JP2941016B2 - Solid titanium catalyst component for olefin polymerization, olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a solid catalyst component, a catalyst, and a polymerization method for producing a homopolymer of ethylene or α-olefin or a copolymer thereof.

Technical background of the invention Conventionally, as a catalyst used for producing an olefin polymer such as ethylene, α-olefin homopolymer or ethylene / α-olefin copolymer, supported on an active magnesium halide. Catalysts containing titanium compounds are known.

Examples of such an olefin polymerization catalyst (hereinafter, the polymerization catalyst may include a copolymerization catalyst) include a solid titanium catalyst component comprising magnesium, titanium, halogen and an electron donor, and an organic metal catalyst. Catalysts composed of compounds are known.

This catalyst, like the polymerization of ethylene, propylene,
Polymerization or copolymerization of α-olefins such as butene-1 (hereinafter, polymerization may include copolymerization)
Has high activity, and also has high stereospecificity of a polymer (hereinafter, a polymer may include a copolymer).

Among these catalysts, in particular, a solid titanium catalyst component carrying an electron donor selected from carboxylate esters, typically phthalate esters, an aluminum-alkyl compound as a co-catalyst component, and at least It is known that excellent performance is exhibited when a silicon compound having one Si-OR (where R is a hydrocarbon group) is used.

The present inventors have conducted a study for the purpose of obtaining a catalyst for olefin polymerization having a further excellent polymerization activity and stereoregularity.As a result, magnesium, halogen, titanium and two or more represented by a specific formula are obtained. A solid titanium catalyst component and a catalyst comprising a compound having an ether bond, magnesium, titanium, a halogen and an electron donor (unless otherwise specified, the electron donor excludes the compound having two or more ether bonds described above) )), A catalyst comprising an organometallic compound and the above compound having two or more ether bonds achieves the object of the present invention, and has completed the present invention.

A solid catalyst component obtained by contacting a solid component containing magnesium, titanium, a halogen atom and an electron donor with an alkoxy group-containing aromatic compound having a benzene ring substituted with 1 to 6 alkoxy groups, It has been found that a polymer having low stereoregularity can be produced by using a catalyst system comprising a combination with an organoaluminum compound (see JP-A-1-236203).

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and provides an olefin (co) polymer having high catalytic activity and high stereospecificity, and can be produced using a special electron donor. It is an object of the present invention to provide a solid titanium catalyst component for olefin polymerization for obtaining a catalyst to be obtained, a catalyst for olefin polymerization and a method for polymerizing olefin using the same.

SUMMARY OF THE INVENTION The solid titanium catalyst component for olefin polymerization according to the present invention has a general formula X _n Mg (OR) _2-n (where X is a halogen, R is a hydrocarbon group, and n is 0 ≦ n < 2), a compound having two or more ether bonds represented by a specific formula, and a titanium compound in a liquid state, which are obtained by contacting these compounds. A magnesium compound or a component derived from the magnesium compound,
Forming a compound having two or more ether bonds and a step of contacting the compound in the absence of the liquid titanium compound, wherein titanium, magnesium, halogen and the compound having two or more ether bonds are formed. It is characterized by containing.

According to the solid titanium catalyst component for olefin polymerization according to the present invention, the compound having two or more ether bonds as described above is used as the electron donor. A polymer having high activity and high stereospecificity can be produced without using a compound (in the present specification, an electron donor does not include a compound having two or more ether bonds unless otherwise specified). It is possible to obtain an olefin polymerization catalyst.

Further, according to the solid titanium catalyst component according to the present invention,
By further using a compound having two or more ether bonds or a specific electron donor at the time of polymerization, it is possible to obtain an olefin polymerization catalyst capable of producing a polymer having higher stereoregularity.

The olefin polymerization catalyst according to the present invention has the following general formula: [Ia] General formula X _n Mg (OR) _2-n (where X is a halogen, R is a hydrocarbon group, and n is 0 ≦ n <2) Is formed by bringing a compound having two or more ether bonds represented by a specific formula into contact with a titanium compound in a liquid state, and in the step of contacting these compounds, the magnesium compound or A component derived from the magnesium compound,
Forming including the step of contacting the compound having a plurality of ether bonds and the titanium compound in a liquid state in the absence of the liquid state, including titanium, magnesium, halogen, and the compound having two or more ether bonds. And [II] an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table.

Further, the olefin polymerization method according to the present invention is characterized in that ethylene and / or α-olefin is polymerized or copolymerized using the olefin polymerization catalyst.

According to the olefin polymerization catalyst and the olefin polymerization method according to the present invention, when the organometallic compound catalyst component [II] is used together with the solid titanium catalyst component [I] according to the present invention, the polymerization reaction has high catalytic activity and the polymerization reaction can be performed efficiently. In addition to the above, a polymer having high stereospecificity can be obtained.

Further, the catalyst for olefin polymerization and the method for olefin polymerization according to the present invention may comprise a catalyst containing a compound having two or more ether bonds or a specific electron donor together with the organometallic compound catalyst component [II] in addition to the above two components. By using, a polymer having higher stereoregularity can be obtained.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the solid catalyst component for olefin polymerization, the catalyst for olefin polymerization, and the method for polymerizing olefin according to the present invention will be specifically described.

The solid titanium catalyst component [Ia] for olefin polymerization according to the present invention specifies a specific magnesium compound, a titanium compound in a liquid state, and a compound having two or more ether bonds represented by a specific formula. In this order.

The olefin polymerization catalyst according to the present invention contains such a solid titanium catalyst component [Ia].

In the present invention, the magnesium compound used for preparing such a solid titanium catalyst component [Ia] has a general formula X _n Mg (O
R) _2-n (where X is a halogen, R is a hydrocarbon group,
n is a magnesium compound represented by 0 ≦ n <2).

Specific examples of such magnesium compounds include alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, and octoxy magnesium chloride; and phenoxy magnesium chloride and methyl phenoxy magnesium chloride. Allyloxymagnesium halides; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; and allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium Can be. Even if these magnesium compounds are used alone,
Two or more kinds may be used in combination.

The magnesium compound may be derived from another magnesium compound or magnesium metal.

Examples of the titanium compound in a liquid state used for preparing the solid titanium catalyst component [Ia] according to the present invention include, for example, Ti
(OR) _g X _4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦
g ≦ 4). More specifically, titanium tetrahalides such as TiCl ₄ , 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 (OisoC 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 Dihalogenated alkoxytitaniums such as (O _n -C ₄ H ₉ ) ₂ Cl ₂ and Ti (OC 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 monohalogenated alkoxy titanium such as _{Br, Ti (OCH 3) 4} , Ti (OC 2 H 5) 4, Ti (O n -C _{4 H 9) 4 Ti (Oiso} -C 4 H 9) 4 Ti (O-2- ethylhexyl) such as tetra-alkoxy titanium such as ₄ can be cited.

Of these, titanium tetrahalides are preferred, and titanium tetrachloride is particularly preferred. These titanium compounds may be used alone or in the form of a mixture. Further, it may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon.

In the solid titanium catalyst component [Ia] according to the present invention, a compound having two or more ether bonds represented by a specific formula is used in addition to the compounds described above.

As the compound having two or more ether bonds used for preparing the solid titanium catalyst component [Ia] according to the present invention, the atom existing between these ether bonds may be carbon, silicon, oxygen, sulfur, phosphorus, boron, or the like. Alternatively, there may be mentioned two or more compounds selected from these. Among them, a relatively bulky substituent is bonded to an atom between ether bonds, and an atom existing between two or more ether bonds is included. Compounds containing a plurality of carbon atoms are preferred.

Such compounds having two or more ether bonds include, for example, the following formula: (Where n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶
Is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any of R ^{1 to} R ²⁶ , preferably R ¹
To R ²ⁿ may together form a ring other than a benzene ring, and an atom other than carbon may be contained in the main chain.)

Examples of the compound having two or more ether bonds as described above include 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, and 2-butyl-1,3- Dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2 -(2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (diphenyl Methyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (pt-butylphenyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2 -Diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl- 2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis ( 2-cyclo Xylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diisobutyl- 1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2,2-di-s -Butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimet Shipuropan, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,
3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane, 2,3 -Diisopropyl-1,4-diethoxybutane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3-bis (p-chlorophenyl) -1,4-dimethoxybutane, 2, 3-bis (p-fluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1 , 5-Dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3-diiso Amiloxypropane, 1, 2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,2-diisoamyloxyethane, 1,3-diisoamyloxypropane, 1,2-diisoneopentyloxyethane, 1,3-di Neopentyloxypropane, 2,2-tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2 -Bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro [5,5] undecane, 3,7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] Octane, 3,3-diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane, 1,1-bis (methoxymethyl) cyclohexane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis "Methoxymethyl" bicyclo [2,2,1 Heptane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2 -Methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2 -Ethoxymethyl-1,3-dimethoxycyclohexane, 2-isoprop Propyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2- Isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, -T-butylbis (methoxymethyl) silane, cyclohexyl-t-butyldis (methoxymethyl)
Examples include silane and i-propyl-t-butylbis (methoxymethyl) silane.

The solid titanium catalyst component [Ia] according to the present invention includes:
In addition to the magnesium compound, the compound having two or more ether bonds, the titanium compound in a liquid state,
It may be prepared by bringing a carrier compound and an electron donor (a) described below into contact with each other.

Such carrier compounds include Al ₂ O ₃ , SiO ₂ , B
Resins such as ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, ZnO ₂ , SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer are used. Among them, Al ₂ O ₃ , SiO ₂ and styrene-divinylbenzene copolymer are preferred.

Further, the electron donor (a) does not necessarily need to be used as a starting material, and can be generated in the process of preparing the solid titanium catalyst component [Ia].

As the electron donor (a) used in the present invention, a polycarboxylic acid ester can be mentioned as a particularly preferred example.

As such a polycarboxylic acid ester, the following general formula: (However, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² ,
R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group,
R ³ and R ⁴ are hydrogen or a substituted or unsubstituted hydrocarbon group, preferably at least one of them is a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ may be linked to each other. Often, when the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent contains a heteroatom such as N, O, S, etc.
O-C, COOR, COOH, OH, SO 3 H, -C-N-C-, NH 2
Etc.) can be exemplified.

As such a polyvalent carboxylic acid ester, specifically, diethyl succinate, dibutyl succinate, diethyl methyl succinate, isobutyl α-methylglutarate,
Diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, diethyl butyl malonate, diethyl phenyl malonate, diethyl diethyl malonate, diethyl dibutyl malonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, butyl maleate Dibutyl acid, diethyl butyl maleate,
aliphatic polycarboxylic acid esters such as β-methylglutaric acid diisopropyl, ethyl succinate diallyl, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconic acid, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclohexanecarboxylic acid Alicyclic polycarboxylic acid esters such as diisobutyl acid, diethyl tetrahydrophthalate, diethyl nadic acid, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, phthalate Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-phthalate
Aromas such as 2-ethylhexyl, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, and dibutyl trimellitate Preferred examples include heterocyclic polycarboxylic acid esters such as group III polycarboxylic acid esters and 3,4-furandicarboxylic acid.

Other examples of the polycarboxylic acid ester include long adipates such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Esters of chain dicarboxylic acids and the like can be mentioned.

Other compounds used as the electron donor (a) include organic acid esters, organic acid halides, organic acid anhydrides,
Examples include ethers, ketones, aldehydes, tertiary amines, phosphites, phosphates, phosphoric amides, carboxamides, nitriles, and the like.Specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, C3-15 ketones such as cyclohexanone and benzoquinone; acetaldehyde, propionaldehyde, octylaldehyde,
C2 to C15 aldehydes such as benzaldehyde, 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, benzoic acid Cyclohexyl, phenyl benzoate, benzyl benzoate, methyl toluate,
Ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc.
To 18 organic acid esters; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole Ethers having 2 to 20 carbon atoms such as diphenyl ether; acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide; trimethylamine, triethylamine, tributylamine; Tertiary amines such as tribenzylamine and tetramethylethylenediamine; and nitriles such as acetonitrile, benzonitrile and trinitrile can be exemplified. Of these, α-carboxylic acid esters are preferably used, and Polycarboxylic acid esters, especially it is preferred to use phthalic acid esters. Two or more of these compounds can be used in combination.

These electron donors (a) need not necessarily be used as starting materials, and may be used as a solid titanium catalyst component [Ib].
It can also be generated during the preparation process.

Other compounds that may be added include halogen-containing compounds, for example, halogens in elemental state: for example, chlorine, bromine, iodo-hydrogen halides: for example, hydrogen chloride, hydrogen bromide, and hydrogen iodide haloalkanes: for example, carbon tetrachloride , Chloroform,
Ethane dichloride, ethane tetrachloride, methylene chloride, trichlene, methyl chloride, ethyl chloride, n-butyl chloride, n-octyl chloride Nonmetal oxyhalides: for example, sulfuryl chloride, thionyl chloride, nitrosyl chloride, phosphorus oxychloride ,
Phosgene Nonmetal halides: for example, phosphorus trichloride, phosphorus pentachloride Metal and ammonium halides: for example, aluminum chloride, ammonium chloride, halogen-containing alcohols: for example, 2-chloroethanol, 1-chloro-2-propanol, 3- Chlor-
1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro-
1-pentanol, 6-chloro-1-hexanol, 3
Chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o,
p) -Chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol, 6-chloro-
(M, o) -cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m, o,
p) -chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorothymol, 4-chlororesorcin, 2-chlorophenol
Bromoethanol, 3-bromo-1-propanol, 1
-Bromo-2-propanol, 1-bromo-2-butanol, 2-bromo-p-cresol, 1-bromo-2-
Naphthol, 6-bromo-2-naphthol, (m, o, p)
-Bromophenol, 4-bromoresorcinol, (m, o,
p) -Fluorophenol, p-iodophenol: 2,2-
Dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro-
1- (α-chloromethyl) -1-propanol, 2,3-
Dibromo-1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4-dibromo-1-naphthol: 2,2,2-trichloroethanol, 1,1,
1-trichloro-2-propanol, β, β, β-trichloro-tert-butanol, 2,3,4-trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4 , 6-Tribromophenol, 2,3,5-
Tribromo-2-hydroxytoluene, 2,3,5-tribromo-4-hydroxytoluene, 2,2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,6-trii Odophenol: 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromobisphenol A, 2,2,3,3-tetrafluoro-1-propanol, 2,
3,5,6-tetrafluorophenol, tetrafluororesorcin, and a general formula R ¹ _n SiX _4-n (wherein R ¹ represents a hydrocarbon group having ¹ to 16 carbon atoms or a halohydrocarbon group, and X represents A halogen atom, and 0 ≦ n ≦ 3).

The halogen-containing silicon compound represented by the above formula, when R ^1, the alkyl group, may be exemplified a cycloalkyl group, a halogen-containing silicon compound is an aryl group as a preferred example, X or R ¹ is more present, these X Or
R ¹ may be the same or different.

Such a halogen-containing silicon compound has a general formula
The tetrahalosilane represented by SiX ₄ (in the above formula, n = 0), specifically, tetrahalosilane is tetrachlorosilane, tetrabromosilane, tetraiodosilane, tetrafluorosilane, trichlorobromosilane, trichloroiodo. Silane, trichlorofluorosilane, dichlorodibromosilane, dichlorodiiodosilane, dichlorodifluorosilane, chlorotribromosilane, chlorotriiodosilane, chlorotrifluorosilane, bromotriiodosilane, bromotrifluorosilane, dibromo Examples thereof include diiodosilane, dibromodifluorosilane, tribromoiodosilane, trifluorobromosilane, iodotrichlorosilane, diiododifluorosilane, and triiodofluorosilane. Buromushiran, trichlorosilane bromine silane, dichlorprop dibromostyrene silane and chloro-tribromophenyl silane Preferably, optimal is tetrachlorosilane.

Further, as the halogen-containing silicon compound, a compound represented by the general formula R ¹ SiX ₃ (n = 1 in the above formula);
For example, methyltrichlorosilane, ethyltrichlorosilane, n- and i-propyltrichlorosilane, n
-, I-, sec- and tert-butyltrichlorosilane, n- and i-amyltrichlorosilane, n-hexyltrichlorosilane, n-heptyltrichlorosilane, n-octyltrichlorosilane, n-dodecyltrichlorosilane, n-tetra Decyltrichlorosilane, n
An alkyltrichlorosilane containing a saturated alkyl group having up to 16 carbon atoms such as hexadecyltrichlorosilane; an unsaturated alkyl group containing an unsaturated alkyl group having 1 to 4 carbon atoms such as vinyltrichlorosilane and isobutenyltrichlorosilane; Alkyltrichlorosilane; chloromethyltrichlorosilane, dichloromethyltrichlorosilane, trichloromethyltrichlorosilane,
Haloalkyl or unsaturated haloalkyltrichlorosilane such as (2-chloroethyl) trichlorosilane, (1,2-dibromoethyl) trichlorosilane, trifluoromethyltrichlorosilane, (vinyl-1-chloro) trichlorosilane; cyclopropyltrichlorosilane, cyclopentyltrichlor Silane, cyclohexenyltrichlorosilane,
Saturated or unsaturated cycloalkyltrichlorosilane such as 3-cyclohexenyltrichlorosilane; aryl or aralkyltrichlorosilane such as phenytrichlorosilane, 2-, 3- and 4-tolyltrichlorosilane, benzyltrichlorosilane; methyldifluorochlorosilane Phenyldifluorochloro, methylfluorodichlorosilane, ethyldifluorochlorosilane, ethylfluorodichlorosilane, n- and i-propyldifluorochlorosilane, n-butyldifluorochlorosilane, n-butylfluorodichlorosilane; Alkyl or haloalkyl mixed with silane, methyldichlorobromosilane, ethyldichlorobromosilane, methyldichloroiodosilane, (trifluoromethyl) difluorobromosilane Halosilanes such as: (wherein, n = 2) General formula R ¹ ₂ SiX ₂ dialkyldihalosilane represented by, for example, dimethyldichlorosilane, diethyl dichlorosilane, di -n- and -i- propyl dichlorosilane , Di-n-, -i-, -sec- and -tert-butyldichlorosilane, di-n- and-
i-amyldichlorosilane, di-n-hexyldichlorosilane, di-n-heptyldichlorosilane, di-n-octyldichlorosilane; dicycloalkyldihalosilane, for example, dicyclopentyldichlorosilane, dicyclohexyldi Chlorosilane, dicyclohexyldibromosilane, dicyclohexyldiiodosilane, dicyclohexyldifluorosilane; diaryl or diaralkyldihalosilane, such as diphenyldichlorosilane, di-2-, -3- or -4-tolyldichlorosilane, benzyl dichlorosilane: (wherein, n = 3) the formula R ¹ ₃ SiX trialkylhalosilane represented by, for example, trimethylchlorosilane,
Triethylchlorosilane, tri (n- and i-propyl) chlorosilane, tri (n- and i-butyl) chlorosilane, tri (n-hexyl) chlorosilane, tri (n-heptyl) chlorosilane, tri (n-octyl)
Chlorosilane, dimethyl (ethyl) chlorosilane, methyl (diethyl) chlorosilane; triaryl or triaralkylhalosilanes, such as triphenylchlorosilane, tri (2-, 3- or 4-tolyl) chlorosilane, tribenzylchlorosilane and the like; .

Among them, silicon tetrachloride and mono, di and trichlorosilanes in which R ³ is methyl, ethyl and phenyl are preferred.

Furthermore, in the preparation of the solid titanium catalyst component [Ia] according to the present invention, an organometallic compound described below may be used.

The solid titanium catalyst component [Ia] according to the present invention includes the magnesium compound as described above, a compound having two or more ether bonds and a titanium compound in a liquid state, and if necessary, a halogen-containing compound, a carrier compound, It is prepared by contacting an electron donor (a), a halogen-containing compound and an organometallic compound.

In the present invention, during the contacting step of these compounds, the magnesium compound or a component derived from the magnesium compound is mixed with the compound having two or more ether bonds and in the absence of the liquid titanium compound. In contact.

The method for preparing such a solid titanium catalyst component [Ia] is not particularly limited. For example, (1) a compound obtained by contacting the magnesium compound with the compound having two or more ether bonds (2) a method of obtaining a solid titanium composite by contacting a titanium compound in a liquid state with the compound; (2) a compound obtained by contacting the magnesium compound with the titanium compound in a liquid state; (3) contacting the magnesium compound, the compound having two or more ether bonds, the halogen-containing compound and / or the organometallic compound, A method for obtaining a solid titanium composite by bringing the titanium compound in a liquid state into contact with the compound obtained by the above-mentioned process; A compound having two or more ether bonds and a halogen-containing compound and / or an organometallic compound with a compound obtained by contacting the titanium compound in the liquid state with the titanium compound in the liquid state to obtain solid titanium. (5) In the method of (1) to (4), a compound having two or more ether bonds and an electron donor are used instead of the compound having two or more ether bonds. (6) A method of further contacting the titanium compound in a liquid state with the component obtained by the method of (1) to (5), (7) A component obtained by the method of (1) to (5) And a method of further reacting the compound having two or more ether bonds.

By such a method, the solid titanium catalyst component [I
In the production of a), the amounts of the magnesium compound, the titanium compound in a liquid state and the compound having two or more ether bonds vary depending on the type, contact conditions, contact order, and the like. The titanium compound in the liquid state is contained in an amount of 0.1 mol per mol of magnesium.
The compound having two or more ether bonds is used in an amount of from 1 mol to 1000 mol, particularly preferably from 1 mol to 200 mol, and preferably from 0.01 mol to 5 mol, particularly preferably from 0.1 mol to 1 mol.
It is used in molar amounts.

The temperature for contacting these compounds is usually -70 ° C.
To 200 ° C, preferably 10 ° C to 150 ° C.

The solid titanium catalyst component [Ia] thus obtained
Contains titanium, magnesium, and halogen, and an ether compound having two or more ether bonds existing through a plurality of atoms.

In this solid titanium catalyst component [Ia], halogen / titanium (atomic ratio) is 2 to 100, preferably 4 to 90, and the compound having two or more ether bonds / titanium (molar ratio) is: It is 0.07-100, preferably 0.2-10, and magnesium / titanium (atomic ratio) is desirably 2-100, preferably 4-50.

The catalyst for olefin polymerization according to the present invention comprises a solid titanium catalyst component [Ia] thus obtained and an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table. [II].

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

As such organometallic compound catalyst component [II],
For example, an organic aluminum compound, a complex alkylated product of a Group I metal and aluminum, an organic metal compound of a Group II metal, and the like can be used.

Examples of such organic aluminum compounds, for example in R ^a _n AlX _3-n (wherein, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, n represents 1 to 3 Can be exemplified.

In the above formula, ^Ra is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. Group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds.

Trimethyl aluminum, triethyl aluminum,
Trialkyl aluminums such as triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum and tri 2-ethylhexyl aluminum.

Alkenyl aluminum such as isoprenyl aluminum.

Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide.

Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide.

Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide;

Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

The organic as an aluminum ^{_{compound, R a n AlY 3-n}} ( wherein R ^a is as defined above, Y is -OR ^b group,
-OSiR ^c ₃ groups, -OAlR ^d ₂ groups, -NR ^e ₂ groups, -SiR ^f ₃ groups or N is 1-2, R ^b , R ^c , R ^d and R ^h are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ^e is hydrogen, A methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, and the like, and R ^f and R ^g are a methyl group, an ethyl group, and the like).

As such an organoaluminum compound, specifically, the following compounds are used.

(I) R ^a _n Al (OR ^b ) _3-n dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc. (ii) R ^a _n Al (OSiR ^c ₃ ) _3-n Et ₂ Al (OSiMe ₃ ) (iso-Bu) ₂ Al (OSiMe ₃ ) (iso-Bu) ₂ Al (OSiEt ₃ ), etc. (iii) R ^a _n Al (OAR ^d ₂ ) _3-n Et ₂ AlOAlEt ₂ (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc., (iv) R ^a _n Al (NR ^e ₂ ) _3-n Me ₂ AlNEt ₂ Et ₂ AlNHMe Me ₂ AlNHEt Et ₂ AlN (Me ₃ Si) ₂ (iso-Bu) ₂ such as _{AlN (Me 3 Si) 2,} (v) such as _{^{R a n Al (SiR f 3}} ) 3-n (iso-Bu) 2 AlSiMe 3, Preferred examples of the organoaluminum compound as described above include organoaluminum compounds represented by R ^a ₃ Al, R ^a _n Al (OR ^b ) _3-n , and R ^a _n Al (OAlR ^d ₂ ) _3-n. be able to.

The complex alkylated product of a Group I metal and aluminum is represented by the general formula M ¹ AlR ^j ₄ (where M ¹ is Li, Na, K, and R ^j is a hydrocarbon group having 1 to 15 carbon atoms). The compound represented can be exemplified, specifically, LiAl (C ₂ H ₅ )
₄ , LiAl (C ₇ H ₁₅ ) _{4 and the} like.

Group II metal organometallic compounds include compounds of the general formula R ^k R ¹ M
₂ (however, R ^k and R ¹ are a hydrocarbon group having 1 to 15 carbon atoms or halogen, which may be the same or different from each other, except that all are halogen. M ₂ is Mg, Zn,
Cd) can be exemplified, specifically,
Examples thereof include diethylzinc, diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, and butylmagnesium chloride.

These compounds may be used in combination of two or more.

As the organometallic compound catalyst component [II], the above-mentioned compound having two or more ether bonds and the electron donor (b) may be used, if necessary. (B) is the electron donor (a) described above.
Preferably, an organosilicon compound can be used.
The organosilicon compound is, for example, one represented by the following general formula.

R _n Si (OR ′) _{4-n wherein} R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compounds generally represented as above include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t-butylmethyldimethoxy. Silane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyl Dimethoxysilane, bis p-
Tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n
-Propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane,
Vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyl Dimethoxysilane,
Ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane; cyclopentyltrimethoxysilane, 2-methylcyclopentyl Trimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxy Silane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxy Silane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane are used.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane Silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxy Silane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferably used. That.

Examples of the electron donor (b) that can be used in addition to the organic silicon compound include a nitrogen-containing compound, another oxygen-containing compound, and a phosphorus-containing compound.

As such a nitrogen-containing compound, specifically, the following compounds can be used.

2,6-substituted piperidines such as; 2,5-substituted piperidines such as: N, N, N ', N'-tetramethylmethylenediamine, N, N,
Substituted methylenediamines such as N ', N'-tetraethylmethylenediamine: 1,3-dibenzylimidazolidine, 1,3-dibenzyl-
Substituted imidazolidines such as 2-phenylimidazolidine and the like.

As the phosphorus-containing compound, specifically, the following phosphites can be used.

Phosphites such as triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, and diethylphanyl phosphite;

Further, as the oxygen-containing compound, the following compounds can be used.

2,6-substituted tetrahydropyrans such as: 2,5-substituted tetrahydropyrans.

The olefin polymerization method according to the present invention performs olefin polymerization using the olefin polymerization catalyst according to the present invention.

In the first olefin polymerization method according to the present invention, it is preferable that the α-olefin is preliminarily polymerized on the olefin polymerization catalyst. This prepolymerization is carried out by prepolymerizing the α-olefin in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g, per 1 g of the olefin polymerization catalyst.

In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. The concentration of the solid titanium catalyst component [I] in the prepolymerization is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, particularly preferably about 0.01 to 50 mmol, per liter of the liquid medium, in terms of titanium atoms.
Desirably, the range is 0.1 to 20 mmol.

The amount of the organometallic compound catalyst component [II] is 0.1 to 1000 g, preferably 0.3 to 500 g per 1 g of the solid titanium catalyst component [Ia].
Any amount may be used so long as the polymer of the formula (I) is produced.
It is desirable that the amount is 1 to 300 mol, preferably about 0.5 to 100 mol, particularly preferably 1 to 50 mol.

In the prepolymerization, if necessary, the compound having two or more ether bonds or the electron donor (b) can be used. In this case, these components are composed of titanium atom 1 in the solid titanium catalyst component [Ia]. It is used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol, per mol.

The prepolymerization can be carried out under mild conditions by adding an olefin and the above-mentioned catalyst component to an inert hydrocarbon medium.

As the inert hydrocarbon medium used at this time, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. When an inert hydrocarbon medium is used, the prepolymerization is preferably performed in a batch system. On the other hand, the olefin itself can be pre-polymerized in a solvent or can be pre-polymerized in a substantially solvent-free state. In this case, the prepolymerization is preferably performed continuously.

The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described below, and specifically, it is preferably propylene.

The reaction temperature during the prepolymerization is usually about -20 to + 100 ° C,
Preferably about -20 to + 80 ° C, more preferably 0 to +40
It is desirable to be in the range of ° C.

In the prepolymerization, a molecular weight regulator such as hydrogen can be used. Such molecular weight regulators are
It is desirable to use the polymer in an amount such that the intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 135 ° C. is about 0.2 dl / g or more, preferably about 0.5 to 10 dl / g.

As described above, the prepolymerization is performed in an amount of about 0.1 to 1000 g, preferably about 0.3 to 500 g, per 1 g of the solid titanium catalyst component [I].
Particularly preferably, the reaction is carried out so as to produce 1 to 200 g of a polymer. If the prepolymerization amount is too large, the production efficiency of the olefin polymer may decrease.

The prepolymerization can be performed in a batch system or a continuous system.

Examples of the olefin that can be used in the main polymerization include ethylene and α-olefins having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene,
3-methyl-1-butene, 1-hexene, 4-methyl-
1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene,
Examples thereof include tetracyclododecene and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

In the polymerization method of the present invention, these olefins can be used alone or in combination.
Further aromatic vinyl compounds such as styrene and allylbenzene, alicyclic vinyl compounds such as vinylcyclohexane,
6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6 -Methyl-1,6-nonadiene, 7-methyl-1,6
-Nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6 −
Compounds having polyunsaturation such as conjugated dienes and non-conjugated dienes such as dienes such as undecadiene, isoprene, and butadiene can also be used as the polymerization raw material.

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.

When the main polymerization takes a reaction mode of slurry polymerization, the above-mentioned inert hydrocarbon can be used as the reaction solvent, and an olefin liquid at the reaction temperature can be used.

In the polymerization method of the present invention, the solid titanium catalyst component [Ia] is converted into Ti atoms per liter of polymerization volume,
Usually about 0.001-0.5 mmol, preferably about 0.005-0.1
Used in millimolar amounts. The organometallic compound catalyst component [II] has a metal atom of usually about 1 to 2,000 moles per mole of a titanium atom in the prepolymerization catalyst component in the polymerization system.
Preferably, it is used in an amount of about 5 to 500 mol.

If hydrogen is used during the main polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained.

In the present invention, the polymerization temperature of the olefin is usually about
At 20-200 ° C, preferably about 50-150 ° C, the pressure is usually
The pressure is set at normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² . In the polymerization method of the present invention, the polymerization is a batch type,
It can be carried out by any of a semi-continuous method and a continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The olefin polymer thus obtained may be any of a homopolymer, a random copolymer and a block copolymer.

When olefin polymerization, particularly propylene polymerization, is carried out using the olefin polymerization catalyst as described above, the isotactic index (II) indicated by the boiling heptane extraction residue is 70% or more, preferably 85% or more, and particularly preferably 95% or more.
% Of propylene-based polymer is obtained. At this time, the stereoregularity can be easily controlled by adjusting the amount of the compound having two or more ether bonds or the electron donor.

In the present invention, the catalyst for olefin polymerization may contain other components useful for olefin polymerization, in addition to the above components.

Effects of the Invention The solid titanium catalyst component for olefin polymerization [Ia] according to the present invention has a general formula X _n Mg (OR) _2-n (where X is a halogen,
R is a hydrocarbon group, n is 0 ≦ n <2), a compound having two or more ether bonds represented by a specific formula, and a titanium compound in a liquid state. In the step of contacting these compounds, the magnesium compound or a component derived from the magnesium compound is
The compound having two or more ether bonds and the compound having the step of contacting in the absence of the liquid state titanium compound, titanium, magnesium, halogen and the compound having two or more ether bonds are formed. Contains.

Therefore, according to the solid titanium catalyst component [Ia], an olefin polymerization catalyst having high catalytic activity and high stereospecificity of the obtained polymer can be obtained without using an electron donor during polymerization. Further, by using the compound having two or more ether bonds and another electron donor during the polymerization, it is possible to obtain a polymer having higher catalytic activity and higher stereospecificity. Can be manufactured.

The olefin polymerization catalyst according to the present invention comprises the above-mentioned solid titanium catalyst component [Ia] and an organometallic compound catalyst component [II] containing a metal selected from Groups I to III of the periodic table.
In the olefin polymerization method according to the present invention, a monomer selected from ethylene and an α-olefin is polymerized or copolymerized using the olefin polymerization catalyst. Therefore, according to the olefin polymerization catalyst and the olefin polymerization method according to the present invention,
A polymer having high catalytic activity and efficient polymerization can be obtained, and a polymer having high stereospecificity can be obtained.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of Solid Titanium Catalyst Component (A) 3 g of diethoxymagnesium was charged into a nitrogen-purged reactor equipped with a stirrer, and 2-isopentyl-2-isopropyl-1,3-dimethoxy was added thereto. Propane (IPAMP) 6.03ml
And 37.5 ml of silicon tetrachloride, and the mixture was heated to 40 ° C. and kept for 1 hour. After filtration, 120 ml of titanium tetrachloride was added, the mixture was heated to 100 ° C. and kept for 2 hours. This was filtered at 100 ° C., washed twice with hot decane, and then mixed with 120 ml of titanium tetrachloride.
Was added, heated to 110 ° C., and kept for 2 hours. After this, 110 ° C
, And washed twice with hot decane, and further five times with n-hexane to obtain a solid titanium catalyst component (A).

The composition was 3.4% by weight of titanium, 18% by weight of magnesium, 60% by weight of chlorine, and 10.2% by weight of IPAMP.

[Polymerization] 750 ml of purified n-hexane was inserted into an autoclave having an internal volume of 2 liters. 0.015 mmol Ti was added in terms of titanium atoms.

After heating to 60 ° C., 200 ml of hydrogen was introduced, the temperature was raised to 70 ° C., and this was maintained for 2 hours to carry out polymerization. 7k pressure during polymerization
g / cm ² G. After the completion of the polymerization, the fullery containing the purified solid was filtered to separate into a white powder and a liquid phase. The yield of the dried white powdery polymer was 203.6 g, the extraction residual ratio with boiling heptane was 95.96%, and the MFR was 6.9 dg / min. On the other hand, the liquid phase was concentrated to obtain 10.3 g of a solvent-soluble polymer. Therefore, the activity is 14,300 g-PP / mM-Ti, and II
(T-II) was 91.3%.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that IPAMP was used instead of CMMS.

 The results are shown in Table 1.

Example 3 [Preparation of solid titanium catalyst component (B)] Diisobutyl phthalate (DIBP) was used instead of IPAMP.
A solid titanium catalyst component (B) was obtained in the same manner as in Example 1 except that 7.59 ml was used. Its composition is titanium 1.3% by weight, magnesium 21% by weight, chlorine 65% by weight, DIBP 7.55
% By weight.

[Polymerization] Polymerization was carried out in the same manner as in Example 2 except that the solid titanium catalyst component (B) was used.

 The results are shown in Table 1.

[Brief description of the drawings]

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

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-57-141410 (JP, A) JP-A-1-168707 (JP, A) JP-A-54-94591 (JP, A) JP-A-4- 4206 (JP, A) European Publication 362705 (EP, A1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (3)

(57) [Claims] 1. A magnesium compound represented by the general formula X _n Mg (OR) _2-n (where X is a halogen, R is a hydrocarbon group and n is 0 ≦ n <2), formula (Where n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶
Is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any of R ^{1 to} R ²⁶ together form a ring other than a benzene ring May be formed, and an atom other than carbon may be contained in the main chain) .A compound having two or more ether bonds represented by In the step of contacting these compounds, the magnesium compound or a component derived from the magnesium compound is
Forming a compound having two or more ether bonds and a step of contacting the compound in the absence of the liquid state titanium compound, titanium, magnesium, halogen and the compound having two or more ether bonds. A solid titanium catalyst component for olefin polymerization, comprising: 2. Ia: a magnesium compound represented by the general formula X _n Mg (OR) _2-n , wherein X is a halogen, R is a hydrocarbon group, and n is 0 ≦ n <2. And the following equation (Where n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶
Is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any of R ^{1 to} R ²⁶ together form a ring other than a benzene ring And a compound having two or more ether bonds represented by the following formula:
It is obtained by contacting a titanium compound in a liquid state, and during the contacting step of these compounds, the magnesium compound or a component derived from the magnesium compound is
Forming a compound having two or more ether bonds and a step of contacting the compound in the absence of the liquid state titanium compound, titanium, magnesium, halogen and the compound having two or more ether bonds. A catalyst for olefin polymerization, comprising: a solid titanium catalyst component containing: and [II] an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table. 3. A method for polymerizing olefins, comprising polymerizing ethylene and / or an α-olefin using the catalyst for olefin polymerization according to claim 2.