JP2000191718A - Olefin polymerization catalyst and polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an olefin polymerization catalyst having high polymerization activity and giving an olefin (co)polymer having broad molecular weight distribution and excellent moldability and provide a process for the polymerization of an olefin. SOLUTION: The objective olefin polymerization catalyst is composed of (A) a titanium catalyst component containing magnesium, titanium and a halogen as essential components, (B) a transition metal imine compound of the formula and (C) at least one kind of compound selected from (C-1) an organometallic compound, (C-2) an organic aluminumoxy compound and (C-3) a compound reacting with the transition metal imine compound B to form an ion pair. An olefin is polymerized by using the polymerization catalyst.

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 polymerizing olefin using the catalyst. More specifically, an olefin (co) polymer having a high polymerization activity and a wide molecular weight distribution can be obtained. Such a novel olefin polymerization catalyst and a method for polymerizing olefins using the catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a catalyst for producing an olefin polymer such as an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst comprising a titanium compound and an organoaluminum compound, and a vanadium compound There is known a vanadium-based catalyst comprising an organic aluminum compound.

A Ziegler catalyst comprising a metallocene compound such as zirconocene and an organic aluminum oxy compound (aluminoxane) is known as a catalyst capable of producing an olefin polymer with high polymerization activity.

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 such as ethylene polymers have excellent mechanical strength and chemical resistance.
It is used as various molding materials. However, a catalyst comprising a transition metal amide compound such as a titanium amide compound as described above and an aluminoxane has high polymerization activity, but an olefin polymer obtained using the same has a narrow molecular weight distribution and a low moldability. Is not always good. For this reason, there has been a demand for an improvement in a catalyst containing a transition metal amide compound that can obtain an olefin polymer having a wide molecular weight distribution and excellent moldability without impairing high polymerization activity.

[0007]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide an olefin (co) polymer having a high polymerization activity, a wide molecular weight distribution and excellent moldability. It is intended to provide such an olefin polymerization catalyst.

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 titanium catalyst component containing magnesium, titanium and halogen as essential components, (B) a transition metal imine compound represented by the following general formula (I), (C) (C-1) an organometallic compound, C-2) An olefin polymerization comprising an organoaluminum oxy compound and (C-3) at least one compound selected from compounds which react with the transition metal imine compound (B) to form an ion pair. Catalyst for use;

Embedded image (Wherein, M represents a transition metal atom belonging to Groups 8 to 11 of the periodic table,
R ^{1 to} R ⁴ 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,
R ⁵ and R ⁶ 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, and a sulfur-containing group. R ¹ , R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁵
May be linked to each other to form a ring, and R ² and R ⁶
May be linked to each other to form a ring, and R ¹ and R ³
May be linked to each other to form a ring, and R ² and R ⁴
May be connected to each other to form a ring, and R ³ and R ⁴
May be connected to each other to form a ring, n represents a valence of M, X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon group having 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 of Group 15 or 16 of the periodic table. ).

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

[0011]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst of the present invention and the olefin polymerization method using the catalyst will be described in detail.

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 titanium catalyst component containing magnesium, titanium and halogen as essential components, (B) a transition metal imine compound represented by the above general formula (I), (C) (C-1) an organometallic compound, Olefin polymerization characterized by comprising: C-2) an organic aluminum oxy compound; and (C-3) at least one compound selected from compounds which react with the transition metal imine compound (B) to form an ion pair. Catalyst.

First, each catalyst component forming the olefin polymerization catalyst of the present invention will be described. (A) Titanium catalyst component containing magnesium, titanium and halogen as essential components (A) The titanium catalyst component containing magnesium, titanium and halogen as essential components (hereinafter referred to as “titanium catalyst component”) is magnesium. , Titanium and halogen as essential components and, if necessary, an electron donor.

Such a titanium catalyst component (A) can be prepared by contacting the following magnesium compound and titanium compound, and if necessary, an electron donor.

(A) Specific examples of the titanium compound used for preparing the titanium catalyst component include a tetravalent titanium compound represented by the following formula. Ti (OR) _d X _4-d (wherein, R represents a hydrocarbon group, X represents a halogen atom, and d satisfies 0 ≦ d ≦ 4) As such a titanium compound, specifically, TiCl
₄ , titanium tetrahalides such as TiBr ₄ and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ ,
_{Ti (O-n-C 4} H 9) Cl 3, Ti (OC 2 H 5) Br 3,
_{Ti (O-iso-C 4} H 9) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 Cl 2, Ti (OC 2
_{H 5) 2 Cl 2, Ti} (O-n-C 4 H 9) 2 Cl 2, Ti (O
Dialkoxytitanium dihalides such as C ₂ H ₅ ) ₂ Br ₂ ; Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl,
_{Ti (O-n-C 4} H 9) 3 Cl, Ti (OC 2 H 5) 3 Br
Monohalogenated trialkoxy titanium such as Ti;
CH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ )
_{4, Ti (O-iso-} C 4 H 9) 4, Ti (O-2- ethylhexyl) such as tetra-alkoxy titanium such as ₄ can be exemplified.

Of these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Examples of the magnesium compound used for preparing the titanium catalyst component (A) include a magnesium compound having a reducing property and a magnesium compound having no reducing property.

As the magnesium compound having a reducing property, a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond can be exemplified. Specific examples of such a reducing magnesium compound include dimethyl magnesium, diethyl magnesium, dipropyl magnesium,
Dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride, and the like. it can. These magnesium compounds may be used alone, or may be ones which form a complex compound with an organometallic compound as described later. These magnesium compounds may be liquid or solid, or may be derived by reacting metallic magnesium with a corresponding compound. Furthermore, it can be derived from metallic magnesium during the catalyst preparation using the above-mentioned method.

Specific examples of the non-reducing magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, and isopropoxy magnesium chloride. Alkoxy magnesium halides such as butoxymagnesium chloride and octoxymagnesium chloride; allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxy Alkoxy magnesium such as magnesium; allylo such as phenoxy magnesium and dimethyl phenoxy magnesium And magnesium carboxylate such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned magnesium compound having a reducing property or a compound derived during the preparation of the catalyst component.

The magnesium compound having no reducing property is
In order to derive from a reducing magnesium compound,
For example, a reducing magnesium compound is contacted with a halogen, a halogen-containing organosilicon compound, a halogen-containing aluminum compound such as a halogen-containing aluminum compound, a compound having an active carbon-oxygen bond such as an alcohol, an ester, a ketone, or an aldehyde, or a polysiloxane compound. It should be done.

In addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property, the magnesium compound may be a complex compound, a double compound or another metal compound of the above-mentioned magnesium compound and another metal. It may be a mixture. In addition, the above compound is
It may be used in combination of more than one kind.

As the magnesium compound used for preparing the titanium catalyst component (A), many magnesium compounds other than those described above can be used. In the finally obtained titanium catalyst component (A), a halogen-containing magnesium compound is used. Preferably, the compound is in the form of a compound. Therefore, when a halogen-free magnesium compound is used, it is preferable to carry out a contact reaction with a halogen-containing compound during the preparation.

Among the above-mentioned magnesium compounds, magnesium compounds having no reducing property are preferred, magnesium compounds containing halogen are more preferred, and magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are particularly preferred.

In preparing the titanium catalyst component (A),
It is preferable to use an electron donor, and as the electron donor, alcohols, phenols, ketones, aldehydes, carboxylic acids, acid halides, esters of organic or inorganic acids, ethers, acid amides, Acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, oxygen-containing cyclic compounds, and the like.
More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl Alcohols having 1 to 18 carbon atoms such as alcohols;
Halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol; having lower alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol Phenols having 6 to 20 carbon atoms; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde; Aldehydes having 2 to 15 carbon atoms, such as tolualdehyde and naphthaldehyde;
Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, δ-
Organic acid esters having 2 to 30 carbon atoms such as valerolactone, coumarin, phthalide, ethyl carbonate; acetyl chloride, benzoyl chloride, toluic acid chloride,
Acid halides having 2 to 15 carbon atoms such as anisic acid chloride; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-
Acid amides such as dimethylamide; amines such as methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylenediamine, hexamethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile Acetic anhydride,
Acid anhydrides such as phthalic anhydride and benzoic anhydride; pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole; pyrroline; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethyl Pyridines such as pyridine, phenylpyridine, benzylpyridine and pyridine chloride; piperidines, quinolines,
Nitrogen-containing cyclic compounds such as isoquinolines; cyclic compounds such as tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, and ditedropyran Oxygen-containing compounds are exemplified.

As the organic acid ester, a polycarboxylic acid ester having a skeleton represented by the following general formula (II) can be mentioned as a particularly preferred example.

[0028]

Embedded image

In the above formula, R ³¹ represents a substituted or unsubstituted hydrocarbon group, R ³² , R ³⁵ and R ³⁶ represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and R ³³ and R ³⁴ Represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group,
Preferably, at least one of them is a substituted or unsubstituted hydrocarbon group. R ³³ and R ³⁴ may be connected to each other to form a cyclic structure. Hydrocarbon groups R ^{31 to} R ³⁶
Is substituted, contains a hetero atom such as N, O, S, and is, for example, C—O—C, COOR, COO.
It has groups such as H, OH, SO ₃ H, —C—N—C—, and NH ₂ .

Specific examples of such polycarboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate, and isopropyl malonate. Diethyl acrylate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, β-methyl glutar Polycarboxylic acid esters such as diisopropyl acrylate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate and dioctyl citraconic acid; diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclohexyl Alicyclic polycarboxylic acid esters such as diisobutyl hexanecarboxylate, diethyl tetrahydrophthalate and diethyl nadicate; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate; Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, phthalic acid Aromatic polycarboxylic acid esters such as didecyl, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate; heterogeneous groups such as 3,4-furandicarboxylic acid Cyclic polycarboxylic acid esters and the like.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Long-chain dicarboxylic acid esters and the like can be mentioned.

In the present invention, as the electron donor, an organosilicon compound represented by the following general formula (II-1) or (II-3), a polyether compound represented by the following general formula (III), and the like can be used. It can also be used.

(R ^p ) _i -Si- (OR ^q ) _4-i (II-1) (where i is 1, 2 or 3 and when i is 1, R ^p
Represents a secondary or tertiary hydrocarbon group, and i represents 2 or 3
At least one of R ^{p represents} a secondary or tertiary hydrocarbon group, the other represents a hydrocarbon group, a plurality of R ^p may be the same or different, and R ^q is a carbon atom. Numbers 1-4
When 4-i is 2 or 3, R ^q may be the same or different from each other. ) In the silicon compound represented by the formula (II-1), as the secondary or tertiary hydrocarbon group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a group having a substituent, A hydrocarbon group in which the adjacent carbon is secondary or tertiary is exemplified.

Among these, dimethoxysilanes, particularly dimethoxysilanes represented by the following formula (II-2), are preferred.

[0035]

Embedded image

(Wherein R ^j and R ^k each independently represent a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group,
Represents a hydrocarbon group in which the carbon adjacent to is a secondary or tertiary carbon. Examples of the organosilicon compound represented by the general formula (II-2) include dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, and di (3-methyl Cyclopentyl) dimethoxysilane, di-t-amyldimethoxysilane and the like.

As the organosilicon compound, an organosilicon compound represented by the following general formula (II-3) can also be used. (R) _l- Si- (OR ') _4-l ... (II-3) (wherein R and R' are hydrocarbon groups such as alkyl group, aryl group and alkylidene group, and 0 <l < Specific examples of the organosilicon compound represented by the general formula (II-3) include diphenyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxy. Examples include silane, phenyltriethoxysilane, and n-propyltriethoxysilane.

Further, as compounds similar to the organosilicon compound represented by the general formula (II-3), γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyl silicate, silica Butyl acid, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy siloxane, and the like.

The organosilicon compound represented by the general formula (II-3) may include the organosilicon compound represented by the general formula (II-1). The organosilicon compounds can be used alone or in combination of two or more.

Examples of the polyether compound include compounds represented by the following general formula (III).

[0041]

Embedded image

In the formula, v is an integer of 2 ≦ v ≦ 10, and R ⁵¹
To R ^{56 + 2v} represent a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any of R ^{51 to} R
^{56 + 2v} , preferably R ^{56 + 1 to} R ^{56 + 2v} may form a ring other than a benzene ring together, and the main chain may contain an atom other than a carbon atom.

As the polyether compound as described above, 1,3-diethers are preferably used.
Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3 -Dimethoxypropane, 9,9-
Dimethoxymethylfluorene is preferably used.

In addition to these, water, anionic, cationic and nonionic surfactants can also be used.
These electron donors are used alone or in combination of two or more.

When the above-mentioned titanium compound, magnesium compound and electron donor are brought into contact with each other, a carrier-supported titanium catalyst component (A) is prepared by using a particulate carrier (D) as described below. Can also.

The titanium catalyst component (A) can be produced by bringing the above-mentioned titanium compound and magnesium compound into contact with an electron donor, if necessary, and can be produced by any method including a known method. Can be. The above components are, for example, silicon, phosphorus,
The contact may be performed in the presence of another reactant such as aluminum.

The method for producing the titanium catalyst component (A) will be briefly described below with reference to several examples. In the method for producing the titanium catalyst component (A) described below, an example in which an electron donor is used will be described, but this electron donor is not necessarily required. (1) A method in which a solution comprising a magnesium compound, an electron donor, and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or a contact reaction is performed with a titanium compound while the solid is precipitated. (2) A method comprising bringing a complex comprising a magnesium compound and an electron donor into contact with and reacting with an organometallic compound, followed by a contact reaction with a titanium compound. (3) In the contact substance between the inorganic carrier and the organomagnesium compound,
A method in which a titanium compound and preferably an electron donor are contacted and reacted. At this time, the contacted product may be brought into contact with a halogen-containing compound and / or an organometallic compound in advance. (4) a method of obtaining a magnesium compound-supported inorganic or organic carrier from a mixture of a magnesium compound, an electron donor, and optionally a solution containing a hydrocarbon solvent and an inorganic or organic carrier, and then contacting the titanium compound . (5) magnesium compound, titanium compound, electron donor,
A method of obtaining a solid titanium catalyst component carrying magnesium and titanium by contacting a solution containing a hydrocarbon solvent with an inorganic or organic carrier, if necessary. (6) A method of contacting a liquid state organomagnesium compound with a halogen-containing titanium compound. At this time, the electron donor is used once. (7) A method in which a liquid state organomagnesium compound is brought into contact with a halogen-containing compound and then brought into contact with a titanium compound.
At this time, the electron donor is used once. (8) A method of contacting an alkoxy group-containing magnesium compound with a halogen-containing titanium compound. At this time, the electron donor is used once. (9) A method comprising contacting a complex comprising an alkoxy group-containing magnesium compound and an electron donor with a titanium compound. (10) A method comprising bringing a complex comprising an alkoxy group-containing magnesium compound and an electron donor into contact with an organometallic compound and then contacting with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor, and a titanium compound in an arbitrary order. In this reaction, each component may be pretreated with an electron donor and / or a reaction auxiliary such as an organometallic compound or a halogen-containing silicon compound. In this method, the electron donor is preferably used at least once. (12) A method of reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor, to precipitate a solid magnesium-titanium composite. (13) A method in which a titanium compound is further reacted with the reaction product obtained in (12). (14) A method in which an electron donor and a titanium compound are further reacted with the reaction product obtained in (11) or (12). (15) A method in which a solid obtained by pulverizing a magnesium compound, preferably an electron donor, and a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. In addition, this method may include a step of pulverizing only the magnesium compound, a complex compound including the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. Examples of the reaction assistant include an organometallic compound and a halogen-containing silicon compound. (16) A method of pulverizing a magnesium compound and then contacting and reacting with a titanium compound. At this time, it is preferable to use an electron donor or a reaction assistant at the time of pulverization and / or contact / reaction. (17) A method of treating the compound obtained in the above (11) to (16) with a halogen, a halogen compound or an aromatic hydrocarbon. (18) A method in which a contact reaction product of a metal oxide, an organomagnesium and a halogen-containing compound is preferably brought into contact with an electron donor and a titanium compound. (19) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium with a titanium compound and / or a halogen-containing hydrocarbon and preferably an electron donor. (20) A method of contacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium with a titanium compound and / or an electron donor. At this time, it is preferable to coexist a halogen-containing compound such as a halogen-containing silicon compound. (21) reacting a magnesium compound in a liquid state having no reducing ability with an organometallic compound to form a solid magnesium compound;
A method in which a metal (aluminum) composite is precipitated, and then an electron donor and a titanium compound are reacted.

The amount of each of the above components used in preparing the titanium catalyst component (A) depends on the preparation method and cannot be specified unconditionally.
The electron donor is used in an amount of 0.01 to 20 mol, preferably 0.1 to 10 mol, and the titanium compound is used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol, per mol. Can be

The thus obtained titanium catalyst component (A) contains magnesium, titanium and halogen as essential components and optionally contains an electron donor. In this titanium catalyst component (A), halogen / titanium (atomic ratio) is about 2 to 200, preferably about 4 to 100,
The electron donor / titanium (molar ratio) is about 0.01 to 10
0, preferably about 0.2-10, magnesium /
Titanium (atomic ratio) is about 1-100, preferably about 2-5
Desirably, it is 0.

When the titanium catalyst component (A) is in a solid state, it is compared with a commercially available magnesium halide.
It contains magnesium halide having a small crystal size and usually has a specific surface area of about 10 m 2 / g or more, preferably about 3 m 2 / g.
0-1000 m2 / g, more preferably about 50-800
m2 / g. And this titanium catalyst component (A)
Since the above-mentioned components are combined to form a catalyst component, the composition does not substantially change by washing with hexane.

The titanium catalyst component (A) used in the present invention
Is, in combination with the organoaluminum compound,
Ethylene polymerization activity is 200 g-polymer / mmol-T
i × time × atm, preferably 500 g-polymer / mmol—Ti × time × atm or more is desirable.

The transition metal imine compound (B) used in the present invention is a compound represented by the following general formula (I).

[0053]

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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 having 1 to 20 carbon atoms.
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, p-toluene sulfonate. Sulfonate groups such as benzoate, 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 monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyls 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.

[0070]

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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, osmium, cobalt, rhodium, and iridium. Preferred are iron and cobalt.

R7 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, 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.

R11 may be the same or different from each other, and may be a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a residue of a heterocyclic compound, 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 the oxygen of the 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, etc., 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) Compounds are more preferred.

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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 groups in which the aforementioned 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 R
20 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. May be.

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 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.

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 sulfonate 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 above-mentioned oxygen-containing group is substituted with sulfur, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate. Sulfonate groups such as benzoate, 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 silyl substituted with monohydrocarbons such as methylsilyl and phenylsilyl; silyl 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; 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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[0183]

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 may be used.

These compounds may be used alone,
Two or more kinds may be used in combination. (C-1) Organometallic compound As the (C-1) organometallic compound used in the present invention,
Specifically, the following Periodic Tables 1 and 2 and 1
An organic metal compound belonging to Group 2 or 13 is used.

[0186] (C-1a) of the general formula _{^{R a s Al (OR b)}} t H u X w ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X represents a halogen atom, and s represents 0 <s
≦ 3, t is 0 ≦ t <3, u is 0 ≦ u <3, w is 0 ≦ w <3
And s + t + u + w = 3. The organoaluminum compound represented by).

[0187] (C-1b) Formula M ² AlR ^a ₄ (wherein, M ² represents Li, Na, and 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:

(C-1c) Formula R ^a R ^b M ³ (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 dialkyl compound of a Group 2 or Group 12 metal represented by a hydrocarbon group, wherein M ³ is Mg, Zn or Cd.

As the organoaluminum compound belonging to the above (C-1a), the following compounds can be exemplified. In the formula _{^{R a x Al (OR b)}} 3-x ( 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, x is preferably a number 1.5 ≦ x ≦ 3.) an organoaluminum compound represented by the general formula R ^a _y AlX _3-y (wherein, R ^a is 1 to carbon atoms 15, preferably 1
4 represents a hydrocarbon group, X represents a halogen atom, and y preferably satisfies 0 <y <3. An organoaluminum compound represented by), the general formula R ^a _z AlH _3-z (wherein, R ^a is the number of carbon atoms 1 to 15, preferably 1 to
4 represents a hydrocarbon group, and z preferably satisfies 2 ≦ z <3. An organoaluminum compound represented by), the general formula _{^{R a e Al (OR b)}} g X f ( wherein, R ^a and Rb, which 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 e represents 0 <
e ≦ 3, g is a number satisfying 0 ≦ g <3, f is a number satisfying 0 ≦ f <3,
And e + g + f = 3. The organoaluminum compound represented by).

More specifically, aluminum compounds belonging to (C-1a) include tri-n-alkylaluminums such as triethylaluminum and tri-n-butylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum -Butylaluminum, tri-2-methylbutylaluminum, tri3-
Methyl butyl aluminum, tri 2-methyl pentyl aluminum, tri 3-methyl pentyl aluminum, tri 4-
Methylpentyl aluminum, Tri 2-methylhexyl aluminum, Tri 3-methylhexyl aluminum, Tri
Tri-branched alkyl aluminum such as 2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum hydride such as diisobutyl aluminum hydride; triisoprenyl aluminum and the like Trialkenyl aluminum; alkyl aluminum alkoxides such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide, and isobutyl aluminum isopropoxide;
Dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; Ra2.5 Al (ORb) 0.5 Alkyl aluminum alkoxylated to: diethyl aluminum (2,6-
Di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6-di-t-butyl-4-methylphenoxide),
Diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,6-di
alkyl aluminum aryloxides such as -t-butyl-4-methylphenoxide); dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide Diethyl aluminum hydride;
Dialkylaluminum hydrides such as dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxy Partially alkoxylated and halogenated alkylaluminums such as bromide can be mentioned.

Also, compounds similar to (C-1a) can be used, and examples thereof include organic aluminum compounds 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 .

Compounds belonging to the above (C-1b) include Li
Al (C_TwoH_Five)_Four, LiAl (C₇H ₁₅)_FourEtc.
be able to.

Other examples of the (C-1) organometallic compound include a compound represented by the general formula (i-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (where x, y and z are positive Is an integer and z ≧ 2x).

Furthermore, (C-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 be used.

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

(C-2) Organoaluminum oxy compound The (C-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 are described above (C
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to -1) can be mentioned.

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 aluminoxane 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.

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

[0205]

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In the formula, R ⁴¹ represents a hydrocarbon group having 1 to 10 carbon atoms. R ⁴² may be the same or different and each has a hydrogen atom, a halogen atom or a carbon atom number of 1 to
Shows 10 hydrocarbon groups.

The boron-containing organoaluminum oxy compound represented by the general formula (V) is represented by the following general formula (V-
An alkylboronic acid represented by 2) and R ⁴¹ -B- (OH) ₂ ... (V-2) (wherein R ⁴¹ represents the same group as described above). The reaction can be carried out in an inert solvent at a temperature of -80 ° C to room temperature for 1 minute to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (V) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. 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.

Specific examples of such an organoaluminum compound to be reacted with an alkylboronic acid are those described above (C
The same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to -1) can be mentioned.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. (C
-2) The organoaluminum oxy compounds are used alone or in combination of two or more.

(C-3) Compound which forms an ion pair by reacting with a transition metal imine compound Compound (C-3) which reacts with a transition metal imine compound (B) used in the present invention to form an ion pair Hereinafter, referred to as "ionized ionic compound."
01950, JP-A-1-50203, JP-A-3-179005, JP-A-3-179006
JP, JP-A-3-207703, JP-A-3-2703
Examples thereof include Lewis acids, ionic compounds, borane compounds, carborane compounds, and the like described in JP 07704, USP-5321106, and the like.

Specifically, as the Lewis acid, BR ₃
(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).

[0214]

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In the formula, R 43 includes H +, carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R44 to R47 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.

[0219] R43 is preferably a carbonium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbonium cation, an N, N-dimethylanilinium cation, or an N, N-diethylanilinium cation.

Examples of ionic compounds include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts,
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, 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, for example, 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 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 boron compounds represented by the following formulas (VII) and (VIII) can also be mentioned.

[0225]

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

[0227]

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Specific examples of the borane compound include, for example, 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-mentioned (C-3) ionized ionic compounds are used alone or in combination of two or more. Further, the catalyst for olefin polymerization according to the present invention comprises the above titanium catalyst component (A), a transition metal imine compound (B),
Along with at least one compound (C) selected from (C-1) an organometallic compound, (C-2) an organoaluminum oxy compound, and (C-3) an ionized ionic compound, if necessary, A particulate carrier (D) can also be used.

(D) Particulate carrier The (D) 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 , Ca
O, ZnO, BaO, ThO _{2 and the} like, 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 -Cr
Examples include ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, and the like. 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
(NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li
_It may contain carbonate, sulfate, nitrate and oxide components such as ₂ O.

The properties of the fine particle carrier (D) 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 (D) 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.

The catalyst for olefin polymerization according to the present invention comprises the above titanium catalyst component (A), a transition metal imine compound (B), (C-1) an organometallic compound, and (C-2) an organoaluminum. It comprises at least one compound (C) selected from oxy compounds and (C-3) ionized ionic compounds, and, if necessary, a particulate carrier (D).

At the time of polymerization, the method of use and the order of addition of each component are arbitrarily selected, and the following methods are exemplified. (1) A method in which the components (A), (B) and (C) are added in any order. (2) A method in which the catalyst component in which the component (B) is carried on the solid component (A) and the component (C) are added in an arbitrary order. (3) A method in which the catalyst component in which the component (C) is supported on the solid component (A) and the component (B) are added in an arbitrary order. (4) A method of adding a catalyst component carrying the components (B) and (C) to the solid component (A). (5) A method in which the catalyst component in which the component (B) is supported on the carrier (D), the component (A) and the component (C) are added in an arbitrary order. (6) A method in which the catalyst component in which the component (C) is supported on the carrier (D), the component (A) and the component (B) are added in an arbitrary order. (7) A method in which the catalyst component in which the component (B) and the component (C) are supported on the carrier (D) and the component (A) are added in an arbitrary order. (8) A method in which the catalyst component carrying component (A) and the component (C) are added in any order to the solid carrying component (B). (9) A method of adding a catalyst component carrying components (A) and (C) to a solid carrying component (B).

In each of the above methods (1) to (9), if necessary, the organosilicon compound represented by the general formula (II-1) or (II-3) and the organic compound represented by the general formula (III) An electron donor such as a polyether compound represented by the formula (1) may be used.

In each of the above methods (1) to (3) and (5) to (8), at least two or more of the respective catalyst components may be brought into contact with each other in advance. The above component (C) is supported
In each of the methods (3), (4), (6), (7), and (9), the unsupported component (C) may be added in any order, if necessary. In this case, the components (C) may be the same or different.

The solid catalyst component in which the component (C) is supported on the component (A), the solid catalyst component in which the component (B) and the component (C) are supported on the component (A), and the component (D) A solid catalyst component having component (B) and component (C) supported thereon,
Component (D) includes component (A), component (B) and component (C)
The olefin may be pre-polymerized in the solid catalyst component on which is carried, and the catalyst component may be further supported on the pre-polymerized solid catalyst component. In the prepolymerization, if necessary, the organosilicon compound represented by the general formula (II-1) or (II-3),
An electron donor such as the polyether compound represented by I) may be used.

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 the 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. Specifically as the inert hydrocarbon medium used in the liquid phase polymerization method, propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; Ethylene chloride, chloro Examples thereof include halogenated hydrocarbons such as benzene and dichloromethane, and mixtures thereof, and olefin itself can be used as a solvent. Among these inert hydrocarbon media, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred. It is also preferable to use an α-olefin, an alicyclic vinyl compound, or a cyclic olefin itself used as a solvent in the polymerization.

When olefin polymerization is carried out using the olefin polymerization catalyst as described above, the titanium catalyst component (A) is usually used in an amount of 10 ^-8 to 10 ^-3 in terms of titanium atom per liter of reaction volume. Mol, preferably 10 ^-7 to 10
^-4 mol, and component (B) is usually 1
It is used in such an amount as to be 0 ^-8 to 10 ^-2 mol, preferably 10 ^-7 to 10 ^-3 mol. The component (B) has a molar ratio ((B) / (A)) of the component (B) to the component (A) (in terms of titanium atom) of usually 0.02 to 100, preferably 0.1 to 100. It is used in such an amount as to be from 0.5 to 50.

The component (C-1) is composed of the component (C-1) and the component (A)
And a molar ratio [(C-1) / M] to all transition metal atoms (M) in the component (B) is usually 0.01 to 5,000, preferably 0.05 to 2,000. Can be

The component (C-2) has a molar ratio of the aluminum atom in the component (C-2) to the total transition metal atoms (M) in the components (A) and (B) [(C-2 ) / M] is usually 10 to 5
000, preferably 20 to 2,000.

The component (C-3) is composed of the component (C-3) and the component (A)
And the molar ratio [(C-3) / M] to all transition metal atoms (M) in component (B) is usually 1 to 10, preferably 1 to 5.

The polymerization temperature of olefin using such an olefin polymerization catalyst is usually -50 to 200 ° C.
Preferably it is in the range of 0 to 170C. The polymerization pressure is usually from normal pressure to 100 kg / cm 2, preferably from normal pressure to 50 k
g / cm @ 2, and 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. Examples of the olefin that can be polymerized by such an olefin polymerization catalyst include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-methyl-1-pentene. 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
Α-olefins having 2 to 20 carbon atoms, such as -hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene;
Aromatic vinyl compounds such as styrene, dimethylstyrenes, allylbenzene, allyltoluenes, vinylnaphthalenes and allylnaphthalenes; vinylcyclohexane,
Alicyclic vinyl compounds such as vinylcyclopentane, vinylcycloheptane and allylnorbornane; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-
Cyclic olefins such as dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,5,9 A chain polyene having 4 to 20 carbon atoms such as -decatriene; and a cyclic polyene such as 5-ethylidene norbornene and dicyclopentadiene.

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

[0249]

The olefin polymerization catalyst according to the present invention has a high polymerization activity and an olefin having a wide molecular weight distribution (co).
A polymer can be obtained, and an olefin copolymer having a narrow composition distribution when two or more olefins are copolymerized can be obtained.

According to the olefin polymerization method of the present invention, an olefin (co) polymer having a high polymerization activity and a wide molecular weight distribution can be obtained, and the composition distribution is narrow when two or more olefins are copolymerized. An olefin polymer can be obtained. Olefin (co) obtained by the method of the present invention
Polymers are excellent in moldability because of their wide molecular weight distribution.

[0251]

[Example 1] [Preparation of titanium catalyst component (A-1)] 5.1 g of commercially available anhydrous magnesium chloride and 194 ml of decane were mixed in 40 parts.
The mixture was charged into a 0 ml glass flask, and 18.8 ml of ethanol was added dropwise with stirring over 10 minutes. After the addition, the mixture was stirred at room temperature for 1 hour. Thereafter, 17.5 ml of diethylaluminum chloride diluted with 20 ml of decane was added dropwise over 1 hour. At this time, the temperature in the system was maintained at 35 to 40 ° C. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour. Subsequently, 70.6 ml of titanium tetrachloride was added dropwise over 30 minutes, and then the temperature was raised to 80 ° C and the mixture was stirred at 80 ° C for 2 hours. The reaction product was filtered through a jacketed glass filter kept at 80 ° C., and washed several times with decane to obtain 4.8% by weight of titanium and 14% by weight of magnesium.
Thus, a solid titanium catalyst component (A-1) having a weight percentage of 57% by weight, chlorine of 57% by weight, aluminum of 2.2% by weight, and an ethoxy group of 9.7% by weight was obtained.

[Polymerization] Cyclohexane 4 was placed in a 1-liter stainless steel autoclave sufficiently purged with nitrogen.
00 ml and then 100 ml of 1-hexene were charged, and the temperature of the system was raised to 60 ° C. Thereafter, 1.0 mmol of methylaluminoxane was converted to aluminum atom, and the titanium catalyst component (A-1) obtained above was converted to titanium atom at 0.0 mmol.
002 mmol and 0.0004 mmol of the transition metal imine compound (B-1) represented by the following formula (a) were injected with ethylene to initiate polymerization. Polymerization was carried out at 70 ° C. for 15 minutes at a total pressure of 8 kg / cm 2 -G while continuously supplying ethylene, and then a small amount of methanol was added by injection to terminate the polymerization. The polymerization reaction solution was treated with a large excess
The resulting polymer was added to a hydrochloric acid solution at 130 ° C. for 12 hours.
Dry under reduced pressure for hours. As a result, [η] is 2.98
10.0 g of polymer having dl / g and Mw / Mn of 11.8
was gotten.

[0253]

Embedded image

[0254]

COMPARATIVE EXAMPLE 1 In the polymerization of Example 1, 1-hexene was not charged and cyclohexane was made up to 500 ml. Then, methylaluminoxane was converted to 0.5 as an aluminum atom without using the titanium catalyst component (A-1). Mmol and the above formula (a)
The polymerization was carried out in the same manner except that the amount of the transition metal imine compound (B-1) was 0.0002 mmol. As a result, 19.9 g of a polymer having [η] of 1.76 dl / g and Mw / Mn of 6.9 was obtained.

[0255]

Comparative Example 2 In the polymerization of Example 1, the transition metal imine compound (B-1) was not used, the titanium catalyst component (A-1) was used in an amount of 0.0004 mmol in terms of titanium atoms, and methylaluminoxane was converted in terms of aluminum atoms. To 0.5 mmol,
Polymerization was carried out in the same manner except that hydrogen was introduced at 2.5 kg / cm 2 -G and the polymerization time was set to 30 minutes. as a result,
10.7 g of a polymer having [η] of 1.97 dl / g and Mw / Mn of 6.9 was obtained.

[0256]

Example 2 In the polymerization of Example 1, a titanium catalyst component
(A-1) is converted to 0.0004 mmol in terms of titanium atom, and the following formula (b) is substituted for the transition metal imine compound (B-1).
The transition metal imine compound (B-2) represented by
Polymerization was carried out in the same manner except that the mmol was used. As a result, [η] was 3.40 dl / g, and Mw / Mn was 8.40 dl / g.
6.80 g of a polymer of 80 were obtained.

[0257]

Embedded image

[0258]

COMPARATIVE EXAMPLE 3 In the polymerization of Example 2, 1-hexene was not charged, cyclohexane was made 500 ml, the titanium catalyst component (A-1) was not used, and methylaluminoxane was converted to aluminum atom by 0.5%. Polymerization was carried out in the same manner except that the amount was changed to mmol. As a result, [η] is 1.4.
Polymer 2.13 with 4 dl / g and Mw / Mn 4.45
g was obtained.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Terunori Fujita 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture F-term (Reference) 4J028 AA02A AB01A AC04A AC05A AC06A AC07A AC45A AC46A AC47A BA01A BA01B BA02A BA02B BA03A BA03B BA04A BA04B BA05A BB00A BB00B BB01A BB01B BB02A BB02B BC01A BC01B BC05A BC06A BC06B BC12A BC12B BC13A BC13B BC15A BC15B BC16A BC16B BC19A BC19B BC24A BC24B BC25A BC25B BC27A BC27B BC29A BC29B BC34A BC39A CA02C CA15A CA16A CA17A CA17B CA25A CA25B CA25C CA26A CA26B CA26C CA27A CA27B CA27C CA28A CA28B CA28C CA29A CA29B CA29C CB09A CB09B CB09C CB23A CB25A CB26A CB27A CB28A CB36A CB43A CB44A CB47A CB49A CB52A CB53A CB56A CB57A CB58A CB63A CB64A CB64B CB65A CB65B CB66A CB68A CB73A CB74A CB87A CB87B CB94A CB94B EA01 EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB16 EB18 EB21 EB26 EC01 EC02 F A01 FA02 FA03 FA04 FA07 FA09 GA04 GA06

Claims (4)

[Claims] 1. A titanium catalyst component comprising (A) magnesium, titanium and a halogen as essential components; (B) a transition metal imine compound represented by the following general formula (I); and (C)
(C-1) an organometallic compound, (C-2) an organoaluminum oxy compound, and (C-3)
An olefin polymerization catalyst comprising at least one compound selected from compounds which form an ion pair by reacting with a transition metal imine compound (B); (Wherein, M represents a transition metal atom belonging to Groups 8 to 11 of the periodic table,
R ^{1 to} R ⁴ 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,
R ⁵ and R ⁶ 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, and a sulfur-containing group. R ¹ , R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁵
May be linked to each other to form a ring, and R ² and R ⁶
May be linked to each other to form a ring, and R ¹ and R ³
May be linked to each other to form a ring, and R ² and R ⁴
May be linked to each other to form a ring, and R3 and R4
May be connected to each other to form a ring, n represents a valence of M, X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a carbon group having 1 to 20 carbon atoms. And when 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 of Group 15 or 16 of the periodic table. ) 2. The method according to claim 1, wherein the transition metal imine compound (B) is a compound represented by the following general formula (Ia). 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 method according to claim 1, wherein the transition metal imine compound (B) is a compound represented by the following general formula (Ib). 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. ) 4. A method for polymerizing an olefin, comprising polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 3.