JPH10147611A - Catalyst for olefin polymerization, preliminary polymerization catalyst and polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for olefin polymerization capable of producing a high stereoregular polyolefin having wide distribution of molecular weight and excellent moldability in excellent polymerization activity, and to provide a method for polymerization of an olefin using the catalyst for the olefin polymerization. SOLUTION: This catalyst for olefin polymerization comprises (A) a solid-like titanium catalyst component containing magnesium, titanium, a halogen and a polyfunctional carboxylic acid ester or a polyether, (B) an organoaluminum compound and (C) an organosilane compound of the formula (cyclo-R<1> ) and (cyclo-R<2> )Si(OR<a> )2 [OR<a> is methoxy or ethoxy group and (cyclo-R<1> ) and (cyclo-R<2> ) are each a 3-10C cycloalkyl group which may have a substituent group and the ring carbon number of (cyclo-R<1> ) is different by >=2 from the ring carbon number of (cyclo-R<2> ). The catalyst component may preliminarily be polymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst and a olefin polymerization method capable of producing a highly stereoregular polyolefin having a wide molecular weight distribution and excellent moldability with high polymerization activity.

[0002]

BACKGROUND OF THE INVENTION As a catalyst for polyolefin production, a Ziegler-Natta catalyst comprising a titanium catalyst component and an organoaluminum compound has been widely used. In particular, a carrier-supported solid titanium catalyst component has been used as the titanium catalyst component. It is known that a catalyst containing the compound exhibits high polymerization activity. Particularly, a catalyst containing a magnesium chloride-supported titanium catalyst component among solid titanium catalyst components exhibits high polymerization activity and can produce a polyolefin having high stereoregularity when an olefin such as propylene is polymerized. Known as a catalyst.

Various studies have been conducted on a catalyst containing such a solid titanium catalyst component in order to improve the polymerization activity and obtain a polyolefin having desired characteristics.
For example, as a component when preparing a solid titanium catalyst component,
Alternatively, it has been proposed to use various electron donors when forming an olefin polymerization catalyst from a solid titanium catalyst component and an organoaluminum compound.

[0004] The applicant of the present invention has also disclosed in Japanese Patent Application Laid-Open No. 58-83006 that a highly stereoregular polyolefin can be produced in a high yield and that the particle size, particle size distribution, particle properties and bulk specific gravity are excellent. As a catalyst for polyolefin production, a solid titanium catalyst component containing at least a carboxylic acid ester as an internal donor (internal electron donor), an organoaluminum compound, and Si—O—C or Si as an external donor (external electron donor). An olefin polymerization catalyst comprising an -silicon compound having an -NC bond has been proposed.

[0005] Si-O- as such an electron donor
Specific examples of the organosilicon compound having a C bond include alkoxysilanes such as tetraethoxysilane, phenyltriethoxysilane, and diphenyldimethoxysilane.

Among such alkoxysilanes, cyclopentyl, substituted cyclopentyl, cyclopentenyl, substituted cyclopentenyl, cyclopentadienyl, substituted cyclopentadienyl represented by dicyclopentyldimethoxysilane, etc. Group or S
An olefin polymerization catalyst using dimethoxysilane having two hydrocarbon groups in which the carbon adjacent to i is a secondary or tertiary carbon as an electron donor has also been proposed.

The inventor of the present invention has continued his research on such olefin polymerization catalysts. As a result, he has found that, in addition to the solid titanium catalyst component and the organoaluminum compound, among the organosilicon compounds as an external electron donor, a cycloalkyl group is particularly preferred. An olefin polymerization catalyst formed using a dialkoxysilane compound having two or more ring carbon atoms different from each other in these cycloalkyl groups has excellent polymerization activity, has a wide molecular weight distribution, and has good moldability. It has been found that the present invention is excellent in that it can produce a highly stereoregular polyolefin, and has completed the present invention.

[0008]

An object of the present invention is to provide an olefin polymerization catalyst capable of producing a highly stereoregular polyolefin having a wide molecular weight distribution and excellent moldability with high polymerization activity, and a method for polymerizing olefins using the olefin polymerization catalyst. It is intended to provide.

[0009]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises:
(A) a solid titanium catalyst component containing magnesium, titanium, halogen, and a polycarboxylic acid ester or polyether, (B) an organoaluminum compound, and (C) (cyclo-R ¹ ) (cyclo-R ² ) Si (OR ^a ) ₂ (1) wherein the OR ^a group is a methoxy group or an ethoxy group, and (cyclo-R ¹ ) and (cyclo-R ² ) each have a substituent. And a cycloalkyl group having 3 to 10 ring carbon atoms, and the number of ring carbon atoms of (cyclo-R ¹ ) is different from that of (cyclo-R ² ) by 2 or more. And an organosilane compound represented by the formula:

The olefin polymerization catalyst according to the present invention comprises: [I] the (A) solid titanium catalyst component described above, (B) an organoaluminum compound, and if necessary, (D) an electron donor. The olefin polymerization catalyst may be formed from a prepolymerized catalyst in which an olefin is prepolymerized, [II] the organic silane compound (C), and [III] an organic aluminum compound (B) as required.

The electron donor (D) at the time of the prepolymerization may be the above-mentioned organic silane compound (C). The olefin polymerization method according to the present invention is characterized in that an olefin is polymerized in the presence of the olefin polymerization catalyst as described above.

[0012]

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

In the present invention, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization. The term "polymer" means not only homopolymer but also copolymer. Is sometimes used in a sense that also encompasses

First, the solid titanium catalyst component (A) used in forming the olefin polymerization catalyst according to the present invention will be described. The solid titanium catalyst component used in the present invention contains at least magnesium, titanium, halogen, and a polycarboxylic acid ester or polyether as essential components. The solid titanium catalyst component is
The preparation method is not limited as long as these components are contained, and (a-1) a magnesium compound, (a-2) a titanium compound and (a-3) a polyvalent carboxylic acid ester or polyether by various methods. Can be prepared by contact with The components used when preparing the solid titanium catalyst component are shown below.

(A-1) Magnesium Compound In the present invention, examples of the magnesium compound include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

Examples of the magnesium compound having a reducing ability include an organic magnesium compound represented by the following formula. X _n MgR _{2-n In the} formula, n is 0 ≦ n <2, and R is hydrogen or carbon atom 1
20 to 20 alkyl groups, aryl groups or cycloalkyl groups, and when n is 0, two Rs may be the same or different. X is a halogen.

Specific examples of such an organomagnesium compound having a reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, and the like.
Dialkyl magnesium compounds such as dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium, and ethyl butyl magnesium; alkyl magnesium such as ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, and amyl magnesium chloride Examples thereof include alkyl magnesium alkoxides such as halide, butyl ethoxy magnesium, ethyl butoxy magnesium and octyl butoxy magnesium, and other butyl magnesium hydrides.

Specific examples of the magnesium compound having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, methoxymagnesium chloride, ethoxymagnesium chloride and isopropoxymagnesium chloride. Alkoxy magnesium halides such as butoxymagnesium chloride, octoxymagnesium chloride, allyoxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride, ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxy Alkoxy magnesium such as magnesium,
Examples include allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium, and magnesium carboxylate such as magnesium laurate and magnesium stearate. In addition, magnesium metal and magnesium hydride can be used.

The magnesium compound having no reducing ability may be a compound derived from the magnesium compound having the reducing ability described above or a compound derived at the time of preparing the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having reducing ability, for example, a magnesium compound having reducing ability is converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, It may be brought into contact with a halogen-containing compound or a compound having an OH group or an active carbon-oxygen bond.

The above-mentioned magnesium compound having a reducing ability and the magnesium compound having no reducing ability form complex compounds and complex compounds with other metals such as aluminum, zinc, boron, beryllium, sodium and potassium. Or a mixture with another metal compound. Further, the magnesium compound may be used alone, or two or more of the above compounds may be used in combination.

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

Of these, magnesium compounds having no reducing ability are preferred, and halogen-containing magnesium compounds are particularly preferred. Of these, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferred.

In the present invention, when preparing the solid titanium catalyst component, the magnesium compound (a-1)
Is preferably used in a liquid state. When the magnesium compound is a solid among the above magnesium compounds, the magnesium compound can be made into a liquid state by using the electron donor (a-4).

As the electron donor (a-4), alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and the like described later as the electron donor (a-6) can be used. Can be used.

Further, metal acid esters such as tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium can also be used. .

Of these, alcohols and metal acid esters are particularly preferably used. The reaction between the solid magnesium compound and the electron donor (a-4) is generally carried out by bringing the solid magnesium compound into contact with the electron donor (a-4) and, if necessary, heating. This contact is usually performed at a temperature of 0 to 200 ° C, preferably 20 to 180 ° C, more preferably 50 to 150 ° C.

The above reaction may be carried out in the presence of a hydrocarbon solvent (a-5). Specific examples of such a hydrocarbon solvent include pentane, hexane, heptane, octane, decane, dodecane, tetradecane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, Alicyclic hydrocarbons such as cyclohexene, halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene, and chlorobenzene, and aromatic hydrocarbons such as benzene, toluene, and xylene are used.

(A-2) Titanium Compound In the present invention, the titanium compound (a-2) is preferably a liquid titanium compound, and particularly preferably a tetravalent titanium compound. Examples of such a tetravalent titanium compound include a compound represented by the following formula.

Ti (OR) _g X _{4-g In the} formula, R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4. Specific examples of such a compound include titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ , Ti (OCH ₃ ) Cl ₃ , and Ti (OC ₂ H ₅ ) Cl.
_{3, Ti (On-C 4} H 9) Cl 3, Ti (OC 2 H 5) Br 3, Ti (O-
iso-C ₄ H ₉₎ trihalide, alkoxy titanium such as _{Br 3, Ti (OCH 3)} 2 Cl 2, Ti (OC 2 H 5) 2 Cl 2, Ti (On
-Dialkoxytitanium dihalides such as -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)
Monohalogenated trialkoxy titanium such as ₃ Br, T
i (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ ,
Tetraalkoxy titanium such as Ti (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, titanium tetrahalides are preferred, and titanium tetrachloride is particularly preferred. These titanium compounds can be used in combination of two or more. The above titanium compound may be used after being diluted with a hydrocarbon, a halogenated hydrocarbon or an aromatic hydrocarbon.

(A-3) Polycarboxylic acid ester or poly
In preparing the ether solid titanium catalyst component, a polycarboxylic acid ester or a polyether is used as an electron donor.

The polycarboxylic acid ester is represented, for example, by the following general formula.

[0033]

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In the above formula, 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, and R ³ and R ⁴ are hydrogen or a substituted hydrocarbon group. Or an unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other to form a cyclic structure. When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent contains a different atom such as N, O, S, and is, for example, C—O—C, COOR, COOH, OH, SO
_It has groups such as ₃ H, —C—N—C—, and NH ₂ .

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

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

Of these, phthalic esters are particularly preferred. These may be used in combination of two or more.
As the polyether, a polyether compound having two or more ether bonds existing through a plurality of atoms can be used.

Examples of the polyether include carbon, silicon, oxygen, nitrogen, phosphorus, boron, sulfur, and compounds in which two or more kinds of atoms are present between ether bonds. Among these, a compound in which a relatively bulky substituent is bonded to an atom between ether bonds and a plurality of carbon atoms are contained in an atom existing between two or more ether bonds is preferable. For example, a compound represented by the following formula: Polyethers are preferred.

[0039]

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(Where n is an integer of 2 ≦ n ≦ 10,
R ^{1 to} R ²⁶ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and arbitrary R ^{1 to} R ²⁶ ,
Preferably, R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and atoms other than carbon may be contained in the main chain. As the above polyether, specifically, 2- (2-
Ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 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- (diphenylmethyl) -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-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane , 2,2-diisopropyl-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-cyclohexylethyl) -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- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-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-dimethoxypropane, 2-
Phenyl-2-isopropyl-1,3-dimethoxypropane, 2-
Phenyl-2-s-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl
2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2- Isopropyl-1,3-dimethoxypropane,
2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-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-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3-diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-di Isoamyloxypropane, 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) bicyclo [2,2,1] heptane , 1,1-dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxy Methyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxycyclo Hexane, 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-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 and the like. As polyethers, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis (methoxymethyl) silane Silane, cyclohexyl-t-butylbis (methoxymethyl)
Silane, i-propyl-t-butylbis (methoxymethyl)
Silane and the like can also be mentioned.

Among these, 1,3-diethers are preferably used, and in particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, -Isopropyl-2-isopentyl-1,3-
Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl)-
1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-s-
Butyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-
Dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane and the like are preferably used. These may be used in combination of two or more.

In preparing the solid titanium catalyst component, both the above-mentioned polyvalent carboxylic acid ester and polyether may be used, and other electron donors may be used together with the polyvalent carboxylic acid ester or polyether. (a-6) can be used.

Specific examples of other electron donors (a-6) include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. Products, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, oxygen-containing cyclic compounds, and the like. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl Alcohols having 1 to 18 carbon atoms such as alcohols, halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol And phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as naphthol, acetone and methyl ethyl ketone. Emissions, methyl isobutyl ketone, acetophenone, benzophenone, carbon atoms such as benzoquinone 3-1
Aldehydes having 2 to 15 carbon atoms such as ketones 5, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, vinyl propyl acetate, octyl acetate, acetic acid Cyclohexyl, 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, ethoxy Organic acid esters having 2 to 18 carbon atoms such as ethyl benzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, and the like, and the number of carbon atoms 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, anisole, diphenyl ether and other ethers having 2 to 20 carbon atoms, acetic acid N, N-dimethylamide, benzoic acid N, Acid amides such as N-diethylamide, toluic acid N, N-dimethylamide, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylenediamine, hexamethyamine Amines such as diamine; nitriles such as acetonitrile, benzonitrile and trinitrile; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride; pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole; pyrroline; Indole; pyridines such as pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, pyridine such as trimethylpyridine, phenylpyridine, benzylpyridine and pyridine chloride; nitrogen-containing cyclic compounds such as piperidine, quinoline and isoquinoline , Tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, dite Ropiran like cyclic oxygen-containing compound such as.

As the electron donor (a-6), an organic silane compound, water or an anionic, cationic or nonionic surfactant as described later can be used as a catalyst component.

These electron donors (a-6) can be used in combination of two or more. Preparation of Solid Titanium Catalyst Component (A) In preparing the solid titanium catalyst component, in addition to the above compounds, an organic compound or an inorganic compound containing silicon, phosphorus, aluminum or the like used as a carrier and a reaction aid, etc. A compound or the like may be used.

Examples of such carriers include Al ₂ O ₃ and Si.
O ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, Sn
Examples include resins such as O ₂ , BaO, ThO, and styrene-divinylbenzene copolymer. Of these,
Al ₂ O ₃ , SiO ₂ , and styrene-divinylbenzene copolymer are preferably used.

The solid titanium catalyst component (A) includes the magnesium compound (a-1) and the titanium compound (a-2) as described above.
And polycarboxylic acid esters or polyethers
It can be prepared by contacting (a-3), can be prepared by any method including known methods, the preparation method is not particularly limited, in the present invention,
It is preferable to contact the liquid state magnesium compound (a-1), liquid titanium compound (a-2) and polycarboxylic acid ester or polyether (a-3).

When the compounds (a-1) to (a-3) are brought into contact with each other to prepare a solid titanium catalyst component, a hydrocarbon can be used if necessary. The same hydrocarbon solvents as those used when liquefying compound (a-1) can be used.

Hereinafter, a specific method for preparing a solid titanium catalyst component will be briefly described with reference to several examples. In the following method, as the organoaluminum compound, those described below as the organoaluminum compound (B) are used.

(1) Magnesium compound, electron donor (a-
4) and a magnesium compound (a-1) in a liquid state comprising a hydrocarbon solvent is contact-reacted with an organoaluminum compound to precipitate a solid, or is contacted and reacted with a titanium compound (a-2) during the precipitation. .

In this process, the polycarboxylic acid ester or polyether (a-3) (hereinafter referred to as electron donor (a-3)) is brought into contact with the contact product at least once. (2) The titanium compound (a-2) and the electron donor (a-3) are contact-reacted with a contact product of the inorganic carrier and the organomagnesium compound (a-1).

At this time, the contact product between the inorganic carrier and the organomagnesium compound (a-1) is previously converted to a halogen-containing compound and / or
Or you may make it contact-react with an organoaluminum compound. (3) a magnesium compound, an electron donor (a-4), a magnesium compound in a liquid state (a-1) optionally further comprising a hydrocarbon solvent, and a mixture of an inorganic carrier or an organic carrier; A supported inorganic or organic carrier is prepared, and then contacted with a titanium compound (a-2).

In this step, the electron donor (a-3) is brought into contact with the contact product at least once. (4) magnesium compound (a-1), titanium compound (a-2),
An electron donor (a-4), optionally a solution further containing a hydrocarbon solvent, an inorganic or organic carrier, and an electron donor
(a-3) and.

(5) Liquid state organomagnesium compound (a
-1) is contacted with a halogen-containing titanium compound (a-2) and an electron donor (a-3). (6) After contacting the liquid state organomagnesium compound (a-1) with a halogen-containing compound, the titanium compound (a-2)
Contact.

In this step, the electron donor (a-3) is used at least once. (7) an alkoxy group-containing magnesium compound (a-1), a halogen-containing titanium compound (a-2) and an electron donor (a-3)
And contact reaction.

(8) A liquid magnesium compound (a-1) comprising an alkoxy group-containing magnesium compound and an electron donor (a-4) is converted into a titanium compound (a-2) and an electron donor (a-
3) Contact reaction with.

(9) A liquid magnesium compound (a-1) comprising an alkoxy group-containing magnesium compound and an electron donor (a-4) is brought into contact with an organoaluminum compound, and then a titanium compound (a-2) And contact reaction.

In this step, the electron donor (a-3) is brought into contact with the contact product at least once. (10) Liquid magnesium compound having no reducing ability (a-1)
And the titanium compound (a-2) in the presence or absence of the electron donor (a-3).

In this process, the electron donor (a-3) is brought into contact with the contact product at least once. (11) The reaction product obtained in (1) to (10) is further contacted with a titanium compound (a-2).

(12) An electron donor (a-3) and a titanium compound (a-2) are further added to the reaction products obtained in (1) to (11).
Contact. Contact of each component as described above is usually -7.
The reaction is performed at a temperature of 0 ° C to 200 ° C, preferably -50 ° C to 150 ° C, and more preferably -30 to 130 ° C.

The amount of each component used in preparing the solid titanium catalyst component varies depending on the preparation method and cannot be specified unconditionally.
The polycarboxylic acid ester or polyether (a-3) is used in an amount of 0.01 to 10 mol, preferably 0.1 to 5 mol, and the titanium compound (a-2) in a liquid state is preferably used in an amount of 0.01 to 1000 mol. Can be used in an amount of 0.1 to 200 mol.

In the present invention, the solid titanium catalyst component thus obtained is preferably washed with a hydrocarbon solvent at 0 to 150 ° C. As the hydrocarbon solvent, the hydrocarbon solvent (a-5) as described above for liquefying the magnesium compound can be used.
Aliphatic hydrocarbon solvents or halogen-free aromatic hydrocarbon solvents are preferably used.

In washing the solid titanium catalyst component,
The hydrocarbon solvent is usually from 10 to 500 per gram of the solid.
It can be used in an amount of about ml. The solid titanium catalyst component (A) thus obtained contains magnesium,
It contains titanium, halogen and a polycarboxylic acid ester or polyether, and contains titanium in an amount of 0.1 to 10% by weight, preferably 0.2 to 7.0% by weight, and magnesium and halogen in a total amount of 95%. In the amount of 0.5 to 30% by weight,
It is desirable to contain it in an amount of% by weight.

(B) Organoaluminum Compound In the present invention, the organoaluminum compound used for forming the olefin polymerization catalyst is represented by the following formula, for example.

[0065] 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, and n is 1 to 3. R ^a 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, Examples include a pentyl group, a hexyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group. Specific examples of such an organoaluminum compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum, and alkenyl such as isoprenylaluminum. Dialkylaluminum halides such as aluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquichloride B Alkylaluminum sesquihalide such as bromide, methyl aluminum dichloride, ethyl aluminum dichloride,
Examples thereof include alkylaluminum dihalides such as isopropylaluminum dichloride and ethylaluminum dibromide, and alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

Further, examples of the organoaluminum compound include compounds represented by the following formula. In R ^a _n AlY _3-n the above formulas, 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 -N (R ^g) AlR ^h ₂ group, n is ^{1~2, R b, R c,} R d and R ^h
Is a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., ^Re is hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group, etc., and R ^f and R ^g Represents a methyl group, an ethyl group or the like.

Specific examples of such an organoaluminum compound include the following compounds. _{^{(i) R a n Al (}} OR b) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (ii) R a n Al}} (OSiR c) 3-n Et 2 Al (OSiMe 3 ), (Iso-Bu) ₂ Al (OSiM
_{e 3), (iso-Bu} ) 2 Al (OSiEt 3) , _{^{etc., (iii) R a n Al}} (OAlR d 2) 3-n Et 2 AlOAlEt 2, (iso-Bu) 2 AlOAl (iso-Bu)
Such as ^{_{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}} ( such as ^{_{SiR f 3) 3-n (}} iso-Bu) 2 AlSiMe 3, (vi) R a n Al [N (R ^g) -AlR ^h _{2] 3-n} such as _{Et 2 AlN (Me) -AlEt 2} (iso-Bu) 2 AlN (Et) Al (iso-Bu) 2.

Further, there may be mentioned similar compounds, for example, organic aluminum compounds in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. More specifically, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ ,
(C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ Al
N (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ and the like, and aluminoxanes such as methylaluminoxane.

Among the above-mentioned organoaluminum compounds, ^Ra ₃ Al, R ^a _n Al (OR ^b ) _3-n and R ^a _n Al
An organoaluminum compound represented by (OAlR ^d ₂ ) _3-n is preferably used.

As the organoaluminum compound, a complex alkylated compound represented by the following general formula can also be used. M ¹ AlR ^j ₄ (M ¹ is Li, Na, K, and R ^j has 1 to 15 carbon atoms.
Specifically, LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ )
_{4 and the} like.

These compounds can be used in combination of two or more kinds. (C) Organosilane Compound In the present invention, when preparing an olefin polymerization catalyst,
In addition to the solid titanium catalyst component (A) and the organoaluminum compound (B) as described above, a dialkoxysilane compound containing a cycloalkyl group having a specific number of carbon atoms as represented by the following general formula (1) is used. Can be

(Cyclo-R ¹ ) (cyclo-R ² ) Si (OR ^a ) ₂ (1) wherein the OR ^a group is a methoxy group or an ethoxy group, and (cyclo-R ¹ ) and (cyclo-R ¹ ) -R ² ) is a cycloalkyl group having 3 to 10 ring carbon atoms, each of which may have a substituent, and (cyclo-R ¹ ) has the number of ring carbon atoms and (cyclo-R ² ) Is different from the ring member carbon number by 2 or more. In the above, specific examples of the cycloalkyl group having 3 to 10 ring members include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

These cycloalkyl groups include an alkyl group,
It may have a substituent such as a cycloalkyl group, an aryl group or an aralkyl group. Further, although the number of ring carbon atoms of the above (cyclo-R ¹ ) and the number of ring carbon atoms of the (cyclo-R ² ) are different from each other by 2 or more, a combination of such cycloalkyl groups having a ring member carbon number difference may be used. Specific examples include a combination of a cyclohexyl group and a cyclopropyl group, a combination of a cyclopropyl group and a cyclopentyl group, a combination of a cyclobutyl group and a cyclohexyl group, and the like.

It is desirable to have at least a cyclopentyl group or a cyclohexyl group. The number of ring carbon atoms of the two cycloalkyl groups is different by 2 or more, but is preferably 2 to 4, and more preferably 2 to 3.

Specific examples of such organic silane compounds include, for example, cyclopropylcyclopentyldimethoxysilane (cyclopentylcyclopropyldimethoxysilane), cyclopropylcyclohexyldimethoxysilane (cyclohexylcyclopropyldimethoxysilane), cyclopropylcycloheptyldimethoxysilane, cyclopropyl Propylcyclooctyldimethoxysilane,
Cyclopropylcyclononyldimethoxysilane, cyclopropylcyclodecyldimethoxysilane, cyclobutylcyclohexyldimethoxysilane, cyclobutylcycloheptyldimethoxysilane, cyclobutylcyclooctyldimethoxysilane, cyclobutylcyclononyldimethoxysilane, cyclobutylcyclodecyldimethoxysilane, cyclopentylcyclo Heptyldimethoxysilane,
Cyclopentylcyclooctyldimethoxysilane, cyclopentylcyclononyldimethoxysilane, cyclopentylcyclodecyldimethoxysilane, cyclohexylcyclooctyldimethoxysilane, cyclohexylcyclononyldimethoxysilane, cyclohexylcyclodecyldimethoxysilane, cycloheptylcyclononyldimethoxysilane, cycloheptylcyclodecyldimethoxysilane, Cyclooctylcyclodecyldimethoxysilane,
Cyclopropylcyclopentyldiethoxysilane (cyclopentylcyclopropyldiethoxysilane), cyclopropylcyclohexyldiethoxysilane (cyclohexylcyclopropyldiethoxysilane), cyclopropylcycloheptyldiethoxysilane, cyclopropylcyclooctyldiethoxysilane, cyclopropylcyclononyl Diethoxysilane, cyclopropylcyclodecyldiethoxysilane, cyclobutylcyclohexyldiethoxysilane, cyclobutylcycloheptyldiethoxysilane, cyclobutylcyclooctyldiethoxysilane,
Cyclobutylcyclononyldiethoxysilane, cyclobutylcyclodecyldiethoxysilane, cyclopentylcycloheptyldiethoxysilane, cyclopentylcyclooctyldiethoxysilane, cyclopentylcyclononyldiethoxysilane, cyclopentylcyclodecyldiethoxysilane, cyclohexylcyclooctyldiethoxysilane , Cyclohexylcyclononyldiethoxysilane, cyclohexylcyclodecyldiethoxysilane, cycloheptylcyclononyldiethoxysilane, cycloheptylcyclodecyldiethoxysilane, cyclooctylcyclodecyldiethoxysilane, and the like.

Of these, cyclohexylcyclopropyldimethoxysilane and cyclobutylcyclohexyldimethoxysilane are particularly preferably used. Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention comprises (A) a solid titanium catalyst component, (B) an organoaluminum compound, and (C) an organosilane compound represented by the formula (1). Formed from

FIG. 1 shows a process for preparing such an olefin polymerization catalyst. In the present invention, a prepolymerized catalyst [I] can be formed by preliminarily (co) polymerizing an olefin with the above catalyst component, and specifically, [I] the solid titanium catalyst component (A) An olefin polymerization catalyst comprising (B) an organoaluminum compound and, if necessary, (D) an electron donor, a prepolymerized catalyst obtained by prepolymerizing an olefin; [II] the organosilane compound (C) And [III] an organoaluminum compound (B), if necessary, to form an olefin polymerization catalyst.

The electron donor (D) can be used if necessary during the prepolymerization.
Specifically, the organic silane compound (C) described above can be used, and other electron donors can also be used.

Examples of other electron donors include the above-mentioned polyether compounds, 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, Nitrogen-containing electrons such as substituted methylenediamines such as N, N, N ', N'-tetraethylmethylenediamine, and substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine Donors, phosphites such as triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite, etc. Oxygen-containing electron donors such as phosphorus-containing electron donors, 2,6-substituted tetrahydropyrans, and 2,5-substituted tetrahydropyrans may also be used. Can, it is also possible to further use of the organic silane compound other than the above (C) Other electron donor. As other organic silane compounds, specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane,
Diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-
Propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, Phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxysilane, methyltriaryloxy (allyloxy) silane, vinyltris (β-methoxyethoxysilane) , Vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, ethyl silicate, butyl silicate and the like.

As another organic silane compound, an organic silane compound having a bulky group represented by the following formula (2) can also be mentioned. During _{^{R a n Si (OR b)}} 4-n ... (2) ( wherein, n is 1, 2 or 3, when n is 1, R ^a is an secondary or tertiary hydrocarbon group , N is 2
Or when 3, at least one of R ^a is a secondary or tertiary hydrocarbon group, R ^a may be the same or different, and R ^b is a hydrocarbon having 1 to 4 carbon atoms. When (4-n) is 2 or 3, OR ^b may be the same or different. The organic silane compound (C) is not included in the compound represented by the formula (2).

In the organosilane compound having a bulky group represented by the formula (2), the secondary or tertiary hydrocarbon group may be a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a substituent And hydrocarbon groups in which the carbon adjacent to Si is secondary or tertiary.

Specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di-t-amyldimethoxysilane and the like can be mentioned. Can be

These can be used in combination of two or more.
Examples of the olefin used at the time of the prepolymerization include ethylene, propylene, 1-butene, 1-pentene, and 1-pentene.
Hexene, 3-methyl-1-butene, 3-methyl-1-pentene,
3-ethyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl
1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. Α-olefins having 2 or more carbon atoms are exemplified. Further, other vinyl compounds and polyene compounds as described later can also be used at the time of preliminary polymerization. These may be used in combination of two or more.

The α-olefin used in the prepolymerization is
It may be the same as or different from the α-olefin used in the main polymerization described below. In the present invention, there is no particular limitation on the method of performing the prepolymerization, for example, olefins, polyene compound can be performed in a liquid state,
Further, the reaction can be carried out in the presence of an inert solvent, and furthermore, can be carried out under gas phase conditions. Of these, it is preferable to add olefins and various catalyst components to the inert solvent in the presence of an inert solvent, and to carry out prepolymerization under relatively mild conditions. At this time, the reaction may be carried out under a condition in which the produced prepolymer is dissolved in the polymerization medium or under a condition in which the prepolymer is not dissolved, but it is preferably carried out under a condition in which the prepolymer is not dissolved.

The prepolymerization is usually carried out at about -20 to + 100 ° C, preferably at about -20 to + 80 ° C, and more preferably at -10 to + 80 ° C.
It is desirable to carry out at + 40 ° C. The prepolymerization can be performed in any of a batch system, a semi-continuous system, and a continuous system.

In the preliminary polymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. Although the concentration of the catalyst component in the prepolymerization varies depending on the type of the catalyst component, the concentration of the solid titanium catalyst component (A) is as follows.
Usually, about 0.001 to 5000 mmol, preferably about 0.01 to 1 in terms of titanium atom per liter of polymerization volume.
000 mmol, particularly preferably 0.1 to 500 mmol.

The organoaluminum compound (B) is usually used in an amount of about 0.1 to about 0.1 mol per mol of titanium in the solid titanium catalyst component.
It can be used in an amount of 1000 mol, preferably about 0.5 to 500 mol, particularly preferably 1 to 100 mol.

At the time of prepolymerization, the electron donor (D)
Is used as needed in an amount of usually 0.01 to 50 mol, preferably 0.05 to 30 mol, more preferably 0.1 to 10 mol, per 1 mol of titanium atoms in the solid titanium catalyst component (A). Can be.

At the time of prepolymerization, a molecular weight modifier such as hydrogen can be used. In the prepolymerization as described above, 0.01 to 2000 per g of the solid titanium catalyst component (A).
g preferably 0.03 to 1000 g, more preferably 0.1 to 1000 g.
From 0.5 to 200 g of the preliminary (co) polymer can be produced.

When the prepolymerized catalyst is obtained in a suspended state, the prepolymerized catalyst can be used as it is in a suspended state in the (main) polymerization of the next step, or the prepolymerized catalyst formed from the suspension can be used. The polymerization catalyst can be used separately.

The olefin polymerization catalyst according to the present invention may contain other components useful for olefin polymerization in addition to the above-mentioned components. Olefin Polymerization Method In the olefin polymerization method according to the present invention, an olefin polymerization catalyst comprising (A) a solid titanium catalyst component, (B) an organoaluminum compound and (C) a specific organosilane compound, or [I] a prepolymerized catalyst, [I
I] Organosilane compound (C) and if necessary [III]
The olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising the organoaluminum compound (B).

When an olefin is polymerized using such an olefin polymerization catalyst, a polyolefin having a wide molecular weight distribution and excellent moldability can be obtained. Examples of the olefin to be polymerized in the present invention include α-olefins having 2 or more carbon atoms as specifically shown in the preliminary polymerization.

Further, cyclopentene, cycloheptene,
Norbornene, 5-ethyl-2-norbornene, tetracyclododecene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,
Cycloolefins such as 5,8,8a-octahydronaphthalene, styrene, dimethylstyrenes, allylnaphthalene, allylnorbornane, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclopentane,
Vinyl compounds such as vinylcyclohexane, vinylcycloheptane, and allyltrialkylsilanes can also be used.

Among them, ethylene, propylene, 1-
Butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-
Methyl-1-pentene, vinylcyclohexane, dimethylstyrene, allyltrimethylsilane, allylnaphthalene and the like are preferably used.

Further, a small amount of a diene compound may be copolymerized with an olefin. As such a diene compound, specifically, 1,3-butadiene, 1,3-pentadiene,
1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5
-Methyl-1,4-hexadiene, 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,
Examples include 6-decadiene, 6-methyl-1,6-undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene. They are,
Two or more kinds may be used in combination.

In the present invention, the polymerization can be carried out by any of liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization. When the polymerization takes a reaction form of slurry polymerization, the above-mentioned inert organic solvent can be used as the reaction solvent, or an olefin that is liquid at the reaction temperature can be used.

In the polymerization, the solid titanium catalyst component (A) or the prepolymerized catalyst [I] is usually used in an amount of about 0.001 to 1 in terms of titanium atom per liter of polymerization volume.
It can be used in an amount of 00 mmol, preferably about 0.005 to 20 mmol.

The organoaluminum compound (B) (or [III]) is generally used in an amount of about 1 to 2000 mol, preferably about 2 to 500 mol per 1 mol of titanium atom in the polymerization system. It can be used in a molar amount.

When the prepolymerized catalyst [I] is used, the organoaluminum compound [III] may not be used in some cases. Organosilane compound (C) (or [I
I]) is a metal atom 1 of the organoaluminum compound (B).
It can be used in an amount of usually about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, per mol.

When hydrogen is used at the time of 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 olefin polymerization method according to the present invention, the polymerization is usually carried out at a temperature of about 20 to 300 ° C., preferably about 50 to 150 ° C., and a normal pressure to 100 kg / cm ² , although it varies depending on the kind of the olefin, the form of the polymerization, and the like.
It is preferably carried out under a pressure of about ^{2 to} 50 kg / cm ² .

In the polymerization method of the present invention, the polymerization can be carried out by any of a batch system, a semi-continuous system and a continuous system. Further, the polymerization was carried out by changing the reaction conditions.
It can also be performed in multiple stages.

In the present invention, an olefin homopolymer may be produced, or a random copolymer or a block copolymer may be produced from two or more olefins. In the present invention as described above, for example, when propylene is polymerized, polypropylene having a molecular weight distribution (Mw / Mn) of 5 or more, preferably 5 to 10 can be obtained.

[0103]

According to the present invention using the above specific organic silane compound as an external electron donor, a highly stereoregular polyolefin having a wide molecular weight distribution and excellent moldability can be obtained with high polymerization activity. .

[0104]

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

In the following Examples and Comparative Examples, the boiling heptane extraction residue ratio (t-II), which is an index of the stereoregularity of polyolefin, was determined by Soxhlet extraction with boiling heptane until the extraction residue became a constant weight. .

The amount of n-decane soluble component (t-DS) at 23 ° C. of the polyolefin was measured as follows. In a 1 liter flask, 3 g of sample (polyolefin), 20 mg of 2,
6-di-tert-butyl-4-methylphenol, 500 ml of n-
Add decane and heat at 145 ° C to dissolve. Cool to 23 ° C. over 8 hours after dissolution and maintain at 23 ° C. for 8 hours. The precipitated solid and an n-decane solution containing the dissolved polymer are separated by filtration through a glass filter. The liquid phase is dried at 150 ° C. under reduced pressure until a constant weight is obtained, and its weight is measured. The obtained polymer dissolution amount is calculated as a percentage with respect to the weight of the sample, and is defined as the amount of a 23 ° C. decane-soluble component of polypropylene.

The melt flow rate of the polyolefin (M
FR) is 230 ° C. according to ASTM D1238,
It was measured under a 2.16 kg load. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyolefin were determined by GPC.

[0108]

Example 1 [Preparation of solid titanium catalyst component] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C for 2 hours to form a homogeneous solution. 21.3 g of phthalic anhydride was added to this solution.
Was added and further stirred and mixed at 130 ° C. for 1 hour to dissolve.

After cooling the thus obtained homogeneous solution to room temperature, 30 ml of this homogeneous solution was dropped into 80 ml of titanium tetrachloride (TiCl ₄ ) maintained at -20 ° C. over 1 hour. .

The temperature of the resulting mixture was raised to 11 over 4 hours.
The temperature was raised to 0 ° C., and when the temperature reached 110 ° C., 2.1 g of diisobutyl phthalate (DIBP) was added, and the mixture was stirred and maintained at the same temperature for 2 hours.

After completion of the reaction, a solid portion was collected by hot filtration.
After resuspending the solid portion of TiCl ₄ 110 ml,
The resulting suspension was heated again at 110 ° C. for 2 hours. After the completion of the reaction, a 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 obtained as described above was stored as a hexane slurry. A portion of the solid titanium catalyst component hexane slurry was collected and dried, and the composition of the catalyst component was analyzed.

The solid titanium catalyst component comprises titanium at 2.2.
19.0% by weight of magnesium, 59.0% by weight of chlorine
% Of DIBP and 19.8% by weight of DIBP. [Polymerization] 400 ml of purified heptane was charged into an autoclave having an inner volume of 1 liter, and 0.4 mmol of triethylaluminum, 0.4 mmol of cyclohexylcyclopropyldimethoxysilane and 0.4 mmol of solid titanium obtained above were added at 60 ° C. in a propylene atmosphere. The catalyst component was charged at 0.008 mmol in terms of titanium atoms.

After 100 ml of hydrogen was introduced and the temperature was raised to 70 ° C., the temperature was maintained for 1 hour to polymerize propylene. During the polymerization, the pressure was kept at 5 kg / cm ² G. After completion of the polymerization, the slurry containing the produced polymer (solid) was filtered to separate into a white powder and a liquid phase.

The yield of the polymer obtained in the form of a white powder was 5
It was 5.2 g. Boiling heptane extraction residual ratio (t-II) of the powdery polymer was 98.94% by weight, and n-decane soluble component (t-DS) at 23 ° C. was 0.55% by weight. The melt flow rate (MFR) is 1.7 g / 10 min.
The weight average molecular weight distribution (Mw) measured by PC was 4.17.
× 10 ⁵ , and Mw / Mn was 5.72.

The liquid phase was concentrated to obtain 0.2 g.
Of a solvent-soluble polymer was obtained. Therefore, the polymerization activity was 6930 g-PP / mmol-Ti, 3180 g-PP / g-cat. The boiling heptane extraction residual ratio (t-II) of the entire polypropylene thus obtained was 98.6% by weight,
The n-decane soluble component (t-DS) at 23 ° C. was 0.75% by weight. Table 1 shows the results.

[0117]

Example 2 [Polymerization] Propylene was polymerized in the same manner as in Example 1 except that cyclobutylcyclohexyldimethoxysilane was used instead of cyclohexylcyclopropyldimethoxysilane.

The polymer was obtained in the form of a white powder, and no solvent-soluble polymer was obtained even when the liquid phase was concentrated. Table 1 shows the results.

[0119]

Comparative Example 1 [Polymerization] Propylene was polymerized in the same manner as in Example 1 except that dicyclopentyldimethoxysilane was used instead of cyclohexylcyclopropyldimethoxysilane. Table 1 shows the results.

[0120]

Comparative Example 2 [Polymerization] Propylene was polymerized in the same manner as in Example 1 except that cyclobutylcyclopentyldimethoxysilane was used instead of cyclohexylcyclopropyldimethoxysilane. Table 1 shows the results.

[0121]

Reference Example 1 Propylene was polymerized in the same manner as in Example 1 except that dicyclopropyldimethoxysilane was used instead of cyclohexylcyclopropyldimethoxysilane. Table 1 shows the results.

[0122]

[Table 1]

[Brief description of the drawings]

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

Claims (4)

[Claims] (A) magnesium, titanium, halogen,
And a solid titanium catalyst component containing a polycarboxylic acid ester or a polyether, (B) an organoaluminum compound, and (C) (cyclo-R ¹ ) (cyclo-R ² ) Si (OR ^a ) ₂ . 1) [wherein the OR ^a group is a methoxy group or an ethoxy group, and (cyclo-R ¹ ) and (cyclo-R ² ) each have 3 to 10 ring carbon atoms which may have a substituent. And the number of ring carbon atoms of (cyclo-R ¹ ) is different from that of (cyclo-R ² ) by 2 or more. An olefin polymerization catalyst comprising: an organosilane compound represented by the formula: 2. [I] (A) a solid titanium catalyst component containing magnesium, titanium, halogen, and a polycarboxylic acid ester or polyether, (B) an organoaluminum compound, and if necessary, (D) ) An olefin polymerization catalyst comprising an electron donor, a prepolymerized catalyst obtained by prepolymerizing an olefin, and [II] (cyclo-R ¹ ) (cyclo-R ² ) Si (OR ^a ) ₂ ... (1) [ wherein, oR ^a group is methoxy group or ethoxy group, (cyclo-R ¹⁾ and (cyclo-R ²⁾ are each cycloalkyl optionally ring members 3 to 10 carbon atoms which may have a substituent And the number of ring carbon atoms of (cyclo-R ¹ ) is different from that of (cyclo-R ² ) by 2 or more. [III] A catalyst for olefin polymerization, which comprises an organic silane compound (C) represented by the formula [I] and [III] an organic aluminum compound (B) if necessary. (D) The electron donor is (cyclo-R ¹ ) (cyclo-R ² ) Si (OR ^a ) ₂ (1) wherein the OR ^a group is a methoxy group or an ethoxy group. , (Cyclo-R ¹ ) and (cyclo-R ² ) are each a cycloalkyl group having 3 to 10 ring carbon atoms which may have a substituent, and a ring of (cyclo-R ¹ ) The carbon number of the member and the carbon number of the ring of (cyclo-R ² ) are different from each other by 2 or more. 3. The catalyst for olefin polymerization according to claim 2, wherein the catalyst is an organosilane compound (C). 4. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1.