JPH10158317A - Catalyst for polymerizing olefin, prepolymerization catalyst and polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst for polymerizing an olefin capable of producing a polyolefin having a low content of a decane-soluble component and excellent in stereoregularity with a high polymerization activity and to provide a method for polymerizing the olefin using the catalyst for polymerizing the olefin. SOLUTION: This catalyst for polymerizing an olefin comprises (A) a solid titanium catalyst component containing magnesium, titanium, a halogen and a polyether, (B) an organoaluminum compound and (C) a trialkoxysilane compound represented by the formula R<a> Si(OR<b> )3 (R<a> group is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group and OR<b> group is methoxy group or ethoxy group). The olefin may be prepolymerized with the catalyst for polymerizing the olefin comprising the catalyst components A and B and, as necessary, (D) an electron donor.

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 capable of producing a highly stereoregular polyolefin with high polymerization activity, and to a method for polymerizing an olefin using the olefin polymerization catalyst.

[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, and includes a carrier-supported solid titanium catalyst component as the titanium catalyst component. Catalysts are known to exhibit 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 catalysts containing such a solid titanium catalyst component in order to improve polymerization activity and obtain polyolefins having desired properties.
For example, various types of electron donors are used as components (internal donors) at the time of preparing the solid titanium catalyst component or as catalyst components (external donor) at the time of forming a catalyst for olefin polymerization from the solid titanium catalyst component and the organoaluminum compound. It has been proposed to use the body.

For example, as internal donors, monocarboxylic acid esters, polycarboxylic acid esters, polyhydroxy compound esters, aliphatic carboxylic acids, acid anhydrides, ketones, aliphatic ethers, aliphatic carbonates, alcohols containing alkoxy groups, Aryloxy group-containing alcohol,
Organosilicon compound having Si-OC bond, PO-
Organic phosphorus compounds having a C bond are widely used, and polycarboxylic acid esters such as phthalic acid esters are particularly used. As the external donor, a nitrogen-containing electron donor, an oxygen-containing electron donor, an organic phosphorus compound having a P—O—C bond, an organosilicon compound having a Si—O—C bond, and the like are known.

[0005] The applicant of the present invention also disclosed in Japanese Patent Application Laid-Open No. 58-83006, which was able to produce a highly stereoregular polyolefin in high yield and was excellent in particle size, particle size distribution, particle properties and bulk specific gravity. As a polyolefin production catalyst, a solid titanium catalyst component containing at least a carboxylic acid ester as an internal donor (internal electron donor), an organoaluminum compound, and Si—OC or Si as an external donor (external electron donor) An olefin polymerization catalyst comprising an -silicon compound having an -NC bond has been proposed. As the organosilicon compound having an Si-OC bond (external donor), an alkoxysilane compound such as tetraethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane or the like is specifically used.

[0006] Among the alkoxysilane compounds,
Cyclopentyl group represented by dicyclopentyldimethoxysilane, substituted cyclopentyl group, cyclopentenyl group, substituted cyclopentenyl group, cyclopentadienyl group, substituted cyclopentadienyl group, or a carbon adjacent to Si is a secondary carbon or A catalyst having a dimethoxysilane compound having two tertiary carbon-containing hydrocarbon groups and two methoxy groups as an external donor can produce a polyolefin having a particularly high stereoregularity.

The inventor of the present invention has continued research on an olefin polymerization catalyst containing an alkoxysilane compound as an external donor. As a result, a solid titanium catalyst component containing a polyether as an internal donor, an organoaluminum compound, The present inventors have found that the use of a catalyst for olefin polymerization comprising a trialkoxy compound having three alkoxy groups as a donor makes it possible to produce a highly stereoregular polyolefin with high polymerization activity, thereby completing the present invention.

[0008]

An object of the present invention is to provide an olefin polymerization catalyst capable of producing a highly stereoregular polyolefin with high polymerization activity, and an olefin polymerization method using the olefin polymerization catalyst. And

[0009]

Olefin polymerization catalyst according to the present invention SUMMARY OF THE INVENTION, (A) magnesium, the solid titanium catalyst component containing titanium, a halogen and polyether, and (B) an organoaluminum compound, (C) R ^a Si (OR ^b ) ₃ ... (1) [wherein, the ^Ra group is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and the OR ^b group is a methoxy group or an ethoxy group. And a trialkoxysilane compound represented by the formula:

Further, the olefin polymerization catalyst according to the present invention comprises: [I] the above-mentioned (A) a solid titanium catalyst component;
(B) an organoaluminum compound and, if necessary, (D)
The catalyst for olefin polymerization comprising an electron donor may be formed from a prepolymerized catalyst obtained by prepolymerizing an olefin, [II] the trialkoxysilane compound, and [III] an organoaluminum compound as required. .

The electron donor (D) during the prepolymerization may be the above trialkoxysilane compound. 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 polyether as essential components. Solid titanium catalyst component, the preparation method is not limited as long as it contains these components, (a-1) magnesium compound, (a-
2) It can be prepared by bringing a titanium compound and (a-3) a polyether or the like into contact by various methods. 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 or an alkoxy group.

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. , Butoxymagnesium chloride, alkoxymagnesium chloride such as octoxymagnesium chloride, phenoxymagnesium chloride, allyloxymagnesium halide such as methylphenoxymagnesium chloride, diethoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, di-n-octoxymagnesium,
2-ethylhexoxymagnesium, alkoxymagnesium such as ethoxymethoxymagnesium, diphenoxymagnesium, allyloxymagnesium such as dimethylphenoxymagnesium, magnesium laurate,
Examples thereof include magnesium carboxylate such as 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 a reducing ability, for example, a magnesium compound having a reducing ability is converted into a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen, or the like. What is necessary is just to contact with a 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, any magnesium compound other than those described above can be used. However, in the finally obtained solid titanium catalyst component, a magnesium compound containing halogen is present. 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) Polyether When preparing a solid titanium catalyst component, a polyether is used as an electron donor. As the polyether, a compound having two or more ether bonds existing through a plurality of atoms can be used.

Specifically, in such a polyether, the atoms existing between the ether bonds are carbon, silicon,
Oxygen, nitrogen, phosphorus, boron, sulfur, or two or more compounds selected from these can be exemplified. Of these, a relatively bulky substituent is bonded to an atom between ether bonds, and a compound in which a plurality of carbon atoms are contained in atoms present between two or more ether bonds is preferable,
For example, a polyether represented by the following formula is preferable.

[0033]

Embedded image

(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 polyether compound as described above, 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-dimethoxy Propane, 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 -Screw (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-diisoamyloxypropane, 1,3-diiso Neopentyloxyethane, 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-diisobutyldi Oxyheptane, 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-methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1 , 3-Dimethoxycyclohexane, 2-isopropyl-2-
Isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl- 1,
3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-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,
In addition to the polyether (a-3) as described above, another electron donor (a-6) can be used if necessary. Examples of the other electron donor (a-6) include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, esters of polyhydric alcohols, ethers, and acids. Amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, oxygen-containing cyclic compounds, and the like can be used.

Further, as the electron donor (a-6), an organosilicon 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 kinds. 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.

As such a carrier, Al ₂ O ₃ , 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 polyether (a-3) can be prepared by contacting the same, and can be prepared by any method including a known method.The preparation method is not particularly limited. Magnesium compound (a
-1), liquid titanium compound (a-2) and polyether (a-
3) is preferably contacted.

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 the 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 polyether (a-3) is brought into contact with the contact product at least once. (2) The contact product of the inorganic carrier and the organomagnesium compound (a-1) is contact-reacted with the titanium compound (a-2) and the polyether (a-3).

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 process, the polyether (a-3) is brought into contact with the contact product at least once. (4) magnesium compound (a-1), titanium compound (a-2),
Electron donor (a-4) In some cases, a solution containing a hydrocarbon solvent, an inorganic carrier or an organic carrier, and a polyether (a-3)
And contact.

(5) Liquid state organomagnesium compound (a
-1) is contacted with a halogen-containing titanium compound (a-2) and a polyether (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 process, the polyether (a-3) is used at least once. (7) An alkoxy group-containing magnesium compound (a-1) is converted into a halogen-containing titanium compound (a-2) and a polyether (a-
3) Contact reaction with.

(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 a polyether (a
-3) and contact reaction.

(9) A liquid state 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 process, the polyether (a-3) is brought into contact with the contact product at least once.

(10) A liquid magnesium compound (a-1) having no reducing ability and a titanium compound (a-2) are
The contact is made in the presence or absence of (a-3). In this process, the polyether (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) The reaction product obtained in (1) to (11) is further contacted with a polyether (a-3) and a titanium compound (a-2).

In the above, another electron donor (a-6) can be used in an arbitrary step. The contact of each component as described above is usually performed at -70 ° C to 200 ° C, preferably -50 ° C to
It is carried out at a temperature of 150 ° C, 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 polyether (a-3) is used in an amount of 0.01 to 10 mol, preferably 0.1 to 10 mol.
The titanium compound (a-2) in a liquid state can be used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol, in an amount of 1 to 5 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 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,
Contains titanium, halogen and polyether,
0.3 to 10% by weight, preferably 0.5 to 8% by weight of titanium
And magnesium and halogen in a total amount of 10 to 95.
Preferably, the polyether is contained in an amount of 0.5 to 30% by weight in an amount of 0.5% 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.

[0058] 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, as the organoaluminum compound, a compound represented by the following formula can also be mentioned. 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 such as 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) Trialkoxysilane compound In the present invention, the solid titanium catalyst component (A) as described above
When forming an olefin polymerization catalyst from the organic aluminum compound (B) and the organoaluminum compound (B), a trialkoxysilane compound represented by the following general formula (1) is used.

R ^a Si (OR ^b ) ₃ (1) wherein the OR ^b group is a methoxy group or an ethoxy group.
The ^Ra group is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and specifically, methyl, ethyl, (n-, i-) propyl, (n-, i-, t-) butyl, pentyl , Hexyl, heptyl, (n-, i-) octyl, nonyl, decyl, texyl (2,3-dimethyl-2-butyl), etc., a linear or branched alkyl group having 1 to 12 carbon atoms, cyclopropyl, C3-C12 cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl; C6-C21 aryl groups such as phenyl, tolyl, biphenylyl and naphthyl, benzyl and α-methyl It is an aralkyl group having 7 to 16 carbon atoms such as benzyl.

These groups may have a substituent such as a halogen or an amino group. Specific examples of such a trialkoxysilane compound include, for example, methyltrimethoxysilane, ethyltrimethoxysilane, (n
-, I-) propyltrimethoxysilane, (n-, i-, t-)
Butyltrimethoxysilane, pentyltrimethoxysilane, hexyltrimethoxysilane, heptyltrimethoxysilane, (n-, i-) octyltrimethoxysilane, nonyltrimethoxysilane, decyltrimethoxysilane,
Texyltrimethoxysilane, cyclopropyltrimethoxysilane, cyclobutylcyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, cycloheptyltrimethoxysilane, cyclooctyltrimethoxysilane, cyclononyltrimethoxysilane, cyclodecyltrimethoxysilane Methoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, benzyltrimethoxysilane, α-methylbenzyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxy Silane, (n-, i-) propyltriethoxysilane, (n-,
i-, t-) butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, heptyltriethoxysilane, (n-, i-) octyltriethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, texyl Triethoxysilane, cyclopropyltriethoxysilane, cyclobutylcyclohexyltriethoxysilane, cyclopentyltriethoxysilane,
Cyclohexyltriethoxysilane, cycloheptyltriethoxysilane, cyclooctyltriethoxysilane, cyclononyltriethoxysilane, cyclodecyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, γ-chloropropyltriethoxysilane, γ-amino And propyltriethoxysilane. Among these, a trimethoxysilane compound is preferable, and alkyltrimethoxysilane and cycloalkyltrimethoxysilane are preferably used.

Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention comprises (A) a solid titanium catalyst component containing particularly a polyether as an internal donor, (B) an organoaluminum compound,
(C) a trialkoxysilane compound represented by the formula (1). 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. An olefin polymerization catalyst comprising a titanium catalyst component, (B) an organoaluminum compound and, if necessary, (D) an electron donor, a prepolymerized catalyst obtained by prepolymerizing an olefin, and [II] the trialkoxysilane An olefin polymerization catalyst can also be formed from the compound and, if necessary, the [III] organoaluminum compound.

This trialkoxysilane compound [II]
Is a trialkoxysilane compound represented by the formula (1), and the organoaluminum compound [III] is exemplified as the organoaluminum compound (B).

The electron donor (D) can be used if necessary during the prepolymerization.
Specifically, the above trialkoxysilane compounds can be used, and other electron donors can also be used. In the present invention, when the above trialkoxysilane compound is used as the electron donor (D) at the time of preliminary polymerization, the trialkoxysilane [I
I] may be omitted.

Other electron donors include, for example, the aforementioned polyether compounds, 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, N 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 the trialkoxysilane compound (C) other than the organic silicon compound as the other electron donors.
As other organic silicon compounds, specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bism-
Tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di ( 3-methylcyclopentyl) dimethoxysilane, di-t-amyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxysilane, methyltriaryloxy (allyloxy) silane, Chlortriethoxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, ethyl silicate, butyl silicate and the like can be mentioned. Two or more of these can be used in combination.

The olefins used in the prepolymerization include, for example, ethylene, propylene, 1-butene,
Pentene, 1-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, Α-olefins having 2 or more carbon atoms, such as 1-eicosene. Also other vinyl compounds as described below,
Polyene compounds can also be used during prepolymerization. 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, 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 prepolymerization, 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 used in an amount of usually about 0.1 to 1000 mol, preferably about 0.5 to 500 mol, particularly preferably 1 to 100 mol, per 1 mol of titanium in the solid titanium catalyst component (A). Can be used.

In the 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 regulator 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, in the subsequent (main) polymerization, the prepolymerized catalyst can be used as it is in a suspended state, 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 components.

Olefin Polymerization Method In the olefin polymerization method according to the present invention, (A) a solid titanium catalyst component containing a polyether as an internal donor, (B) an organoaluminum compound, and (C) a trialkoxysilane In the presence of an olefin polymerization catalyst comprising a compound, or an olefin polymerization catalyst comprising an [I] prepolymerization catalyst, [II] a trialkoxysilane compound and, if necessary, an [III] organoaluminum compound, an olefin is polymerized or It is copolymerized.

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.

Of these, 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.

In particular, in the present invention, polypropylene having high stereoregularity can be obtained by polymerizing propylene.
When the olefin is copolymerized, an olefin copolymer having a narrow composition distribution can be obtained.

The decane-soluble component content of the polyolefin can be used as an index of such stereoregularity and composition distribution characteristics. Further, the boiling heptane extraction residual ratio can be used as an index of stereoregularity.

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 either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. 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 2,000 moles, preferably about 2 to 500 moles, of aluminum atoms in the organoaluminum compound per mole of titanium atoms in the polymerization system. Can be used in such an amount that

The trialkoxysilane compound (C) (or [II]) is usually used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, per 1 mol of aluminum atom of the organoaluminum compound. Can be used.

When the prepolymerized catalyst [I] is used, the organoaluminum compound [III] may not be used in some cases. When forming an olefin polymerization catalyst including a prepolymerization catalyst, an organoaluminum compound [III]
When [III] is used, this [III] and the organoaluminum compound (B) at the time of preparing the prepolymerization catalyst may be the same compound or different. When an olefin polymerization catalyst is formed from the prepolymerized catalyst prepared using the trialkoxysilane compound (C), the trialkoxysilane compound (C) and the trialkoxysilane compound [II] are the same compound. Or different.

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 in 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. According to the present invention, polyolefins having high stereoregularity, particularly polypropylene, can be obtained. The polypropylene obtained in the present invention has a low decane soluble component at 23 ° C, for example, a content of a decane soluble component at 1.1 ° C of 1.1. % By weight, preferably 1.0% by weight or less, particularly preferably 0.95% by weight or less.

[0095]

As described above, the catalyst for olefin polymerization of the present invention formed from a solid titanium catalyst component containing a polyether as an internal donor, an organoaluminum compound, and a trialkoxysilane compound as an external donor is as follows:
A polyolefin having a low decane-soluble component content and excellent stereoregularity can be obtained with high polymerization activity.

[0096]

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 melt flow rate (MFR) of the polyolefin was AST
It measured at 230 degreeC and 2.16 kg load based on MD1238. The 23 ° C. n-decane soluble component amount (t-DS) of the polyolefin was determined as follows.

A 1 liter flask is charged with 3 g of the sample (polyolefin), 20 mg of 2,6-di-tert-butyl-4-methylphenol and 500 ml of n-decane, and dissolved by heating at 145 ° C. 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 ratio (A) of the obtained polymer dissolution amount to the sample weight is calculated, and the 23 ° C. decane-soluble component amount of the polypropylene is determined by the following formula (I) using the ratio (A).

[0099]

(Equation 1)

[0100]

Example 1 [Preparation of solid titanium catalyst component (A-1)] 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 35.1 m of 2-ethylhexyl alcohol (EHOH)
l (225 mmol) were mixed and heated at 130 ° C. for 2 hours to obtain a homogeneous solution. 2.28 g of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was added to this homogeneous solution.
(11.27 mmol) was added, and the mixture was further stirred at 130 ° C. for 1 hour to dissolve, and then cooled to room temperature.

In 200 ml (1.8 mol) of titanium tetrachloride, 0.0714 g (0.7 mol) of solid anhydrous magnesium chloride was used.
After suspending (5 mmol), the mixture was kept at -20 ° C, and the homogeneous solution obtained above was added dropwise thereto over 1 hour. After dropping, the temperature of the resulting solution was raised to 11 over 4 hours.
The temperature was raised to 0 ° C, and when it reached 110 ° C, 5.03 ml (18.8 mmol) of diisobutyl phthalate was added.
Stir at the above temperature for another 2 hours.

After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was resuspended in 275 ml of TiCl _{4 and} heated again at 110 ° C. for 2 hours. After completion of the reaction, a solid portion was collected by hot filtration and washed with decane and hexane at 110 ° C. This washing was performed until no titanium compound was detected in the washed plants.

As described above, the solid titanium catalyst component (I
A hexane slurry of -1) was obtained. A part of the solid titanium catalyst component (I-1) (hexane slurry) was collected and dried, and the composition of the catalyst component was analyzed.

The solid titanium catalyst component (I-1) contains Ti in an amount of 3.
Contains 3% by weight, 18.0% by weight of Mg, 56.0% by weight of Cl, 1.6% by weight of OEH group, and 17.0% by weight of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane Was.

[Preparation of Preliminary Polymerization Catalyst (I-1)] Purified hexane 100
Then, 0.2 mmol of triethylaluminum (0.6 mmol) and the solid titanium catalyst component (A-1) obtained above were charged in an amount of 0.2 mmol in terms of titanium atoms.
Propylene was fed in the amount of time for 1 hour.

After the supply of propylene was completed, the solid portion obtained by filtration was washed twice with purified hexane, and the obtained prepolymerized catalyst (I-1) was resuspended in decane, and the whole amount was transferred to a catalyst bottle. Thus, a prepolymerized catalyst (I-1) was obtained.

[Main polymerization] 400 ml of purified heptane was charged into an autoclave having an internal volume of 1 liter, and at 60 ° C. in a propylene atmosphere, 0.4 mmol of triethylaluminum, 0.08 mmol of n-propyltrimethoxysilane, and After adding 0.004 mmol of the obtained prepolymerized catalyst (I-1) in terms of titanium atoms, 100 ml of hydrogen was added, the temperature was raised to 70 ° C, and the temperature was maintained for 1 hour to polymerize propylene. Was. During the polymerization, the pressure was kept at 5 kg / cm ² G. After the polymerization, the slurry containing the produced polymer is filtered,
It was separated into a white granular polymer and a liquid phase. Table 1 shows the results.

[0108]

Example 2 [Main polymerization] Cyclopentyltrimethoxysilane 0.0 instead of n-propyltrimethoxysilane 0.08 mmol
The procedure was as in Example 1, except that 8 mmol was used. Table 1 shows the results.

[0109]

Example 3 [Main polymerization] The procedure of Example 1 was repeated, except that 0.08 mmol of i-butyltrimethoxysilane was used instead of 0.08 mmol of n-propyltrimethoxysilane. Table 1 shows the results.

[0110]

Example 4 [Main polymerization] Except that 0.08 mmol of texyltrimethoxysilane (2,3-dimethyl-2-butyltrimethoxysilane) was used instead of 0.08 mmol of n-propyltrimethoxysilane Was performed in the same manner as in Example 1. Table 1 shows the results.

[0111]

Comparative Example 1 [Main Polymerization] The procedure of Example 1 was repeated, except that 0.08 mmol of n-propyltrimethoxysilane was replaced by 0.08 mmol of n-propylcyclopentyldimethoxysilane. Table 1 shows the results.

[0112]

Comparative Example 2 [Main Polymerization] n-propylmethyldimethoxysilane 0.0 instead of 0.08 mmol of n-propyltrimethoxysilane
The procedure was as in Example 1, except that 8 mmol was used. Table 1 shows the results.

[0113]

Comparative Example 3 [Main Polymerization] The procedure of Example 1 was repeated, except that 0.08 mmol of cyclohexylmethyldimethoxysilane was used instead of 0.08 mmol of n-propyltrimethoxysilane. Table 1 shows the results.

[0114]

Comparative Example 4 Preparation of Solid Titanium Catalyst Component (A-2) 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. Phthalic anhydride 22.
2 g was added, and the mixture was further stirred at 130 ° C. for 1 hour to dissolve phthalic anhydride. After the thus obtained homogeneous solution was cooled to room temperature, 75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride kept at -20 ° C over 1 hour. After completion of the charging, the temperature of the mixture was raised to 110 ° C. over 4 hours, and when the temperature reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was obtained.
Was added thereto, and the mixture was stirred and maintained at the same temperature for 2 hours. 2
After the 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, and again stirred at 110 ° 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 solution.

The solid titanium catalyst component (A-2) prepared by the above operation was stored as a decane slurry, and a part thereof was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (A-2) thus obtained was as follows: 2.3% by weight of titanium; 61% by weight of chlorine; 19% by weight of magnesium; and 12.5% by weight of DIBP. Was.

[Preparation of Preliminary Polymerization Catalyst (I-2)] Same as Example 1 except that the solid titanium catalyst component (A-2) was used instead of the solid titanium catalyst component (A-1). To obtain a prepolymerized catalyst (I-2).

[Main polymerization] The procedure of Example 3 was repeated, except that the prepolymerized catalyst (I-2) was used instead of the prepolymerized catalyst (I-1). Table 1 shows the results.

[0118]

[Table 1]

[Brief description of the drawings]

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

Claims (4)

[Claims] 1. A solid titanium catalyst component containing (A) magnesium, titanium, halogen and polyether; (B) an organoaluminum compound; and (C) R ^a Si (OR ^b ) ₃ . wherein, R ^a group is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, oR ^b group is a methoxy group or an ethoxy group. And a trialkoxysilane compound represented by the formula: 2. (I) Consisting of (A) a solid titanium catalyst component containing magnesium, titanium, halogen and polyether, (B) an organoaluminum compound and, if necessary, (D) an electron donor. For olefin polymerization catalysts,
A prepolymerized catalyst an olefin is prepolymerized, a [II] in _{^{R a Si (OR b) 3}} ... (1) [wherein, R ^a group is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, OR ^{The b} group is a methoxy group or an ethoxy group. [III] An olefin polymerization catalyst comprising: a trialkoxysilane compound represented by the formula: Wherein (D) the electron donor, in _{^{R a Si (OR b) 3}} ... (1) [wherein, R ^a group is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, OR ^b The group is a methoxy or ethoxy group. 3. The catalyst for olefin polymerization according to claim 2, which is a trialkoxysilane compound represented by the following formula: 4. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1.