypropylene (maleic anhydride content: 10% by weight, 1 mmol / g) was suspended in 400 ml of xylene. After turbidity, the mixture was heated until boiling, and the maleic anhydride-grafted polypropylene was completely dissolved. In that boiling solution,
Using a dropping funnel, add 12 mmol of a toluene solution of methylaluminoxane in terms of aluminum atoms,
After heating for 4 hours in a boiling state, the mixture was gradually cooled to room temperature over 12 hours and allowed to stand to precipitate a pale yellow solid component.
Further, the supernatant was removed by decantation, 100 ml of toluene was added, and the mixture was stirred at 20 ° C. for 30 minutes and allowed to stand. This washing operation was repeated three times, and the supernatant was removed by decantation to obtain a suspension containing the solid component (a). The concentration of the solid component (a) in this suspension was 0.31 g / ml. The aluminum content in the solid component (a) measured by taking a predetermined amount of the suspension and drying under reduced pressure was 6 mmol / g.

[Preparation of solid catalyst component (b)] In a 200 ml three-necked flask sufficiently purged with nitrogen, 7.5 mmol of the solid component (a) in terms of Al was dissolved in toluene (the following compound (B-1) 0). .03 mmol and a total of 50
Toluene was added to a volume of 1 ml, followed by stirring at room temperature for 1 hour. The supernatant solution is removed by decantation,
Washed three times with 50 ml heptane and resuspended with 20 ml heptane. As a result, 0.01 g of zirconium per gram was obtained.
A solid catalyst component (b) supporting 9 mmol and 4.71 mmol of aluminum was obtained.

[0144]

Embedded image

[Polymerization] 500 ml of heptane was charged into a 1-liter stainless steel autoclave sufficiently purged with nitrogen, and the gas phase and the liquid phase were saturated with ethylene at room temperature. Thereafter, the temperature of the system was raised to 70 ° C., and 0.5 mmol of triisobutylaluminum and 0.0025 mmol of the solid catalyst component (b) in terms of zirconium atoms were added.
The polymerization was started. While continuously supplying ethylene, 8
Polymerization was performed at kg / cm ² G and 75 ° C. for 1 hour. The obtained polymer suspension was filtered with a glass filter, washed twice with 500 ml of hexane, and dried at 80 ° C. for 10 hours under reduced pressure.

The obtained polyethylene was 26.4 g, the polymerization activity was 10.5 kg / mmol-Zr,
The intrinsic viscosity [η] was 8.47 dl / g, and the apparent bulk specific gravity was 0.24 g / cm ³ .

[0147]

Example 2 [Preparation of solid catalyst component (c)] In [Preparation of solid catalyst component (b)] of Example 1, the compound (B-
Except for using the following compound (B-2) instead of 1),
As in Example 1, 0.019 m of titanium per gram
Thus, a solid catalyst component (c) supporting 4.70 mmol of aluminum and 4.70 mmol of aluminum was obtained.

[0148]

Embedded image

[Polymerization] The procedure of Example 1 was repeated, except that the solid catalyst component (c) was replaced by 0.005 mmol in terms of titanium atoms in place of the solid catalyst component (b). Polymerization was carried out in the same manner as in Example 1.

The obtained polyethylene was 18.0 g, the polymerization activity was 3.60 kg / mmol-Ti,
The intrinsic viscosity [η] was 10.0 dl / g, and the apparent bulk specific gravity was 0.26 g / cm ³ .

[0151]

[Comparative Example 1] [Preparation of solid component (d)] In a 400 ml reactor sufficiently purged with nitrogen, 10 g of silica (F-948, manufactured by Fuji Devison) and 150 ml of toluene dried at 200 ° C for 4 hours were charged. The system was brought to 0 ° C. with stirring. To this, a toluene solution of methylaluminoxane was added dropwise over 60 minutes under a 67 mmol nitrogen atmosphere in terms of aluminum atoms. Then at this temperature for 30 minutes,
The reaction was performed at 95 ° C. for 4 hours. The reaction system was allowed to cool, and when the temperature reached 60 ° C., the supernatant solution was removed by decantation, followed by washing three times with 150 ml of toluene at room temperature, and then re-suspended by adding toluene to a total volume of 150 ml. As a result, 6.1 g of Al was added to 1 g of silica.
The solid component (d) having mmol was obtained.

[Preparation of solid catalyst component (e)] In [Preparation of solid catalyst component (b)] of Example 1, except that the solid catalyst component (d) was used instead of the solid component (a). As in Example 1, 0.019 mmol zirconium and 4.62 mmol aluminum per gram.
A supported solid catalyst component (e) was obtained.

[Polymerization] Polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component (e) was used instead of the solid catalyst component (b) in [Polymerization] of Example 1.

The obtained polyethylene was 15.7 g, the polymerization activity was 6.27 kg / mmol-Zr,
The intrinsic viscosity [η] was 14.6 dl / g, and the apparent bulk specific gravity was 0.23 g / cm ³ .

[0155]

Comparative Example 2 [Preparation of solid catalyst component (f)] In [Preparation of solid catalyst component (c)] of Example 2, except that solid component (d) was used instead of solid component (a). In the same manner as in Example 2, the amount of titanium was 0.018 mmol / g.
1, a solid catalyst component (f) carrying 4.65 mmol of aluminum was obtained.

[Polymerization] Polymerization was carried out in the same manner as in Example 2 except that the solid catalyst component (f) was used in place of the solid catalyst component (c) in [Polymerization] of Example 2.

The obtained polyethylene weighed 6.2 g,
The polymerization activity was 1.24 kg / mmol-Ti, the intrinsic viscosity [η] was 11.7 dl / g, and the apparent bulk specific gravity was 0.21 g / cm ³ . Table 1 shows the above results.

[0158]

[Table 1]

[Brief description of the drawings]

FIG. 1 shows a process for preparing an olefin polymerization catalyst according to the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Mitani 6-1, 1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Terunori Fujita Waka-machi, Kuga-gun, Yamaguchi Prefecture 6-1-2 Ki, Mitsui Chemicals, Inc. F-term (reference) 4J028 AA01A AB00A AB01A AC01A AC08A AC09A AC26A AC27A AC31A AC32A AC41A AC42A AC44A AC46A AC47A BA00A BA01B BA02B BB00A BB01B BB02 BC02BBCBBC BCBC BCBC BCBC EB02 EB03 FA01 FA02 GA01 GA09 GB01 4J100 AA02P AA03P AA04P AA05P AA07P AA09P AA15P AA16P AA17P AA21P AB02 AB03 AC03 AG02 AG04 AJ02P AJ08P AJ09P AK08 AK12 AK32 AL03 AS04 AR09 AR03

Claims (3)

[Claims] 1. A carrier comprising an organic polymer containing a carbonyl-containing group represented by the following general formula (I): (B) a transition metal compound represented by the following general formula (II):
(C) An olefin polymerization catalyst comprising an organoaluminum oxy compound supported thereon. Embedded image (Wherein Q is a hydrogen atom, a halogen atom, a hydroxy group,
It represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an oxycarbonyl group, an amino group, an aminocarbonyl group, a hydrazino group or a xyanion. ) (Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different, and may be a hydrogen atom, A halogen atom, 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. Two or more of them may be connected to each other to form a ring, and when m is 2 or more, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ May be the same or different from each other,
When m is 2 or more, R ¹ to R ¹ belonging to one ligand
Well with at least one group of the groups represented by R ^6, even if at least one group of the groups represented by R ¹ to R ⁶ belonging to another ligand coupled, n is a number satisfying a valence of M, a is, -O -, - S -, - N (R 7) - or -Se- indicates,
R ⁷ has the same meaning as R ^{1 to} R ⁶ above; X is a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, and a sulfur-containing group. , Phosphorus-containing groups, aluminum-containing groups,
A halogen-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and when n is 2 or more, Xs may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other To form a ring. ) 2. A carrier comprising an organic polymer containing a carbonyl-containing group represented by the following general formula (I):
(B) a transition metal compound represented by the following general formula (II):
An olefin polymerization catalyst comprising: (C) a solid catalyst component carrying an organoaluminum oxy compound; and (D) an organometallic compound. Embedded image (Wherein Q is a hydrogen atom, a halogen atom, a hydroxy group,
It represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an oxycarbonyl group, an amino group, an aminocarbonyl group, a hydrazino group or an oxyanion. ) (Wherein, M represents a transition metal atom of Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different, and may be a hydrogen atom, A halogen atom, 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. Two or more of them may be connected to each other to form a ring, and when m is 2 or more, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ May be the same or different from each other,
When m is 2 or more, R ¹ to R ¹ belonging to one ligand
Well with at least one group of the groups represented by R ^6, even if at least one group of the groups represented by R ¹ to R ⁶ belonging to another ligand coupled, n is a number satisfying a valence of M, a is, -O -, - S -, - N (R 7) - or -Se- indicates,
R ⁷ has the same meaning as R ^{1 to} R ⁶ above; X is a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, and a sulfur-containing group. , Phosphorus-containing groups, aluminum-containing groups,
A halogen-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, and when n is 2 or more, Xs may be the same or different from each other, and a plurality of groups represented by X may be bonded to each other To form a ring. ) 3. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1 or 2.