JPH09278824A - Olefin polymerization catalyst and method of polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin polymerization catalyst which has a high polymerization activity and can give an olefin (co)polymer with a wide molecular weight distribution by combining a titanium-base catalyst component, a transition metal compound and other compound. SOLUTION: This catalyst is formed from a titanium-base catalyst component (A) containing magnesium, titanium and a halogen as the essential constituents, a transition metal compound (B) of formula I wherein M is any one of groups 8 to 10 transition metal atoms; X<1> and X<2> are each N or P; R<1> and R<2> are each H or a hydrocarbon group; m and n are each 1 or 2; R<3> is a group of formula II (wherein R<6> , R<7> , R<61> , R<62> , R<71> and R<72> are the same as R<1> ); and R<4> and R<5> are each H, hologeno, a hydrocarbon group,-OR<8> ,-SR<9> ,-N(R<10> )2 or-P(R<11> )2 [wherein R<8> to R<11> are each (cyclo)alkyl, aryl, aralkyl or an organic silyl group]}, at least one compound (C) selected among organoaluminumoxy compounds, alkyl borate derivatives, and compounds that react with a transition metal compound to form an ion pair, and if necessary an organometal compound (D).

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.

Recently, as a new olefin polymerization catalyst, an olefin polymerization catalyst comprising a nickel compound or a palladium compound and a cocatalyst such as an aluminoxane or an ionic compound has been proposed (J. Am. Chem. Soc. 1995, 1
17,6414-6415).

By the way, polyolefins such as ethylene polymers are excellent in mechanical strength and chemical resistance.
It is used as various molding materials. However, a catalyst composed of the above nickel compound or palladium compound and a co-catalyst has a high polymerization activity, but an olefin polymer obtained by using this has a narrow molecular weight distribution and does not necessarily have good moldability. is not. Therefore, there has been a demand for improvement of a catalyst comprising a nickel compound or a palladium compound and a cocatalyst so that an olefin polymer having a wide molecular weight distribution and excellent moldability can be obtained without impairing high polymerization activity.

[0006]

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 olefins using a catalyst having such good properties.

[0008]

The olefin polymerization catalyst according to the present invention comprises (A) a titanium catalyst component containing magnesium, titanium and halogen as essential components, and (B) a periodic table No. 8 represented by the following general formula (I). A compound which forms an ion pair by reacting with a transition metal compound of Group 10 to (C) (C-1) organoaluminum oxy compound, (C-2) alkylboronic acid derivative and (C-3) transition metal compound It is characterized by comprising at least one kind of compound selected from the following, and optionally (D) an organometallic compound.

[0009]

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(In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R 1
¹ and R ² may be the same or different from each other,
Represents a hydrogen atom or a hydrocarbon group, m and n may be the same or different from each other, and 1 or 2,
R is a number satisfying the valences of X ¹ and X ² , respectively, and R
³ is

[0011]

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(However, R ⁶ , R ⁷ , R ⁶¹ , R ⁶² , R ⁷¹
And R ^{72, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group. ), R ⁴ and R ^{5, which} may be the same or different, are each a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ , —SR ⁹ ,
-N (R ¹⁰⁾ ₂ or -P (R ¹¹⁾ ₂ (provided that, R ⁸ ~
R ¹¹ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ^{10 s} or R ^{11 s} may be linked to each other to form a ring. )
And R ⁴ and R ⁵ may be linked to each other to form a ring, and R ¹ , R ² , R ⁶ (or R ⁶¹ ,
Two or more of R ⁶² ) and R ⁷ (or R ⁷¹ , R ⁷² ) may be linked to each other to form a ring. In the present invention, the transition metal compound represented by the general formula (I) is preferably a compound represented by the following general formula (I ′).

[0013]

[Chemical 6]

(In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R 1
¹ and R ² may be the same or different from each other,
A hydrogen atom or a hydrocarbon group, R ⁶ and R ⁷ are
They may be the same or different from each other and represent a hydrogen atom or a hydrocarbon group, and R ⁴ and R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ , —SR. ^9, -N (R ¹⁰⁾ ₂ or -P
(R ¹¹ ) ₂ (wherein R ^{8 to} R ¹¹ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ^{10 s} or R ^{11 s} are linked to each other to form a ring. R ⁴ and R ^4
5 may combine with each other to form a ring, and R ¹ , R
^Two or more of ² , R ⁶ and R ⁷ may be linked to each other to form a ring. The olefin polymerization catalyst of the present invention has a high polymerization activity, a wide molecular weight distribution, and an olefin (co) polymer having a narrow composition distribution when two or more olefins are polymerized.

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

[0016]

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

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

The olefin polymerization catalyst according to the present invention comprises (A) a titanium catalyst component containing magnesium, titanium and halogen as essential components, (B) a transition metal compound of Groups 8 to 10 of the periodic table, and (C). (C-1) an organoaluminum oxy compound, (C-2) an alkylboronic acid derivative, and (C-3) at least one compound selected from compounds that form an ion pair by reacting with a transition metal compound; Accordingly, it is formed from (D) an organometallic compound.

First, each catalyst component forming the olefin polymerization catalyst of the present invention will be described. (A) Magnesium, titanium and halogen are essential components
The titanium catalyst component used in the present invention (A) is a titanium catalyst component containing magnesium, titanium and halogen as essential components (hereinafter referred to as “titanium catalyst component”). And 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) Used for preparing titanium catalyst component
Specifically as a titanium compound, for example, represented by the following formula
Tetravalent titanium compound. Ti (OR)_gX_4-n (Wherein, R represents a hydrocarbon group, X represents a halogen atom)
And n is 0 ≦ n ≦ 4) As such a titanium compound, specifically, TiCl
_Four, TiBr_Four, TiI_FourTetrahalogenated titanium such as
Ti (OCH_Three) Cl_Three, Ti (OC_TwoH_Five) C
l_Three, Ti (On-C_FourH₉) Cl _Three, Ti (OC_TwoH_Five)
Br_Three, Ti (O-iso-C_FourH₉) Br_ThreeSuch as trihalo
Alkoxy titanium genide; Ti (OCH_Three)_TwoCl_Two,
Ti (OC_TwoH_Five)_TwoCl_Two, Ti (On-C_FourH₉)_TwoCl
_Two, Ti (OC_TwoH_Five)_TwoBr_TwoDihalogenated dia
Lucoxy titanium; Ti (OCH_Three)_ThreeCl, Ti (OC_Two
H_Five)_ThreeCl, Ti (On-C_FourH₉)_ThreeCl, Ti (OC_Two
H_Five)_ThreeMonohalogenated trialkoxy titanium such as Br
Ti (OCH_Three)_Four, Ti (OC_TwoH_Five)_Four, Ti
(O-n-C_FourH₉)_Four, Ti (O-iso-C_FourH₉)_Four, Ti
(O-2-ethylhexyl)_FourSuch as tetraalkoxy
And the like.

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.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. 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; magnesium methoxy chloride, magnesium ethoxy chloride and magnesium isopropoxy chloride. Alkoxy magnesium halides such as butoxy magnesium chloride and octoxy magnesium chloride; allyoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy Alkoxy magnesium such as magnesium; Phenoxy magnesium, dimethylphenoxy magnesium, etc. And magnesium carboxylate such as magnesium laurate and magnesium stearate.

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

A magnesium compound having no reducing property is
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 reducing magnesium compound and non-reducing magnesium compound, the magnesium compound may be a complex compound of the above-mentioned magnesium compound and another metal, a complex compound or another metal compound. 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 mentioned above can be used. In the finally obtained titanium catalyst component (A), halogen-containing magnesium is used. It is preferable to take the form of a compound, and therefore, when a halogen-free magnesium compound is used, it is preferable to react it with a halogen-containing compound during the preparation.

Among the above-mentioned magnesium compounds, a magnesium compound having no reducing property is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxy magnesium chloride, and aryloxy magnesium chloride are particularly preferable.

When 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 polyvalent carboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferable example.

[0033]

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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 , 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 ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methyl glutarate, diethyl methyl malonate, diethyl ethyl malonate, and isopropyl malonate. Acid diethyl, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butylmaleate, diethyl butylmaleate, β-methylglutar Aliphatic polycarboxylic acid esters such as diisopropyl acid acid, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconic acid, dioctyl citraconic acid; diethyl 1,2-cyclohexanecarboxylic acid, 1,2-sicyl Alicyclic polycarboxylic acid esters such as diisobutyl hexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Di-n-propyl phthalate, Di-isopropyl phthalate, Di-n-butyl phthalate, Diisobutyl 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; 3,4-furandicarboxylic acid, etc. 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. Examples thereof include long chain dicarboxylic acid esters.

In the present invention, an organic silicon compound represented by the following general formula (II-1) and a polyether compound represented by the following general formula (III) can be used as the electron donor.

[0038] In _{^{R p n -Si- (OR q)}} 4-n ... (II-1) ( wherein, n is 1, 2 or 3, when n is 1, R
^p represents a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one of R ^{p represents} a secondary or tertiary hydrocarbon group, and the other represents a hydrocarbon group. ^{May be} the same or different, and ^Rq has 1 to 1 carbon atoms.
When the hydrocarbon group is 4 and 4-n is 2 or 3, R ^q may be the same or different. In the silicon compound represented by the formula (II-1), as the secondary or tertiary hydrocarbon group, a cyclopentyl group,
Examples thereof include a cyclopentenyl group, a cyclopentadienyl group, these groups having a substituent, and a hydrocarbon group in which carbon adjacent to Si is secondary or tertiary.

Of these, dimethoxysilanes, especially dimethoxysilanes represented by the following general formula (II-2), are preferable.

[0040]

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(In the formula, R ^p and R ^s are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or Si.
Represents a hydrocarbon group in which the carbon adjacent to is a secondary or tertiary carbon. Specific examples of the organosilicon compound represented by the general formula (II-2) include dicyclopentyldimethoxysilane and di-t
-Butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl)
Examples include dimethoxysilane and di-t-amyldimethoxysilane.

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

[0043]

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In the formula, n is an integer of 2≤n≤10, and R
^{1 to} R ²⁶ are carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
At least one selected from phosphorus, boron and silicon
R ^{1 to} R ²⁶ , preferably R ^{1 to} R ^2n, may together form a ring other than a benzene ring, and may have a substituent other than a carbon atom in the main chain. Atoms may be included.

As the polyether compound as described above, 1,3-diethers are preferably used, and particularly 2,2-diethers are used.
Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxy Propane, 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 titanium compound, the magnesium compound and the electron donor as described above are brought into contact with each other, a carrier-supported titanium catalyst component (A) is prepared by using a particulate carrier (E) as described later. You 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 known methods. You can The above components are, for example, silicon, phosphorus,
The contact may be performed in the presence of another reactant such as aluminum.

The specific method for producing the titanium catalyst component (A) will be briefly described below by giving some 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 aid during 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 of contacting a reaction product of a metal oxide, an organomagnesium, and a halogen-containing compound, preferably 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 with 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-mentioned components used in preparing the titanium catalyst component (A) varies depending on the preparation method and cannot be specified unconditionally. For example, magnesium compound 1
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 titanium catalyst component (A) thus obtained 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
It is preferably 0.

When the titanium catalyst component (A) is in a solid state, when compared with the 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.
0~1000m ² / g, more preferably about 50 to 800
m ² / 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.

Titanium catalyst component (A) used in the present invention
It is desirable that the ethylene polymerization activity in combination with organoaluminum is 200 g-polymer / mmol-Ti x time x atm, preferably 500 g-polymer / mmol-Ti x time x atm or more.

(B) Transition metal compounds of Groups 8 to 10 of the periodic table
Objects (B) used in the present invention the periodic table transition metal compound of Groups 8-10 is a transition metal compound represented by the following general formula (I).

[0055]

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In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, preferably nickel, palladium or platinum. X ¹ and X ² may be the same or different from each other and represent a nitrogen atom or a phosphorus atom.

R ¹ and R ^{2, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
sec-Butyl group, tert-butyl group, pentyl group, hexyl group, etc., linear or branched alkyl group having 1 to 20 carbon atoms; phenyl group, naphthyl group, etc., having 6 to 20 carbon atoms Group; these aryl groups have 1 to 5 substituents such as an alkyl group having 1 to 20 carbon atoms.
Examples thereof include a substituted aryl group substituted with an individual.

M and n, which may be the same or different, are 1 or 2 and are numbers satisfying the valences of X ¹ and X ² , respectively. R ³ is

[0059]

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Is shown. However, R ⁶ , R ⁷ , R ⁶¹ ,
R ⁶² , R ⁷¹ and R ^{72, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group similar to R ¹ and R ² .

The above R ¹ , R ² , R ⁶ (or R ⁶¹ ,
R ⁶² ) and R ⁷ (or R ⁷¹ , R ⁷² ) may form a ring by connecting two or more of them, preferably adjacent groups, to each other.

R ⁴ and R ^{5, which} may be the same or different, each represents a hydrogen atom, a halogen atom or a hydrocarbon group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

Specific examples of the hydrocarbon group include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and benzyl groups such as R ¹ and R ² described above. 7 to 20 aralkyl groups and the like can be mentioned. One or more substituents such as the alkyl group having 1 to 20 carbon atoms may be substituted on the aryl group and the aralkyl group.

Further, as R ⁴ and R ⁵ , -OR ⁸ ,
-SR ^9, a group represented by -N (R ¹⁰⁾ ₂ or -P (R ¹¹⁾ ₂ is also shown. R ^{8 to} R ¹¹ are the same as R ¹ and R ² described above.
Similarly, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms such as a cyclohexyl group, and a carbon number 7 to 7 such as a benzyl group. 20 aralkyl groups; organic silyl groups such as methylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group and triethylsilyl group. The aryl group and the aralkyl group may be substituted with one or more substituents such as the alkyl group having 1 to 20 carbon atoms. And R
^10's or R ^11's may be linked to each other to form a ring.

R ⁴ and R ⁵ may be linked to each other to form a ring. The transition metal compound represented by the general formula (I) is preferably a compound represented by the following general formula (I ′).

[0066]

[Chemical 12]

(Wherein M, X ¹ , X ² , R ¹ , R ² and R
⁴ , R ⁵ , R ⁶ and R ⁷ are the same as in the general formula (I). ) Specific examples of the transition metal compound represented by the general formula (I ′) include the following compounds.
In the following formula, iPr represents an isopropyl group.

[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

[Chemical 21]

[0077]

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In addition to the above, examples of the transition metal compound represented by the general formula (I ') include compounds in which palladium or nickel in the above compounds is replaced by platinum.

In addition to the above, examples of the compound represented by the general formula (I) include the following compounds. In the following formula, iPr represents an isopropyl group.

[0080]

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[0081]

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In addition to the above, examples of the transition metal compound represented by the general formula (I) include compounds in which palladium or nickel in the above compounds is replaced by platinum.

The above transition metal compounds may be used alone or in combination of two or more. (C-1) Organoaluminum Oxy Compound The (C-1) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or as exemplified in JP-A-2-78687. It may be a benzene-insoluble organoaluminum oxy compound.

The 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 organometallic 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 when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and tri-n-.
Butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, trialkyl aluminum such as tridecyl aluminum, tricyclohexyl aluminum, tricyclooctyl aluminum, etc. Dialkyl aluminum halides such as tricycloalkyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, dialkyl aluminum hydrides such as diethyl aluminum hydride, diisobutyl aluminum hydride, dimethyl aluminum methoxide, diethyl aluminum ethoxy. Dialkylaluminum alkoxides such as, such as dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. Further, as an organoaluminum compound used for preparing aluminoxane, isoprenylaluminum represented by the following general formula can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z (IV) (In the formula, x, y, and z are positive numbers, and z ≧ 2x.) Such organoaluminum compounds may be used alone or in combination of two or more.

As the solvent used for the preparation of aluminoxane, 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 light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. 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, it is insoluble or sparingly soluble in benzene.

The above-mentioned (C-1) organoaluminum oxy compounds may be used alone or in combination of two or more. (C-2) Alkylboronic Acid Derivative Examples of the alkylboronic acid derivative (C-2) used in the present invention include compounds represented by the following general formula (V).

[0092]

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In the formula, R ¹² represents a hydrocarbon group having 1 to 10 carbon atoms. R < ¹³ >, which may be the same or different, each represents a hydrogen atom, a halogen atom, a siloxy group, a lower alkyl group-substituted siloxy group or a hydrocarbon group having 1 to 10 carbon atoms.

The alkylboronic acid derivative (B-2) represented by the general formula (V) includes an alkylboronic acid represented by the following general formula (VI) and R ¹² -B- (OH) ₂ (VI) (In the formula, R ¹² represents the same group as described above.) Reacting with an organoaluminum compound in an inert solvent in an inert gas atmosphere at a temperature of −80 ° C. to room temperature for 1 minute to 24 hours. Can be manufactured by

Specific examples of the alkylboronic acid represented by the general formula (VI) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n. -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Of these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferable. These may be used alone or in combination of two or more.

The organoaluminum compound to be reacted with the alkylboronic acid is represented by the following general formula (VII-
Examples thereof include organoaluminum compounds represented by 1), (VII-2) and (VII-3).

(R ¹³ ) _3-p- Al-Y _p (VII-1) (R ¹³ ) _3-p- Al- [OSi (R ¹⁴ ) ₃ ] _p (VII-2) (R ¹³ ). _{2 -Al-O-Al- (R} 13) 2 ... (VII-3) ( in the formula, Y is a hydrogen atom or a halogen atom, R ¹⁴ is
A hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms, p is 0 ≦ p <3, and R ¹³ is the same group as described above. ) Specific examples of the organoaluminum compounds represented by the general formulas (VII-1), (VII-2) and (VII-3) include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and triisopropylaluminum.
n-butyl aluminum, triisobutyl aluminum,
Trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums, tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums, dimethylaluminum. Chloride, diethylaluminum chloride,
Dialkylaluminum halides such as diethylaluminum bromide and diisobutylaluminum chloride;
Dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; and dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

The above (C-2) alkylboronic acid derivatives may be used alone or in combination of two or more. (C-3) Reaction to form an ion pair by reacting with a transition metal compound
The compound (C-3) (hereinafter, referred to as “ionized ionic compound”) that reacts with the transition metal compound used in the present invention to form an ion pair reacts with the transition metal compound (B). Compounds that form ion pairs, and examples of such compounds include JP-A-1-501950 and JP-A-1
-502036, JP 3-179005, JP 3-179006, and 3-207.
703, JP-A-3-207704, US-
Examples thereof include Lewis acids, ionic compounds, borane compounds and carborane compounds described in Japanese Patent No. 547718.

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

Examples of the ionic compound include compounds represented by the following general formula (VIII).

[0102]

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In the formula, R ¹⁵ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{16 to} R ^{19, which} may be the same or different, are organic groups, preferably aryl groups or substituted aryl groups. Specific examples of the carbonium cation include triphenylcarbonium cation, tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and other trisubstituted carbonium cations.

Specific examples of the ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-diethylaniline. Nium cation, N,
N, N- such as N-2,4,6-pentamethylanilinium cation
Dialkylanilinium cation; di (isopropyl)
Examples thereof include dialkylammonium cations such as ammonium cation and dicyclohexylammonium cation.

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

R ¹⁵ is preferably a carbonium cation, an ammonium cation or the like, particularly preferably a triphenylcarbonium cation or an N, N-diethylanilinium cation.

As the ionic compound, a boron compound represented by the following formula (IX) is preferable.

[0109]

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(In the formula, Et represents an ethyl group.) Further, examples of the ionic compound include a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, and a triarylphosphonium salt. You can also

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron and trimethylammonium tetra (p). -Tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (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-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, Examples include 4,6-pentamethylanilinium tetra (phenyl) boron.

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,
Examples also include N, N-diethylanilinium pentaphenylcyclopentadienyl complex and a boron compound represented by the following formula (X).

[0115]

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

Specific examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14) and dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodeca hydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane (13), 2,
7-dicarbaundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane, dodecahydride-11-methyl-2,7-dicarbaundecaborane, tri (n-butyl) ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarbaundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarbaundecaborate (12),
Tri (n-butyl) ammonium dodeca hydride-8-
Methyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate Salts of anions such as; tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) 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-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (N-Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarbaundecaborate) 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-
Examples thereof include salts of metal carborane anions such as carbaundecaborate) nickelate (IV).

The above-mentioned (C-3) ionized ionic compound is used alone or in combination of two or more kinds. The catalyst for olefin polymerization according to the present invention includes the titanium catalyst component (A), a transition metal compound of Group 8 to 10 of the periodic table (B), an organoaluminum oxy compound (C-1),
-2) at least one compound (C) selected from alkylboronic acid derivatives and (C-3) ionized ionic compounds
At the same time, if necessary, an organometallic compound (D), a particulate carrier (E), etc., which will be described later, can be used.

(D) Organometallic compound As the (D) organometallic compound used as necessary in the present invention, specifically, the following organometallic compounds of Groups 1, 2 and 12 and 13 of the periodic table. A compound is used.

[0120] (D-1) In the general formula _{^{R a m Al (OR b)}} n H p X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms from 1 to 15 , Preferably 1 to 4 hydrocarbon groups, X is a halogen atom, and m is 0 <
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is 0 ≦ q
<3, and m + n + p + q = 3. The organoaluminum compound represented by).

(D-2) General formula M ² AlR ^a ₄ (In the formula, M ² represents Li, Na and K, and R ^a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. A complex alkylated product of a Group 1 metal and aluminum.

(D-3) Formula R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different from each other, and have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). A dialkyl compound of a Group 2 or Group 12 metal, which represents a hydrocarbon group, and M ³ is Mg, Zn or Cd).

Examples of the organoaluminum compound belonging to the above (D-1) include the following compounds. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3.) an organoaluminum compound represented by the general formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1 to
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organoaluminum compound represented by), the general formula R ^a _m AlH _3-m (wherein, R ^a is the number of carbon atoms 1 to 15, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by), the general formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, Preferably, it represents a hydrocarbon group of 1 to 4, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is 0 ≦ n <3, q is a number 0 ≦ q <3,
And m + n + q = 3. The organoaluminum compound represented by).

Specific examples of the aluminum compound belonging to (D-1) include tri-n-alkylaluminum such as triethylaluminum and tri-n-butylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-aluminum. -Butyl aluminum, tri 2-methylbutyl aluminum, tri 3-
Methyl butyl aluminum, tri 2-methyl pentyl aluminum, tri 3-methyl pentyl aluminum, tri 4-
Methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, 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, isobutyl aluminum isopropoxide;
Dialkyl aluminum alkoxides such as diethyl aluminum ethoxide and dibutyl aluminum butoxide; alkyl aluminum sesqui alkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; parts having an average composition represented by R ^a _2.5 Al (OR ^b ) _0.5 Alkyloxylated aluminum; Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide;
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide Diethyl aluminum hydride;
Dialkyl aluminum hydrides such as dibutyl aluminum hydride; Other partially hydrogenated alkyl aluminums such as ethyl aluminum dihydride, alkyl aluminum dihydrides such as propyl aluminum dihydride; ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, ethyl aluminum ethoxy Mention may be made of partially alkoxylated and halogenated alkylaluminum such as bromide.

A compound similar to (D-1) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

Examples of compounds belonging to the above (D-2) include LiAl (C ₂ H ₅ ) ₄ LiAl (C ₇ H ₁₅ ) ₄ .

[0127] Besides, as the organic metal compound (D), the general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y and z are positive numbers And z ≧ 2x), it is also possible to use isoprenylaluminum.

In addition to the above, the organometallic compound (D)
As, methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, It is also possible to use diethyl magnesium, dibutyl magnesium, butyl ethyl magnesium and the like.

It is also possible to use a compound capable of forming 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.

The organometallic compound (D) used in the present invention is preferably an organoaluminum compound. Such an organometallic compound (D) acts as an alkylating agent, and R ⁴ and / or R bound to the transition metal (M) in the transition metal compound (B) represented by the general formula (I) is When R ⁵ is an atom or a group other than an alkyl group, for example, a halogen atom such as chlorine or bromine; a group such as an alkoxy group such as a methoxy group, an ethoxy group or a butoxy group, these are substituted with an alkyl group. The alkyl group-substituted transition metal compound (B) reacts with the component (C), particularly the component (C-3), to form an ionic complex having high catalytic activity.

The (D) organometallic compound is a scavenger.
It also acts as a jar and removes water and other impurities from the system.
Since the reaction system is removed to keep the system clean, the catalyst activity is stable and highly active.
The effect of being able to express is obtained. this
Action binds to transition metal (M) in transition metal compound (B)
Doing R^FourAnd / or R^FiveIs an alkyl group
Is also expressed. Therefore, the organometallic compound (D) is
Transition gold in transition metal compound (B) represented by general formula (I)
R bound to genus (M)^FourAnd / or R ^FiveIs al
When used together with a transition metal compound (B) which is a kill group
Also, the same effect as described above can be obtained.

The (D) organometallic compound as described above is 1
They may be used alone or in combination of two or more.(E) Fine particle carrier (E) Fine particle carrier used as necessary in the present invention
Is an inorganic or organic compound having a particle size of 10 to 3
00 μm, preferably 20-200 μm granular or
Is used as a fine solid. Of these, inorganic compounds
Is preferably a porous oxide, specifically, SiO 2_Two,
Al_TwoO_Three, MgO, ZrO, TiO_Two, B_Two O_Three, Ca
O, ZnO, BaO, ThO_TwoOr a mixture of these
Compound, eg SiO_Two-MgO, SiO_Two-Al_Two O_Three,
SiO_Two-TiO_Two, SiO_Two-V_TwoO_Five, SiO_Two-Cr
_TwoO_Three, SiO_Two-TiO_Two-It is possible to exemplify MgO
Wear. Among these SiO_TwoAnd Al_Two O_ThreeConsists of
Mainly contains at least one component selected from the group
Is preferred.

The above inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ S
O ₄ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg
(NO ₃ ) ₂ , Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, L
It may contain carbonate, sulfate, nitrate and oxide components such as i ₂ O.

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

Further, as the fine particle carrier (A) which can be used in the present invention, a granular or fine particle solid of an organic compound having a particle diameter in the range of 10 to 300 μm can be mentioned. 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 olefin polymerization catalyst according to the present invention comprises the titanium catalyst component (A) as described above and Periodic Table Nos. 8 to 10.
Group transition metal compound (B), (C-1) organoaluminum oxy compound, (C-2) alkylboronic acid derivative and (C
-3) At least one selected from ionized ionic compounds
It comprises a seed compound (C) and, if necessary, an organometallic compound (D) and a particulate carrier (E).

At the time of polymerization, the method of using each component and the order of addition are arbitrarily selected, but 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 any order. (4) A method of adding a catalyst component carrying the components (B) and (C) to the solid component (A). (5) A method of adding the catalyst component in which the component (B) is supported on the carrier (E), the component (A) and the component (C) in any order. (6) A method of adding the catalyst component in which the component (C) is supported on the carrier (E), the component (A) and the component (B) in any order. (7) A method of adding the catalyst component in which the component (B) and the component (C) are supported on the carrier (E) and the component (A) in any 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).

In each of the above methods (1) to (8), the component (D) may be used if necessary. Further, 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 in the component (A), and the component (E) in the component (E). The solid catalyst component carrying B) and component (C) may be prepolymerized with an olefin.

Further, in the present invention, after the components (B) and (C) and, if necessary, the component (D) are brought into contact with each other in advance,
The contact product and the component (A) may be added to the polymerization vessel.
It is presumed that when the component (B) and the component (C) and, if necessary, the component (D) are brought into contact with each other in advance, an ionic coordination compound represented by the following general formula (XI-1) is formed.

[0140]

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(In the formula, M, X ¹ , X ² , R ¹ , R ² ,
m and n are the same as those in the general formula (I), R ²¹ represents a hydrocarbon group, and Z is (C-1) an organoaluminumoxy compound, (C-2) an alkylboronic acid derivative and ( C-3) A molecule formed of at least one compound (C) selected from ionized ionic compounds. ) In the general formula (XI-1), R ²¹ represents the general formula (I).
A hydrocarbon group of R ⁴ or R ⁵ (for example, an alkyl group)
Or an alkyl group introduced by the (D) organometallic compound.

In the general formula (XI-1), Z is a molecule formed from the component (C) upon contact between the component (B) and the component (C) and, if necessary, the component (D). , For example, an anion forming the above-mentioned (C-3) ionized ionic compound, and specific examples thereof include the following formula (XII)
A boron compound represented by

[0143]

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The boron compound represented by the formula (XII) is a molecule formed from the boron compound represented by the formula (IX). Specific examples of Z other than the above include tetrakis (pentafluorophenyl) borate, tetra (phenyl) boron, and the like.

The ionic coordination compound represented by the general formula (XI-1) is an ether compound formed from the component (C) upon contact between the transition metal compound (B) and the component (C). (Ether molecule) may coordinate with the transition metal represented by M. Such an ionic coordination compound is represented by the following general formula (XI-2).

[0146]

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(Wherein M, X ¹ , X ² , R ¹ , R ² ,
m and n are the same as those in the general formula (I), R ²¹ and Z are the same as those in the general formula (XI-1), and R ²² is the transition metal compound (B) and component (C). With contact with (C)
The ether compound (ether molecule) formed from the components is shown. ) Specific examples of the ether compound (ether molecule) represented by R ²² in the general formula (XI-2) include dimethyl ether, diethyl ether, dipropyl ether,
Dibutyl ether and the like.

Specific examples of the ionic coordination compound represented by the general formula (XI-2) include ionic coordination compounds represented by the following formula.

[0149]

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(In the formula, iPr represents an isopropyl group and Et represents an ethyl group.) The component (B), the component (C) and, if necessary, the component (D) are brought into contact with each other in advance, and the general formula (XI- 1) or (XI-2) to form an ionic coordination compound, component (B) and component (C), and optionally component (D) in the reaction medium from -120 to +20. C, preferably -80 to -20
The reaction is carried out at 0 ° C. for 5 minutes to 100 hours, preferably 30 minutes to 5 hours.

As the reaction medium, inert hydrocarbons such as hexane, heptane, octane, cyclohexane, mineral oil, benzene, toluene and xylene; halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane and chlorobenzene can be used. .

Further, in the present invention, when the component (B) and the component (C) and, if necessary, the component (D) are brought into contact with each other in advance, an alkyl (meth) acrylate can be allowed to coexist. In this case, it is preferable to use the (C-3) ionized ionic compound as the component (C).

Examples of the (meth) acrylic acid alkyl ester include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and the like can be mentioned.

The component (B) and the component (C) and, if necessary, the component (D) are brought into contact with each other in the presence of an alkyl (meth) acrylic acid ester to give a compound represented by the following general formula (XI-3). It is speculated that an ionic coordination compound is formed.

[0155]

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(Wherein M, X ¹ , X ² , R ¹ , R ² ,
m and n are the same as in the general formula (I), Z is the same as in the general formula (XI-1), R ²³ represents a residue of a hydrocarbon group, and R ²⁴ and R ²⁵ Shows a part of the residue of (meth) acrylic acid alkyl ester. In the general formula (XI-3), R ²³ is the hydrocarbon group (for example, the residue of an alkyl group) of R ⁴ or R ^{5 in} the general formula (I), or the organic metal (D). It is the residue of an alkyl group introduced by a compound.

Specific examples of the group represented by R ²³ include the following:

[0158]

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And the like. In the general formula (XI-3), R ²⁴ and R ²⁵ are residues formed by the (meth) acrylic acid alkyl ester upon contact between the transition metal compound (B) and the (meth) acrylic acid alkyl ester. Is part of.

Specific examples of the group represented by R ²⁴ include

[0161]

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And the like. Specific examples of the group represented by R ²⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert.
-Butyl group, 2-ethylhexyl group, etc. has 1 carbon atom
~ 20 alkyl groups and the like.

Specific examples of the ionic coordination compound represented by the general formula (XI-3) include ionic coordination compounds represented by the following formula.

[0164]

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(In the formula, iPr represents an isopropyl group.) The component (B) and the component (C) and, if necessary, the component (D) are brought into contact with each other in the presence of the (meth) acrylic acid alkyl ester, and In order to form the ionic coordination compound represented by the general formula (XI-3), the component (B) and the component (C) in the coexistence of the (meth) acrylic acid alkyl ester, and optionally the component (D) ) In the same reaction medium as described above, from -120 to
+ 40 ° C, preferably -80 to 0 ° C for 5 minutes to 100
The reaction is carried out under the condition of time, preferably 30 to 5 hours.

The amount of the (meth) acrylic acid alkyl ester used is such that the molar ratio of the (meth) acrylic acid alkyl ester to the component (B) is usually 0.3 to 3, preferably 0.8.
It is preferable to set to 1.1.

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 above olefin polymerization catalyst.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. As the inert hydrocarbon medium used in the liquid phase polymerization method, specifically, propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene; Ethylene chloride, chlorine Examples thereof include halogenated hydrocarbons such as benzene and dichloromethane, or a mixture thereof, and the olefin itself can be used as a solvent.

When the olefin polymerization is carried out using the above-mentioned olefin polymerization catalyst, the titanium catalyst component (A) is usually 10 ^-8 to 10 ^-3 in terms of titanium atom per 1 liter of reaction volume. Mol, preferably 10 ⁻⁷ to 10
^-4 mol, and component (B) is usually 1
It is used in an amount of 0 ^-8 to 10 ^-3 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) and the component (C-2) are the components (C-
1) or the molar ratio of aluminum atoms in the component (C-2) to all transition metal atoms (M) in the components (A) and (B) [(C-1) / M or (C -2) / M] is usually 1
It is used in an amount of 0 to 5000, preferably 20 to 2000. The component (C-3) has a molar ratio [(C-3) / M] of the component (C-3) to all the transition metal atoms (M) in the components (A) and (B) is usually 1-10, preferably 1
Used in an amount such that

The component (D) used as required is a molar ratio [(D) / M] of the component (D) and all transition metal atoms (M) in the components (A) and (B). But usually 0.0
It is used in an amount of 1 to 5000, preferably 0.05 to 2000.

The olefin polymerization temperature using such an olefin polymerization catalyst is usually -50 to 200 ° C.
It is preferably in the range of 0 to 170 ° C. The polymerization pressure is usually atmospheric pressure to 100 kg / cm ² , preferably atmospheric pressure to 50 k.
It is under the condition of 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 allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. Examples of the olefin that can be polymerized by such an olefin polymerization catalyst include α-olefins having 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; a cyclic olefin having 3 to 20 carbon atoms, for example, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
Examples include a, 5,8,8a-octahydronaphthalene. Further, styrene, vinylcyclohexane, diene and the like can be used.

[0174]

EFFECT OF THE INVENTION The olefin polymerization catalyst according to the present invention has a high polymerization activity, a broad molecular weight distribution, and an olefin (co) polymer having a narrow composition distribution when two or more olefins are copolymerized. You can

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

[0176]

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

In this Example, the molecular weight distribution (Mw
/ Mn) is 140% with o-dichlorobenzene as a solvent.
It measured and determined by gel permeation chromatography (GPC) at ° C.

[0178]

Example 1 [Preparation of titanium catalyst component (a)] Commercially available anhydrous magnesium chloride (5.1 g) and decane (194 ml) were placed in a 400 ml glass flask, and ethanol (18.8 m) was stirred with stirring.
1 was added dropwise 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.
The temperature was raised to 0 ° C., and the mixture was stirred at 80 ° C. for 2 hours. 80 reactants
The solution was filtered through a glass filter equipped with a jacket kept at a temperature of ℃ and washed several times with decane to obtain 4.8% by weight of titanium, 14% by weight of magnesium and 5% by weight of chlorine.
A solid titanium catalyst component (a) having 7% by weight, 2.2% by weight of aluminum and 9.7% by weight of ethoxy group was obtained.

[Polymerization] Internal volume 500 sufficiently replaced with nitrogen
250 ml of toluene was charged into a ml autoclave made of glass, and a mixed gas of ethylene and propylene (each 1
60 liters / hour, 40 liters / hour) were circulated and left at 50 ° C. for 10 minutes. Thereafter, 1.25 mmol of methylaluminoxane in terms of Al atom, then 0.004 g atom of the above titanium catalyst component (a) in terms of titanium atom and a transition metal compound represented by the following formula (A) 0.002 mmol was added to initiate polymerization. A mixed gas of ethylene and propylene was continuously supplied, and polymerization was carried out at 50 ° C. for 1 hour under normal pressure. After the completion of the polymerization, a small amount of methanol was added to stop the polymerization. The polymer solution was added to a large excess of methanol to precipitate the polymer, which was dried under reduced pressure at 130 ° C. for 12 hours. As a result, the weight average molecular weight (Mw) was 2.4 × 10 ⁵ ,
6.1 g of polymer with an Mw / Mn of 8.9 was obtained.

[0180]

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[0181]

Comparative Example 1 Ethylene and propylene were polymerized in the same manner as in Example 1 except that the transition metal compound represented by the formula (A) was not used. As a result, Mw was 4.2 × 10 ⁵ , and Mw / Mn was 5.9.
2.4 g of a polymer of

[0182]

Comparative Example 2 In Example 1, the titanium catalyst component (a)
Ethylene and propylene were polymerized in the same manner as in Example 1 except that was not used. As a result, Mw is 3.8.
× a 10 ^4, Mw / Mn was obtained a polymer 3.9g of 1.8.

[Brief description of drawings]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Hayashi 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A titanium catalyst component containing (A) magnesium, titanium and halogen as essential components, (B) a transition metal compound of Group 8 to 10 of the periodic table represented by the following general formula (I), C) at least one compound selected from the group consisting of (C-1) organoaluminum oxy compound, (C-2) alkylboronic acid derivative and (C-3) transition metal compound to form an ion pair, A catalyst for olefin polymerization, characterized by comprising (D) an organometallic compound, if necessary; (In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R ¹ and R ² May be the same or different from each other and represent a hydrogen atom or a hydrocarbon group, and m and n may be the same or different from each other, 1
Or 2 which are each a number satisfying the valences of X ¹ and X ² , and R ³ is (However, R ⁶ , R ⁷ , R ⁶¹ , R ⁶² , R ⁷¹ and R
⁷² may be the same or different from each other and represent a hydrogen atom or a hydrocarbon group. ), R ⁴ and R ⁵ may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ ,
-SR ⁹ , -N (R ¹⁰ ) ₂ or -P (R ¹¹ ) ₂ (wherein R ^{8 to} R ¹¹ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ¹⁰
Or between R ¹¹ each other may be bonded to form a ring. And R ⁴ and R ⁵ may combine with each other to form a ring, and R ¹ , R ² , R ⁶ (or R ⁶¹ and R ⁶² ) and R ⁷ (or R ⁷¹ and R ⁷²⁾ ), Two or more of these may be linked to each other to form a ring. ) 2. The catalyst for olefin polymerization according to claim 1, wherein the transition metal compound represented by the general formula (I) is a compound represented by the following general formula (I ′); (In the formula, M represents a transition metal atom of Groups 8 to 10 of the periodic table, X ¹ and X ² may be the same or different from each other, represent a nitrogen atom or a phosphorus atom, and R ¹ and R ² R ⁶ and R ⁷ may be the same or different from each other and represent a hydrogen atom or a hydrocarbon group, R ⁶ and R ⁷ may be the same or different and represent a hydrogen atom or a hydrocarbon group, R ⁴ and R ⁵ May be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group, —OR ⁸ , or
-SR ⁹ , -N (R ¹⁰ ) ₂ or -P (R ¹¹ ) ₂ (wherein R ^{8 to} R ¹¹ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an organic silyl group, and R ¹⁰
Or between R ¹¹ each other may be bonded to form a ring. ), R ⁴ and R ⁵ may be linked to each other to form a ring, and R ¹ , R ² , R ⁶ and R ⁷ are ring groups in which two or more of them are linked to each other. May be formed. ) 3. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.