JP2940993B2 - 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.

Background of the Invention Conventionally, as a catalyst used for producing an olefin polymer such as an ethylene or α-olefin homopolymer or an ethylene / α-olefin copolymer, an activated magnesium halide has been supported. A catalyst containing a titanium compound is 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 catalyst using a solid titanium catalyst component comprising a compound having an ether bond, a solid titanium catalyst component comprising magnesium, titanium, a halogen and an electron donor, an organometallic compound, and a compound having two or more ether bonds described above. The present inventors have found that a catalyst consisting of the above achieves the object and 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 organic aluminum 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. An object of the present invention is to provide a solid titanium catalyst component to be used, a catalyst for refin polymerization using the same, and a method for polymerizing an olefin.

SUMMARY OF THE INVENTION The solid titanium catalyst component for olefin polymerization according to the present invention includes (A) a solid titanium component containing titanium, magnesium, halogen, and an electron donor (a); and (B) an electron donor ( b) is contacted, and either one of the electron donor (a) and the electron donor (b) is a compound having two or more ether bonds represented by a specific formula. Features.

According to the solid titanium catalyst component for olefin polymerization according to the present invention, when a compound having two or more ether bonds as described above is used as the electron donor, the polymerization can be performed without using an electron donor. However, it is possible to obtain an olefin polymerization catalyst capable of producing a polymer having high activity and high stereospecificity.

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 catalyst for olefin polymerization according to the present invention comprises: [I] (A) titanium, magnesium, halogen,
A solid titanium component containing an electron donor (a) and (B) an electron donor (b) are formed by contacting with each other, and one of the electron donor (a) and the electron donor (b) is formed. A solid titanium catalyst component for olefin polymerization, which is an ether compound having two or more ether bonds represented by a specific formula, and [II] a metal selected from Groups I to III of the periodic table. And (iii) an electron donor (c) containing a compound having two or more ether bonds, if necessary.

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 of the present invention, when the organometallic compound catalyst component [II] is used together with the solid titanium catalyst component [I] of the present invention, the polymerization reaction has a high catalytic activity and a high efficiency. And 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 titanium catalyst component for olefin polymerization, the catalyst for olefin polymerization, and the olefin polymerization method according to the present invention will be specifically described.

The solid titanium catalyst component [I] for olefin polymerization according to the present invention comprises: a solid titanium catalyst component (A) containing titanium, magnesium, halogen and an electron donor (a);
A catalyst component obtained by contacting the electron donor (b) with the electron donor (B), wherein one of the electron donor (a) and the electron donor (b) is represented by a specific formula. The compound has the above ether bond.

The olefin polymerization catalyst according to the present invention is formed by bringing such a solid titanium catalyst component [I] into contact with an organometallic compound catalyst component [II].

The solid titanium component (A) used for preparing the solid titanium catalyst component [I] includes, for example, a magnesium compound and a titanium compound, and the electron donor (a) containing the compound having two or more ether bonds. And by contacting these compounds.

In the present invention, examples of the magnesium compound that can be used for preparing the solid titanium catalyst component (A) include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

Here, as the magnesium compound having a reducing ability, for example, a compound represented by the formula X _n MgR _2-n (where n is 0 ≦ n ≦ 2, and R is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or When n is 0, two R's may be the same or different and X is a halogen, and X is a halogen).

Specific examples of the organomagnesium compound having such a reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamilmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesiumchloride, Examples thereof include butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium, butyl magnesium hydride and the like. These magnesium compounds may be used alone or may form a complexing compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy chloride. Alkoxy magnesium halides such as magnesium and octoxy magnesium chloride; alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium Magnesium; allyloximers such as phenoxymagnesium and dimethylphenoxymagnesium Neshiumu; magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a compound having a reducing property is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. What is necessary is just to contact with a compound containing, an OH group, or a compound having an active carbon-oxygen bond.

The magnesium compound is a complex compound, a complex compound of the above-mentioned magnesium compound and another metal, or a mixture of another metal compound, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property. You may. Further, a mixture of two or more of the above compounds may be used, and the compound may be used in a liquid state or in a solid state. When the compound is a solid, it can be liquefied using alcohols, carboxylic acids, aldehydes, amines, metal acid esters and the like.

Among these, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

Examples of the liquid titanium compound used in the preparation of the solid titanium component (A) according to the present invention include a general formula: Ti (OR) _g X _4-g (R is a hydrocarbon group, and X is a halogen atom. Atom,
0 ≦ g ≦ 4) tetravalent titanium compound represented by the following formula:
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 (On-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 alkoxy titanium such as _{On-C 4 H 9) 2} Cl 2, Ti (OC 2 H 5) 2 Br 2; Ti (OCH 3) 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (On- _{C 4 H 9) 3 Cl,} Ti (OC 2 H 5) 3 Br; Ti (OCH 3) 4, Ti (OC 2 H 5) 4, Ti (On-C 4 H 9) 4 Ti (Oiso-C 4 _{H 9) 4 Ti (O-} 2- _{ethylhexyl) 4; Ti (OCH 3)} 4, Ti (OC 2 H 5) 4, Ti (On-C 4 H 9) 4, Ti (Oiso-C 4 H 9) ₄ , monohalogenated alkoxytitanium such as tetraalkoxytitanium such as ₄ , Ti (O-2-ethylhexyl) ₄ .

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

In the solid titanium component (A) contained in the olefin polymerization catalyst according to the present invention, two or more ether bonds represented by a specific formula are used as the electron donor (a) in addition to the compounds described above. And / or an electron donor (a) other than the compound having two or more ether bonds.

Examples of the compound having two or more ether bonds used for preparing the solid titanium component (A) used in the present invention include the following formulas: (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-dimethoxy Propane, 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-sik Hexylethyl) -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-Jim Kishipuropan, 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 -Dicyclohexyl-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-methoxymethyl Tetrahydrofuran, 3-methoxymethyl Dioxane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane, 1 , 3-Dineopentyloxypropane, 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-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1 -Bis (methoxymethyl) bisic B [2,2,1] heptane, 1,1-dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxy Propane, 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-ethoxyme Cyl-1,3-dimethoxycyclohexane, 2-isopropyl-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, di-t-butylbis (methoxymethyl) silane, cyclohexyl-t-butylbis (methoxymethyl)
Examples include silane and i-propyl-t-butylbis (methoxymethyl) silane.

Of these, 1,3-diethers are preferred, and in particular, 2,2
-Diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) 1,3 -Dimethoxypropane is preferred.

Examples of the electron donor (a1) other than the compound having two or more ether bonds used in the solid titanium component (A) include organic acid esters, organic acid halides, organic acid anhydrides, ethers, ketones, and the like. Examples include aldehydes, tertiary amines, phosphites, phosphates, phosphoric amides, carboxylic amides, nitriles, and the like. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, cyclohexanone, and benzoquinone. C3-15 ketones; aldehydes having 2-15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate and propyl acetate , Octyl acetate, Cyclohexyl acid, 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 ethyl benzoate, methyl anisate, ethyl anisate,
Organic acid esters having 2 to 18 carbon atoms such as ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; carbon number such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride 2 to 15 acid halides; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran,
C2-C20 ethers such as anisole and diphenyl ether; acetic acid N, N-dimethylamide, benzoic acid N, N-
Acid amides such as diethylamide, toluic acid N, N-dimethylamide, trimethylamine, triethylamine,
Examples include tertiary amines such as tributylamine, tribenzylamine, and tetramethylethylenediamine; and nitriles such as acetonitrile, benzonitrile, and trinitrile. Among these, aromatic carboxylic acid esters are preferable. These compounds can be used in combination of two or more.

Further, as the organic acid ester, 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
And a skeleton represented by the following formula:

Such polycarboxylic acid esters include, specifically, diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate , Diethyl butylmalonate, diethylphenylmalonate, diethyldiethylmalonate, diethyldibutylmalonate, monooctylmaleate, dioctylmaleate, dibutylmaleate, dibutylbutylmaleate, diethylbutylmaleate, diisopropylβ-methylglutanate, Diallyl ethyl succinate, di-2-ethylhexyl fumarate,
Aliphatic polycarboxylates such as aliphatic polycarboxylates such as diethyl itaconate and dioctyl citracone, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate and diethyl nadicate Acid esters, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate,
Ethyl isobutyl phthalate, di-n-propyl phthalate,
Diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, Aromatic polycarboxylic esters such as diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate, and heterocyclic polycarboxylic esters such as 3,4-furandicarboxylic acid. Preferred examples can be given.

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. Among these compounds, it is preferable to use a carboxylic acid ester, particularly a polyvalent carboxylic acid ester,
Particularly, phthalic esters are preferably used.

The solid titanium component (A) used in the present invention
Uses, in addition to the magnesium compound, the liquid titanium compound and the electron donor (a), organic and inorganic compounds containing silicon, phosphorus, aluminum, and the like used as a carrier compound and a reaction aid, and the like, These may be prepared by contacting them.

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 component (A).

The solid titanium component (A) used in the present invention is prepared by contacting the magnesium compound as described above, the titanium compound in a liquid state, and the electron donor (a).

The method for producing the solid titanium component (A) using these compounds is not particularly limited, but this method will be briefly described below with several examples.

(1) A method of contacting and reacting a magnesium compound, the compound having two or more ether bonds, and a titanium compound in an arbitrary order. In this reaction, each component may be pretreated with a compound having two or more ether bonds and / or a reaction auxiliary such as an electron donor (a), an organoaluminum compound, or a halogen-containing silicon compound.

(2) A method in which a liquid magnesium compound having no reducing property is reacted with a liquid titanium compound in the presence of the compound having two or more ether bonds to precipitate a solid magnesium / titanium composite. .

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) The reaction product obtained in (1) or (2)
A method in which the electron donor (a) and the titanium compound are further reacted.

(5) A method in which a solid obtained by pulverizing a magnesium compound, a compound having two or more ether bonds, and a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. Note that this method may include a step of pulverizing only the magnesium compound, or the magnesium compound and the compound having two or more ether bonds, or the step of pulverizing the magnesium compound and the titanium compound. It may be ground down. After the pulverization, a preliminary treatment with a reaction aid may be performed, followed by a treatment with a halogen or the like. In addition,
Examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) A method of contacting a reaction product of a metal oxide, an organomagnesium compound, and a halogen-containing compound with the compound having two or more ether bonds and a titanium compound.

(8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or alloxymagnesium is brought into contact with the compound having two or more ether bonds and a titanium compound and / or a halogen-containing hydrocarbon.

(9) A method of reacting a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium with a titanium compound, the compound having two or more ether bonds, and, if necessary, a halogen-containing compound such as a halogen-containing silicon compound.

(10) A magnesium compound in a liquid state having no reducing property is reacted with an organoaluminum compound to precipitate a solid magnesium-aluminum complex, and then the compound having two or more ether bonds and a titanium-Kagov reaction are performed. Method.

When the solid titanium component (A) is produced by such a method, the amount of the magnesium compound, the titanium compound in the liquid state, and the amount of the electron donor (a) used depends on the type, contact conditions, contact sequence, and the like. Although different, the electron donor (a) is used in an amount of 0.01 mol to 5 mol, particularly preferably 0.1 mol to 1 mol, per mol of magnesium, and the titanium compound in a liquid state is used in an amount of 0.1 mol to 1000 mol,
Particularly preferably, it is used in an amount of 1 mol to 200 mol.

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

The solid titanium component (A) thus obtained is
It contains titanium, magnesium and halogen, and an electron donor (a).

In the solid titanium component (A), halogen / titanium (atomic ratio) is 2 to 100, preferably 4 to 90, and electron donor (a) / titanium (molar ratio) is 0.01 to 10
0, preferably 0.2 to 10, and the magnesium / titanium (atomic ratio) is desirably 2 to 100, preferably 4 to 50.

The solid titanium catalyst component [I] for olefin polymerization according to the present invention comprises the solid titanium component (A) as described above,
It is formed by contacting the electron donors (b) and (B).

As the electron donor (b), the above-described electron donor (a), that is, the compound having two or more ether bonds and the electron donor (a1) can be used. The organic silicon compounds shown can be used, and among them, a compound having two or more ether bonds and an organic silicon compound are particularly preferable.

R _n Si (OR ′) _4-n (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t-butylmethyldimethoxy. Silane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenylethoxysilane, bis-o
-Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxy Silane, ethyltriethoxysilane, vinyltriethoxysilane,
t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-
Norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate,
Trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane; cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3- Dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tri Cyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxy Sisilane, 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, hexenylmethoxysilane, cyclopentyltriethoxysilane , Tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferably used These organosilicon compounds are:
Two or more kinds can be used as a mixture.

Examples of the electron donor (b) that can be used other than the organosilicon 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'-tetramethylmethylenediamine: 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 diethyl phenyl phosphite;

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

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

When the solid titanium catalyst component (A) is brought into contact with the electron donor (b) to obtain the solid titanium catalyst component [I],
The electron donor (b) is used in an amount of 0.1 to 50 mol, preferably 0.5 to 0.5 mol per 1 mol of titanium atom of the solid titanium catalyst component [A].
-30 mol, more preferably 1-10. At this time, if necessary, an organometallic compound catalyst component [II] described later can be used, and the amount thereof is 0.1 to 300 mol, preferably 0.5 to 300 mol per 1 mol of titanium atom of the solid titanium catalyst component (A). It is preferred that the amount is from 100 to 100 mol, particularly preferably from 1 to 50 mol.

As described above, in the solid titanium catalyst component [I [, the electron donor (a) and the electron donor (b) used in the preparation of the solid titanium component (A)] Electron donors other than the above compounds having an ether bond can be used, but the solid titanium component (A)
One of the electron donor (a) and the electron donor (b) used in the above must be a compound having two or more ether bonds.

The catalyst for olefin polymerization according to the present invention comprises the solid titanium catalyst component [I] and a group I to group II of the periodic table.
It is formed from an organometallic compound catalyst component [II] containing a metal selected from Group I and, if necessary, an electron donor (c) [III] containing a compound having two or more ether bonds.

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.

Alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide.

Alkyl aluminum halides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum 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 group, -OAlR ^d ₂ group, -NR ^e ₂ group, a -SiR ^f ₃ group or -NA1R ^h ₂ group, n is ^{1~2, R g, 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, and the like; R ^e is a hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, and the like; ^f
And ^Rg is a methyl group, an ethyl group, or 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₎ (such as _{iso-Bu) 2 Al (OSiMe} 3) (iso-Bu) 2 Al (OSiEt 3), (iii) R a n Al (OAR d 2) 3-n Et 2 AlOAlEt 2 (iso-Bu) such as _{2 AlOAl (iso-Bu) 2} , (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 AlN (Me ₃ Si) ₂ etc., (v) R ^a _n Al (SiR ^f ₃ ) _3-n (iso-Bu) ₂ AlSiMe ₃ etc. 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 alkylated complex with Group I metal and aluminum, with the general formula M ^l AlR ^j ₄ (where, M ^l is Li, Na, K, 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 ₁ R ₂ M
₂ (provided that 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.

For the preparation of the olefin polymerization catalyst according to the present invention, the electron donor (c) [III] containing the compound having two or more ether bonds is used as necessary. For example, the electron donor (b) used for preparing the solid titanium catalyst component [I] according to the present invention can be used.

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

In the olefin polymerization method according to the present invention, it is preferable that the α-olefin is preliminarily polymerized on the olefin polymerization catalyst. This pre-polymerization was performed using 1 g of olefin polymerization catalyst.
The reaction is carried out by pre-polymerizing the α-olefin in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g.

In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. In the method for polymerizing olefins according to the present invention, the concentration of the solid titanium catalyst component [I] in the prepolymerization is as follows:
In terms of titanium atoms, it is usually desired to be in the range of about 0.001 to 100 mmol, preferably about 0.01 to 50 mmol, particularly preferably 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 [I].
Any amount may be used so long as the polymer of the formula (1) 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 olefin polymerization method according to the present invention, in the preliminary polymerization,
If necessary, the electron donor (b) containing the compound having two or more ether bonds can be used.

At this time, in the olefin polymerization method according to the present invention, these compounds are used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, per 1 mol of titanium atom in the solid titanium catalyst component [I].
More preferably, it is used in an amount of 1 to 10 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. As described above, 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, it is preferable to carry out the preliminary polymerization 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 carried out in an amount of about 0.1 to 1000 g, preferably about 0.1 g / g of the solid titanium catalyst component [Ia] or [Ib].
It is desirable to carry out the process so as to produce 0.3 to 500 g, particularly preferably 1 to 200 g, of the polymer.

In the olefin polymerization method according to the present invention, olefins 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, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Octadecene, 1-eicosene and the like can be mentioned.

In the polymerization method according to the present invention, these olefins can be used alone or in combination. Further, styrene, aromatic vinyl compounds such as allylbenzene, alicyclic vinyl compounds such as vinylcyclohexane, cyclopentene, cycloheptene, norbornane,
5-methyl-2-norbornane, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,
Cyclic olefins such as 8a-octahydronaphthalene, 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,
A compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene such as a diene such as 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, isoprene or butadiene is used as a polymerization raw material. You can also.

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 [I] 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] is such that the metal atom is usually about 1 to 2000 mol, preferably about 5 to 500 mol, per 1 mol of titanium atom in the prepolymerization catalyst in the polymerization system. Used in quantity.

Furthermore, in the polymerization method according to the present invention, the electron donor (c) optionally used is a metal (II) of the component [II].
Usually about 0.001 mol to 10 mol, preferably 0.0 mol
It is used in an amount such that it becomes 1 mol to 2 mol.

If hydrogen is used at the time of the main polymerization, the molecular weight of the obtained polymer can be adjusted, and polymerization 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 propylene is polymerized during olefin polymerization using the olefin polymerization catalyst as described above, the isotactic index (I
I) is at least 70%, preferably at least 85%, particularly preferably at least 95%
A propylene-based polymer as described above 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.

Further, the index Mw / Mn of the molecular weight distribution measured using GPC (gel permeation chromatography) is smaller than that of a polymer obtained by a conventional method, and generally a polymer of 5 or less is obtained. .

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

Effect of the Invention The solid titanium catalyst component [I] for olefin polymerization according to the present invention comprises (A) a solid titanium component containing titanium, magnesium, halogen, and an electron donor (a); A compound formed by contacting a donor (a), wherein one of the electron donor (a) and the electron donor (b) has two or more ether bonds represented by a specific formula. is there.

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

The olefin polymerization catalyst according to the present invention comprises the solid titanium catalyst component [I] and an organometallic compound catalyst component [II] containing a metal selected from Groups I to III of the periodic table.
And, if necessary, an electron donor (c) containing two or more of the above ether compounds, and the method for polymerizing an olefin according to the present invention comprises a monomer selected from ethylene and an α-olefin. The polymer 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 stereoactivity and high stereospecificity can be obtained in addition to high catalytic activity and efficient polymerization reaction.

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

Example 1 [Preparation of solid titanium catalyst component [A]] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 2-
After 390.6 g of ethylhexyl alcohol was heated and reacted at 130 ° C. for 2 hours to form a homogeneous solution, 21.3 g of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour. Was dissolved in this homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of this homogeneous solution was maintained at -20 ° C.
The whole amount was dropped in 200 ml over 1 hour. After completion of the charging, the temperature of the mixture was raised to 110 ° C. over 4 hours,
When the temperature reached 10 ° C., 5.22 g of diisobutyl phthalate was added, and the mixture was kept under stirring at the same temperature for 2 hours. 2
After completion of the reaction for a period of time, a solid portion was collected by hot filtration, and the solid portion was resuspended in 275 ml of titanium tetrachloride.
The heating reaction was performed at 10 ° C. for 2 hours. After the completion of the reaction, the solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the washing solution. The solid titanium catalyst component [A] prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The solid titanium catalyst component [A] thus obtained
Was 2.4% by weight of titanium, 60% by weight of chlorine, 20% by weight of magnesium and 13.0% by weight of diisobutyl phthalate.

[Preliminary treatment of solid titanium catalyst component [A]] In a 400 ml four-neck glass reactor equipped with a stirrer, 100 ml of purified hexane, 10 mmol of triethylaluminum, 2-isopropyl-2-isopentyl-1,3-dimethoxy under a nitrogen atmosphere. Washing consisting of 2 mmol of propane (IPAMP), 1 mmol of the above-mentioned solid titanium catalyst component [A] in terms of titanium atom, and stirring and mixing at 20 ° C. for 1 hour, and then allowing to stand, removing the supernatant and adding purified hexane. After performing the operation twice, the suspension was resuspended in purified hexane and the whole amount was transferred to a catalyst bottle. At this time, the measurement of the entire volume was also performed, and the slurry concentration of the catalyst was also measured.

[Polymerization] An autoclave having an internal volume of 2 liters was charged with 750 ml of purified hexane, and 0.75 mmol of triisobutylaluminum and 0.015 mmol of a pretreated solid titanium catalyst component (A) were converted into 0.015 mmol in terms of titanium atoms in a propylene atmosphere at 40 ° C. .

After heating to 60 ° C., 200 ml of hydrogen was introduced and the temperature was raised to 70 ° C., followed by propylene polymerization for 2 hours. 7k pressure during polymerization
g / cm ² G. After completion of the polymerization, the slurry containing the produced solid was filtered to separate into a white powder and a liquid phase. The yield of the white powder polymer after drying was 328.2 g, the extraction residual ratio by boiling heptane was 98.66%, the MFR was 6.9 dg / min, and the apparent bulk specific gravity was 0.4.
It was 3 g / ml. On the other hand, 1.1 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Therefore, the activity was 22,000 g-PP / mmol-Ti, and the total II (tII) was 98.4%.

Mw / Mn measured by GPC (gel permeation chromatography) was 4.44.

Example 2 The pretreatment of the solid titanium catalyst component (A) was carried out in the same manner as in Example 1 except that 10 mmol of IPAMP was used in the pretreatment of the solid titanium catalyst component (A). Propylene was polymerized in the same manner as in Example 1 except that the catalyst component (A) subjected to the pretreatment was used. As a result, the activity was 21,700 g-PP / mmolTi, t-II: 98.3%, the MFR of the white powder was 4.9, and the apparent bulk specific gravity was 0.46 g / ml.

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 Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 4/60-4/70

Claims (3)

(57) [Claims] An electron donor formed by contacting (A) a solid titanium component containing titanium, magnesium, halogen, and an electron donor (a) and (B) an electron donor (b); One of the donor (a) and the electron donor (b) has 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 together form a ring other than a benzene ring Which may have an atom other than carbon in the main chain), which has two or more ether bonds. Titanium catalyst component. 2. [I] (A) titanium, magnesium,
A solid titanium component containing a halogen and an electron donor (a), and (B) an electron donor (b), which are formed by contacting with each other, and any one of the electron donor (a) and the electron donor (b). One of the following formulas (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 the main chain may contain atoms other than carbon.) A solid titanium catalyst component for olefin polymerization, which is a compound having two or more ether bonds represented by [II] an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table, and, if necessary, [III] an electron containing a compound having two or more ether bonds. A catalyst for olefin polymerization, which is formed from the donor (c). 3. A method for polymerizing olefins, comprising polymerizing ethylene and / or an α-olefin using the catalyst for olefin polymerization according to claim 2.