JPH09208615A - Preparation of solid titanium catalyst component, catalyst, and method for polymerizing olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a highly active solid titanium catalyst component for polymn. of an olefin by bringing a liq. magnesium compd., a liq. titanium compd., a salt of a group VIII metal of the periodic table, and a polyether having a specified compsn. into contact with one another. SOLUTION: A liq. magnesium compd. (A) (e.g. magnesium chloride), a liq. titanium compd. (B) (e.g. titanium tetrachloride), a salt of a group VIII metal (C) of the periodic table (e.g. F3Cl2 ), and a polyether (D) having at least two ether bonds present through a plurality of atoms (e.g. 2,2-diisopropyl-1,3- dimethoxypropane) are brought into contact with one another to obtain a solid titanium catalyst component. This solid titanium catalyst component is then combined with an org. metallic compd. (e.g. diethylaluminum chloride), and optionally an organosilane compd. having at least one alkoxy group (e.g. trimethylmethoxysilane) to obtain the objective catalyst for polymn, of an olefin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is capable of polymerizing α-olefins such as ethylene and propylene with high activity,
Moreover, the present invention relates to a method for preparing a solid titanium catalyst component capable of producing a highly stereoregular polyolefin when an α-olefin having 3 or more carbon atoms is polymerized, a catalyst and a method for polymerizing an olefin.

[0002]

BACKGROUND OF THE INVENTION Conventionally, a catalyst formed from a titanium catalyst component and an organoaluminum compound has been widely used as a catalyst for producing polyolefin. Particularly, a carrier-supported solid titanium catalyst component is used as the titanium catalyst component. It is known that the obtained catalyst has high polymerization activity.

[0003] Among such solid titanium catalyst components, a catalyst using a titanium chloride-supporting titanium catalyst component containing titanium, magnesium, halogen and an electron donor exhibits high polymerization activity and also has high polymerization activity, such as propylene and butene. It is known that when an α-olefin having 3 or more carbon atoms is polymerized, a polyolefin having high stereoregularity can be produced.

It is known to use a carboxylic acid ester as an electron donor at the time of preparing such a solid titanium catalyst component. For example, JP-A-3-50207 discloses a magnesium compound, a titanium compound and a halogen. A method of reacting a containing compound and an electron donor in the presence of a transition metal compound of Group 7A or Group 8 of the periodic table to obtain a solid catalyst component having high stereospecificity and high polymerization activity has been proposed. Therefore, carboxylic acid esters are used as this electron donor.

Various catalysts (sometimes referred to as highly stereospecific catalysts) capable of producing a polyolefin having a higher stereoregularity have been proposed. For example, a solid titanium catalyst component supporting magnesium chloride and an organoaluminum compound have been proposed. It has been proposed to use an electron donor as the third component of the catalyst. Further, in such a catalyst, the carboxylic acid ester is used as the electron donor in the solid titanium catalyst component as described above, and Si is used as the third component of the catalyst.
It is known that a catalyst using a silicon compound having —OR (R is a hydrocarbon group) exhibits high stereospecificity.

Further, for example, in JP-A-3-294302, when a solid titanium catalyst component carrying a polyether having two or more ether bonds is used in place of the above carboxylic acid esters, high stereospecificity is obtained. It is shown that a catalyst having high polymerization activity can be obtained.

The present inventor can produce a polyolefin having high stereoregularity when an α-olefin having 3 or more carbon atoms is polymerized, and at the same time, a solid titanium catalyst component capable of exhibiting higher polymerization activity. As a result of research on the catalyst and (a), a liquid magnesium compound, (b) a liquid titanium compound, (c) a metal salt of Group VIII of the periodic table, and (d) two or more atoms existing through a plurality of atoms The present invention has been completed by finding that a solid titanium catalyst component and a catalyst capable of achieving the above object can be obtained by contacting a polyether having an ether bond of 1), preferably by contacting the above (c) in a liquid state. Came to do.

[0008]

An object of the present invention is to produce an α-olefin such as ethylene or propylene with high activity, and to produce a highly stereoregular polyolefin when an α-olefin having 3 or more carbon atoms is polymerized. It is an object of the present invention to provide a method for preparing a solid titanium catalyst component capable of producing a catalyst, a prepolymerization catalyst, a catalyst for olefin polymerization, and a method for polymerizing an olefin containing the solid titanium catalyst component.

[0009]

SUMMARY OF THE INVENTION A method for preparing a solid titanium catalyst component according to the present invention comprises: (a) a liquid magnesium compound, (b) a liquid titanium compound, (c) a periodic table group VIII metal salt, and (d) ) It is characterized in that a polyether having two or more ether bonds existing through a plurality of atoms is brought into contact with each other.
The (c) Group VIII metal salt of the periodic table is preferably contacted in a liquid state.

The olefin polymerization catalyst according to the present invention has (A) the solid titanium catalyst component obtained above, (B) an organometallic compound, and (C) at least one alkoxy group if necessary. It is composed of an organic silane compound.

Further, the prepolymerization catalyst according to the present invention comprises the above-mentioned (A) solid titanium catalyst component, (B) organometallic compound, and (C) organic compound having at least one alkoxy group, if necessary. An olefin is preliminarily polymerized with a silane compound, and from such a prepolymerization catalyst and (B) an organometallic compound and / or (C) an organosilane compound having at least one alkoxy group, if necessary. An olefin polymerization catalyst may be formed.

In the olefin polymerization method according to the present invention, the olefin is polymerized in the presence of the above-mentioned olefin polymerization catalyst, and the olefin can be polymerized with high activity, and moreover, it has 3 or more carbon atoms. When the α-olefin is polymerized, a highly stereoregular polyolefin can be produced.

[0013]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a method for preparing a solid titanium catalyst component according to the present invention, a prepolymerization catalyst containing the solid titanium catalyst component, an olefin polymerization catalyst, and an olefin polymerization method will be described. In the present invention,
The term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may be used to include not only homopolymer but also copolymer. There is.

In the method for preparing a solid titanium catalyst component according to the present invention, (a) a liquid magnesium compound, (b) a liquid titanium compound, (c) a Group VIII metal salt of the periodic table, and (d) a plurality of compounds. Are contacted with a polyether having two or more ether bonds existing through the atoms of Below, each component used when preparing a solid titanium catalyst component is shown.

(A) Liquid Magnesium Compound In the present invention, the magnesium compound is used in a liquid form. However, the liquid magnesium compound may be a liquid magnesium compound itself, or a solid magnesium compound. It may be liquefied. Specific examples of such a magnesium compound include (a-1) a magnesium compound having a reducing ability and (a-2) a magnesium compound having no reducing ability.

Magnesium compound (a-1) having reducing ability
Examples thereof include an organomagnesium compound represented by the following formula. MgX ¹ _n R ¹² _{-n In the} formula, n is 0 ≦ n <2, and R ¹ is hydrogen or an alkyl group, an aryl group, or a cycloalkyl group having 1 to 20 carbon atoms, and when n is 0, Two R ¹ may be the same or different. X ¹ is a halogen, hydrogen or an alkoxy group.

Specific examples of the organomagnesium compound (a-1) having such reducing ability include dimethylmagnesium, diethylmagnesium, dipropylmagnesium,
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 butyl magnesium hydride.

The magnesium compound having no reducing ability (a-
Examples of 2) include a magnesium compound represented by the following formula. Mg (OR ² ) _n X ² _{2-n In the} formula, n is 0 ≦ n ≦ 2, R ² is a hydrocarbon group having 1 to 20 carbon atoms, and when n is 2, two R ² May be the same or different. X ² is halogen or hydrogen.

As the magnesium compound (a-2) having no reducing ability, magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, methoxy magnesium chloride, ethoxy magnesium chloride, Alkoxy magnesium halides such as isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride, phenoxy magnesium chloride, allyloxy magnesium halides such as methylphenoxy magnesium chloride, ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2 -Alkoxy magnesium such as ethylhexoxymagnesium, allyloxy such as phenoxymagnesium, dimethylphenoxymagnesium Magnesium, magnesium hydride and the like.

The magnesium compound having no reducing ability (a-
As 2), it is also possible to use magnesium carboxylates such as magnesium laurate and magnesium stearate, and magnesium metal.

The magnesium compound having no reducing ability (a-2) may be a compound derived from the above-mentioned magnesium compound having reducing ability (a-1) or a compound derived at the time of preparing the catalyst component. Good. A magnesium compound having no reducing ability (a-2) is derived from a magnesium compound having reducing ability (a-1), for example, a magnesium compound having reducing ability (a-1) is a polysiloxane compound, It may be contacted with a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen-containing compound, or a compound having an OH group or an active carbon-oxygen bond.

The magnesium compounds can be used in combination of two or more kinds. The magnesium compound (a-1) having a reducing ability and the magnesium compound (a-2) having no reducing ability include, for example, aluminum, zinc, boron, beryllium, and sodium as described below as the catalyst component (B). May form a complex compound or a double compound with a metal compound such as potassium or potassium, or may be used as a mixture with these metal compounds.

Among these, the magnesium compound (a-2) having no reducing ability is preferable, the halogen-containing magnesium compound is particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride and allyloxy magnesium chloride are preferable.

As the magnesium compound used for preparing the solid titanium catalyst component, magnesium compounds other than those mentioned above can be used, but they are present in the form of halogen-containing magnesium compound in the finally obtained solid titanium catalyst component. Therefore, when a magnesium compound containing no halogen is used, it is preferable to react it with a halogen-containing compound during the preparation.

Among the above magnesium compounds,
When the magnesium compound is a solid, an electron donor
It can be liquefied using (ci). As the electron donor (ci), alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines, etc., which will be described later, can be used.

It is also possible to use metal acid esters such as tetraethoxy titanium, tetra-n-propoxy titanium, tetra-i-propoxy titanium, tetrabutoxy titanium, tetrahexoxy titanium, tetrabutoxy zirconium, tetraethoxy zirconium and the like. . Among these, alcohols and metal acid esters are particularly preferably used.

The solid magnesium compound is converted into an electron donor (c
For dissolution in -i), a method in which a solid magnesium compound and an electron donor (ci) are brought into contact with each other and heated if necessary is common. This contact can be usually performed at a temperature of 0 to 200 ° C, preferably 20 to 180 ° C, more preferably 50 to 150 ° C.

Further, the above contact is preferably carried out in the coexistence of a hydrocarbon solvent. Specific examples of such a hydrocarbon solvent include pentane, hexane, heptane, octane,
Aliphatic hydrocarbons such as decane, dodecane, tetradecane and kerosene, cycloaliphatic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane and cyclohexene, dichloroethane, dichloropropane, trichloroethylene, chlorobenzene, etc. Halogenated hydrocarbons, benzene,
Aromatic hydrocarbons such as toluene and xylene are used.

(B) Liquid Titanium Compound In the present invention, a tetravalent titanium compound is particularly preferably used as the liquid titanium compound. Such a tetravalent titanium compound is represented, for example, 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 titanium compounds include titanium tetrahalides such as TiCl ₄ , TiBr ₄ , TiCl ₂ Br ₂ , 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-C 4 H 9)} 2 Cl 2, Ti (OC 2 H 5) dihalogenated dialkoxy titanium, such as _{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,
Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C
_{4 H 9) 4, Ti (} O-iso-C 4 H 9) 4, etc. tetraalkoxy titanium such as Ti (O-2-ethylhexyl) _4. Among them, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used in combination of two or more. The above liquid titanium compound may be diluted with a hydrocarbon, a halogenated hydrocarbon, or an aromatic hydrocarbon before use.

(C) Polyether In the present invention, a polyether having two or more ether bonds existing via a plurality of atoms (hereinafter simply referred to as polyether) is used. As this polyether,
Examples thereof include compounds in which the atom existing between the ether bonds is carbon, silicon, oxygen, nitrogen, phosphorus, boron, sulfur or two or more selected from these. 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.

[0032]

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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 the main chain may contain an atom other than carbon. )

Specific examples of such a polyether include 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-diethyl -1,3-dimethoxypropane, 2,2-
Dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,
3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-
Methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,
2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-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, 2,2-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-benzyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1 , 4-diethoxybutane,
2,2-dibenzyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-
1,4-diethoxybutane, 2,2-bis (p-methylphenyl)
-1,4-dimethoxybutane, 2,3-bis (p-chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl -1,5-
Dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-
Diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxyethane, 1,3 -Diisoamyloxypropane, 1,3-diisoneopentyloxyethane,
1,3-Dineopentyloxypropane, 2,2-Tetramethylene
-1,3-dimethoxypropane, 2,2-pentamethylene-1,
3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro 5,5 undecane, 3,7-dioxabicyclo [3, 3,1] Nonane, 3,7-dioxabicyclo
[3,3,0] octane, 3,3-diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) 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, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di Examples thereof include -t-butylbis (methoxymethyl) silane, cyclohexyl-t-butylbis (methoxymethyl) silane, and i-propyl-t-butylbis (methoxymethyl) silane. Of these,
1,3-diethers are preferably used, particularly 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3 -Dimethoxypropane, 2-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. Two or more of these polyethers can be used in combination.

When preparing the solid titanium catalyst component, other electron donors may be used in combination with the polyether, such as alcohols, phenols, ketones,
Aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides,
Examples thereof include ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds and oxygen-containing cyclic compounds. More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl. C1-C18 alcohols such as alcohols, C1-C18 halogen-containing alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol, and carbons such as 2-ethoxyethanol, 2-propoxyethanol and 2-butoxyethanol. Alkoxy group-containing alcohols of the number 3 to 20, phenol, cresol,
Xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as naphthol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone,
C3-15 ketones such as benzoquinone, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and other C2-15 aldehydes, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, Propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, benzoate Propyl acid, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl benzoate, anise Methyl, ethyl anisate, ethyl ethoxy benzoate, .gamma.-butyrolactone, .delta.-valerolactone, coumarin, phthalide, organic acid esters having 2 to 18 carbon atoms, such as ethyl carbonate, phthalic acid dichloride,
C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride, and C2 to C2 such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, and diphenyl ether. 20 ethers, acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide, methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, triethylamine, triethylamine Butylamine, tribenzylamine, tetramethylenediamine, hexamethylenediamine, and other amines, acetonitrile, benzonitrile, trinitrile, and other nitriles, acetic anhydride, phthalic anhydride, benzoic anhydride Acid anhydrides such as pyrrole, methylpyrrole, pyrroles such as dimethylpyrrole, pyrroline; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine , Pyridines such as pyridine chloride, nitrogen-containing cyclic compounds such as piperidines, quinolines and isoquinolines, tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran And cyclic oxygen-containing compounds such as coumaran, phthalane, tetrahydropyran, pyran, and ditedropyran.

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

[0037]

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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 Or an unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group. Also 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, etc.
O-C, COOR, COOH, OH, SO 3 H, -C-
With N-C-, a group such as NH _2.

Specific examples of such polycarboxylic acid esters 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. Among the carboxylic acid esters, it is preferable to use polyvalent carboxylic acid esters, especially phthalic acid esters.

As another electron donor, an organic silane compound (C) having at least one alkoxy group as described below, water, or an anion type or a cation type,
A nonionic surfactant or the like can also be used. Two or more of these other electron donors can be used in combination.
In the present invention, as the electron donor other than polyether,
Substituted alcohols, acid anhydrides and carboxylic acid esters are preferred.

(D) Group VIII Metal Salt Periodic Table Group VIII metals include Fe, Co, N
i, Ru, Rh, Rd, Pt and the like, and among these, Fe, Co and Ni are preferable. In the present invention,
As the Group VIII metal salt, halides and alkoxy compounds of these metals are preferably used, and Fe halides, Co halides and Ni halides are preferably used. In particular, chlorides such as FeCl ₂ , CoCl ₂ and NiCl ₂ are preferably used.

Method for Preparing Solid Titanium Catalyst In the method for preparing a solid titanium catalyst component according to the present invention, (a) a liquid magnesium compound, (b) a liquid titanium compound, and (c) a poly (c) Ether and (d) Periodic Table VI
Although a solid titanium catalyst component is obtained as a solid by contacting with a Group II metal salt, the method of contacting each component is not particularly limited, and various components can be contacted.

FIG. 1 shows an example of the preparation process of the solid titanium catalyst component and the preparation process of the olefin polymerization catalyst containing the solid titanium catalyst component. Contact of each component can be carried out in the presence of a hydrocarbon solvent, if necessary. As the hydrocarbon solvent, the hydrocarbon solvent used when the solid magnesium compound (a) is dissolved in the electron donor (ci) can be used.

When preparing the solid titanium catalyst component, in addition to these compounds, an organic compound or an inorganic compound containing silicon, phosphorus, aluminum or the like used as other electron donor, carrier and reaction aid. A compound or the like may be used. As the carrier, Al ₂ O ₃ , SiO ₂ , B ₂
O ₃ , MgO, CaO, TiO ₂ , ZnO, SnO ₂ , BaO,
Resins such as ThO and styrene-divinylbenzene copolymer are used, and Al ₂ O ₃ , SiO ₂ and styrene-divinylbenzene copolymer are particularly preferably used.

Several specific examples of the steps for preparing the solid titanium catalyst component will be shown below. In the following, the magnesium compound not particularly limited is preferably a halogen-containing magnesium compound, and the liquid magnesium compound is usually a magnesium compound solution containing an electron donor (ci) and optionally a hydrocarbon solvent. Further, as the organoaluminum compound, the organometallic compound (B) described below can be used.

(1) The liquid magnesium compound (a) is brought into contact with the liquid aluminum compound (b) while contacting with the organoaluminum compound to precipitate a solid. In this process, the polyether (c) and the Group VIII metal salt (d) are contacted with the contact product at least once. (2) The liquid titanium compound (b), the polyether (c) and the Group VIII metal salt (d) are brought into contact with the contact product of the liquid organomagnesium compound (a) and the carrier. At this time, the contact product of the carrier and the liquid organomagnesium compound (a) may be contacted with the halogen-containing compound and / or the organoaluminum compound in advance. (3) The liquid magnesium compound (a) and the contact product with the carrier, the liquid titanium compound (b), polyether (c) and VI.
Group II metal salt (d) is contacted.

(4) A solution containing a liquid magnesium compound (a), a liquid titanium compound (b), and optionally a hydrocarbon solvent, a carrier, a polyether (c) and a Group VIII metal salt (d). Contact.

(5) The liquid magnesium compound (a) and the liquid titanium compound (b) are brought into contact with each other, and then the polyether (c) and the Group VIII metal salt (d) are brought into contact with each other. (6) After bringing the liquid organomagnesium compound (a) into contact with the halogen-containing compound, it is brought into contact with the liquid titanium compound (b). In this process, polyether (c) and VII
The Group I metal salt (d) is used at least once.

(7) Liquid magnesium compound (a) is converted into polyether (c), Group VIII metal salt (d) and titanium compound.
(b). (8) The liquid magnesium compound (a) and the titanium compound (b) are contacted in the presence or absence of the polyether (c). In this contacting process, the polyether (c) and the Group VIII metal salt (d) are used at least once.

(9) The liquid magnesium compound (a) contains
After the group metal salt (d) is dissolved, it is brought into contact with the titanium compound (b) and the polyether (c).

(10) The solid compound obtained in (1) to (9) is contacted with the titanium compound (b). (11) The polyether (c) and the titanium compound (b) are brought into contact with the solid matter obtained in (1) to (10).

In the present invention, it is preferable that the Group VIII metal salt (d) is brought into contact in a liquid state in the above-mentioned preparation method. Among the above preparation methods, (9) is particularly preferable. The contact of each component as described above is usually −70 ° C. to 200 ° C., preferably −50 ° C. to 150 ° C., and more preferably −30 ° C.
It is carried out at a temperature of 130 ° C. The amount of each component used when preparing the solid titanium catalyst component varies depending on the preparation method and cannot be specified unconditionally, but for example, per mole of the magnesium compound, the polyether (c) is 0.01 to 10 moles, preferably 0.001 mole. In an amount of 1 to 5 mol, the titanium compound (b) is 0.01 to 1000 mol, preferably 0.1 to 200 mol, and the Group VIII metal salt (d) is 0.001 to 1 mol, preferably 0.001 to 1 mol. It can be used in an amount of 0.005-0.5 mol.

In the present invention, the solid substance (solid titanium catalyst component) thus obtained can be used as it is, but it is preferable to wash the solid substance with a hydrocarbon solvent at 0 to 200 ° C. before use. preferable.

Examples of the washing solvent include aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane and cetane, non-halogenated aromatic hydrocarbons such as toluene, xylene and benzene, chlorobenzene, o-dichlorobenzene and m. -Dichlorobenzene, trichlorobenzene,
Halogen-containing aromatic hydrocarbons such as α, α, α-trichlorotoluene, o-chlorotoluene, benzal chloride, and 2-chlorobenzyl chloride are used. Of these, aliphatic hydrocarbons and halogen-containing aromatic hydrocarbons are preferably used.

In washing the solid matter, the hydrocarbon solvent is usually 1 to 10000 ml, preferably 5 to 5000 ml, more preferably 10 to 100 ml, per 1 g of the solid matter.
Used in a volume of 0 ml. This washing is preferably performed until titanium is not eliminated by washing with hexane at room temperature.

The solid titanium catalyst component obtained as described above contains titanium, magnesium, halogen, polyether and Group VIII metal of the periodic table. Specifically, the solid titanium catalyst component contains titanium in an amount of 0.1 to 10
% By weight, preferably 0.2 to 7.0% by weight, particularly preferably 0.3 to 5.0% by weight, the total of magnesium and halogen being 95 to 30% by weight, preferably 90 to 40% by weight. Particularly preferably in an amount of 85 to 50% by weight, polyether in an amount of 1 to 35% by weight, preferably 3 to 30% by weight, particularly preferably 5 to 25% by weight, and a metal salt of Group VIII of the periodic table in an amount of 0. It is desirable that the amount of this component is 0.5 to 20% by weight, preferably 0.1 to 15% by weight, and particularly preferably 0.15 to 10% by weight.

The solid titanium catalyst component according to the present invention includes titanium, magnesium, halogen, and a polyene as described above.
Tellurium and Group VIII metal of the Periodic Table are contained, but they may also contain other components as necessary. When the solid titanium catalyst component (A) according to the present invention as described above is used as a catalyst component for olefin polymerization,
The olefin can be polymerized with extremely high activity, and a polyolefin having a high stereoregularity can be produced.

(B) Organometallic Compound In the present invention, when forming the olefin polymerization catalyst, an organometallic compound is used together with the solid titanium catalyst component (A) as described above. Specific examples of the organometallic compound include an organoaluminum compound and a complex alkyl compound of a Group I metal and aluminum.

Such an organoaluminum compound is represented by the following formula, for example. During 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.

As the organoaluminum compound, compounds 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 (SiR ^f ₃ ) _3-n (iso-Bu) ₂ AlSiMe _3, etc., (vi) R ^a _n Al [N (R ^g ) -AlR ^h ₂ ] _3-n Et ₂ AlN (Me) -AlEt ₂ (iso-Bu) ₂ AlN (Et) A
l (iso-Bu) ₂ etc.

Further, a compound similar to this, for example, an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can be mentioned. 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
Examples thereof include N (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ and aluminoxanes such as methylaluminoxane.

Among the above organometallic compounds,
^{_{R a 3 Al, R a n}} Al (OR b) 3-n, R a n Al (OAl
R ^d ₂ ) An organoaluminum compound represented by _3-n is preferably used.

A complex alkyl compound of a Group I metal and aluminum is represented by the following general formula. 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. In the present invention, the organometallic compound (B) may be used in combination of two or more kinds.

(C) Organosilane Compound When preparing the olefin polymerization catalyst of the present invention,
In addition to the solid titanium catalyst component (A) and the organometallic compound (B) as described above, an organosilane compound having at least one alkoxy group represented by the following general formula (i) is used.

R _n Si (OR ′) _4-n (i) (wherein R and R ′ are hydrocarbon groups, and n is 1, 2
Or 3. Specific examples of the organic silane compound represented by the above formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-
Butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-tolyldimethoxysilane, bism-tolyldimethoxysilane, bis p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxy Silane,
Decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltri Ethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxysilane, methyltriaryloxy (all
yloxy) silane, vinyl tris (β-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane and the like. Ethyl silicate, butyl silicate and the like can also be used.

In the present invention, the organosilane compound represented by the above formula (i) is particularly preferably represented by the following formula (ii). During _{^{R a n Si (OR b)}} 4-n ... (ii) ( 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. In the organosilane compound having a bulky group represented by the formula (ii), the secondary or tertiary hydrocarbon group has a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, and a substituent These groups and Si
And a hydrocarbon group in which the carbon adjacent to is secondary or tertiary. More specifically, as the substituted cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,4-dimethyl Cyclopentyl group, 2,5-dimethylcyclopentyl group,
2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group, 2,
Examples thereof include cyclopentyl groups having an alkyl group such as a 3,4-triethylcyclopentyl group, a tetramethylcyclopentyl group, and a tetraethylcyclopentyl group.

The substituted cyclopentenyl group includes a 2-methylcyclopentenyl group, a 3-methylcyclopentenyl group,
2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethyl Cyclopentenyl groups having an alkyl group such as a cyclopentenyl group, a 2,3,5-trimethylcyclopentenyl group, a 2,3,4-triethylcyclopentenyl group, a tetramethylcyclopentenyl group, and a tetraethylcyclopentenyl group are exemplified.

Examples of the substituted cyclopentadienyl group include 2-
Methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentadienyl group, 2,4-dimethyl Cyclopentadienyl group, 2,5-
Dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3,4-trimethylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group,
3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4,5-tetraethylcyclopentadienyl group, 1,2,3,4, Cyclopentadienyl groups having an alkyl group such as a 5-pentamethylcyclopentadienyl group and a 1,2,3,4,5-pentaethylcyclopentadienyl group are exemplified.

Examples of the hydrocarbon group in which the carbon adjacent to Si is a secondary carbon include i-propyl group, s-butyl group, s-amyl group, α-methylbenzyl group and the like, which are adjacent to Si. A hydrocarbon group whose carbon is a tertiary carbon includes t-
Butyl group, t-amyl group, α, α′-dimethylbenzyl group,
Examples thereof include an admantyl group.

As the organosilane compound represented by the formula (ii), when n is 1, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane , Cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane,
Trialkoxysilanes such as cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, and 2-norbornanetriethoxysilane. When n is 2, dicyclopentyldiethoxysilane, t- Butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,
And dialkoxysilanes such as cyclohexylmethyldiethoxysilane and 2-norbornanemethyldimethoxysilane.

Further, in the organosilane compound represented by the formula (ii), when n is 2, the following formula (ii)
The dimethoxysilane compound represented by i) can be preferably exemplified.

[0075]

Embedded image

In the formula, R ^a and R ^c are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or
A hydrocarbon group in which carbon adjacent to Si is a secondary or tertiary carbon.

Examples of the organosilane compound represented by the formula (iii) include dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane, di (2 -Methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di (2-ethylcyclopentyl) dimethoxysilane, di (2,3-dimethylcyclopentyl) dimethoxysilane, di (2,4-dimethylcyclopentyl) dimethoxysilane , Di (2,5-dimethylcyclopentyl) dimethoxysilane, di (2,3-diethylcyclopentyl) dimethoxysilane, di (2,3,4-trimethylcyclopentyl) dimethoxysilane, di (2,3,5-trimethylcyclopentyl) Dimethoxysilane, di (2,3,4-triethylsilane Lopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane, di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclo Pentenyl) dimethoxysilane, di (2-n-butylcyclopentenyl) dimethoxysilane, di (2,3-dimethylcyclopentenyl) dimethoxysilane, di (2,4-dimethylcyclopentenyl) dimethoxysilane, di (2,5- Dimethylcyclopentenyl) dimethoxysilane, di (2,3,4-trimethylcyclopentenyl) dimethoxysilane, di (2,3,5-trimethylcyclopentenyl) dimethoxysilane, di (2,3,4-triethylcyclopentenyl) dimethoxy Silane, di (tetramethylcyclopenteni ) Dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxysilane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxy Silane, di (2-
n-butylcyclopentenyl) dimethoxysilane, di (2,
3-dimethylcyclopentadienyl) dimethoxysilane,
Di (2,4-dimethylcyclopentadienyl) dimethoxysilane, di (2,5-dimethylcyclopentadienyl) dimethoxysilane, di (2,3-diethylcyclopentadienyl)
Dimethoxysilane, di (2,3,4-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,5-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,4-triethylcyclopentadienyl) ) Dimethoxysilane, di (2,3,4,5-tetramethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane, di (1,2,3 , 4,5-pentamethylcyclopentadienyl) dimethoxysilane, di (1,2,
3,4,5-pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α, α'-dimethylbenzyl) dimethoxysilane, di (admantyl) dimethoxysilane, admantyl-t-butyldimethoxy Examples include silane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, di-s-butyldimethoxysilane, di-s-amyldimethoxysilane, and isopropyl-s-butyldimethoxysilane.

Further, as the organosilane compound represented by the formula (ii), when n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylsilane. Ethoxysilane, cyclopentyldimethylmethoxysilane,
Examples thereof include monoalkoxysilanes such as cyclopentyldiethylmethoxysilane and cyclopentyldimethylethoxysilane.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and represented by the formula (iii) Dimethoxysilanes are preferred. In particular, dimethoxysilanes represented by formula (iii) are preferable, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane. , Di-t-amyldimethoxysilane and the like are preferable. These may be used in combination of two or more.

Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention comprises (A) a solid titanium catalyst component as described above, (B) an organometallic compound, and optionally (C) at least one. It is formed from an organic silane compound having an alkoxy group.

In the present invention, each of these components (A) and (B)
In addition, when forming an olefin polymerization catalyst from (C), if necessary, other components may be used, for example, the above-mentioned polyether compound, 2,6-substituted piperidines, 2, 5-Substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-substituted methylenediamines such as tetraethylmethylenediamine, 1,3-dibenzylimidazolidine, Nitrogen-containing electron donors such as substituted imidazolidines such as 1,3-dibenzyl-2-phenylimidazolidine, triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri
n-butyl phosphite, triisobutyl phosphite,
Phosphorus-containing electron donors such as diethyl n-butyl phosphite and diethyl phenyl phosphite, and oxygen-containing electron donors such as 2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans Can also be used, and these can also be used in combination of 2 or more types. Further, in the present invention, a prepolymerization catalyst may be formed from each of the above components.

The prepolymerization catalyst is a preliminary (co) polymerization of olefins and the like in the presence of the solid titanium catalyst component (A), the organometallic compound (B) and, if necessary, the organosilane compound (C). It is formed by

Examples of the olefins used in the prepolymerization include ethylene, propylene, 1-butene, 1-
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 later. 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 about -20 to + 100 ° C, preferably about -20 to + 80 ° C, more preferably -10 to 10.
It is desirable to carry out at + 40 ° C. Further, the prepolymerization can be carried out in any of batch system, semi-continuous system and 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. The concentration of the catalyst component in the pre-polymerization varies depending on the catalyst component used, etc., but the concentration of the solid titanium catalyst component (A) is expressed in terms of titanium atoms per liter of polymerization volume.
Usually about 0.001 to 5000 mmol, preferably about 0.0
It is preferably from 1 to 1000 mmol, particularly preferably from 0.1 to 500 mmol.

The organometallic compound (B) is used in an amount of 0.01 to 2000 g, preferably 0.03 to 1000 g, and more preferably 0.05 to 200, per 1 g of the solid titanium catalyst component (A).
g of the preliminary (co) polymer are used in an amount such that
It is generally used in an amount of about 0.1 to 1000 mol, preferably about 0.5 to 500 mol, particularly preferably 1 to 100 mol, per mol of titanium in the solid titanium catalyst component.

During the prepolymerization, the organosilane compound (C) is usually added in an amount of 0.01 to 50 mol, preferably 0.05 to 5 mol, per mol of titanium atom in the solid titanium catalyst component (A).
It can be used in an amount of 30 mol, more preferably 0.1 to 10 mol, if necessary.

In the prepolymerization, a molecular weight modifier such as hydrogen can be used. When the prepolymerized catalyst is obtained in a suspended state as described above, in the next step (main) polymerization, the prepolymerized catalyst can be used as it is in a suspended state or can be produced from the suspension. The pre-polymerized catalyst may be used separately.

The above-mentioned prepolymerization catalyst usually forms an olefin polymerization catalyst together with the organometallic compound (B) and the organosilane compound (C), but only the prepolymerization catalyst can be used as the olefin polymerization catalyst. In some cases. When the organosilane compound (C) is not used during the prepolymerization, the olefin polymerization catalyst may be formed by using the organosilane compound (C) together with the prepolymerization catalyst.

The olefin polymerization catalyst according to the present invention may contain other components useful for olefin polymerization in addition to the above-mentioned components.

Method for Polymerizing Olefin In the method for polymerizing an olefin according to the present invention, the solid titanium catalyst component (A), the organometallic compound catalyst component (B) and, if necessary, the organosilane compound (C) are used. The olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst or a catalyst containing a prepolymerization catalyst.

As such an olefin, specifically, an α-olefin having 2 or more carbon atoms similar to that used in the prepolymerization can be used, and further, cyclopentene, cycloheptene, norbornene, 5-ethyl-2- Norbornene, tetracyclododecene, 2-ethyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-Cycloolefins such as octahydronaphthalene, styrene, dimethylstyrenes, allylnaphthalene, allylnorbornane, vinylnaphthalenes, allyltoluenes, allylbenzene, Vinyl compounds such as vinylcyclopentane, 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 prepolymerization catalyst is usually about 0.001 to 100 mmol, preferably about 0.005 in terms of titanium atom per 1 liter of the polymerization volume. Used in an amount of 20 mmol.

The organometallic compound (B) is the compound (B)
The metal atom therein is used in an amount such that it is usually about 1 to 2000 mol, preferably about 2 to 500 mol, per 1 mol of the titanium atom in the polymerization system.

The organosilane compound (C) may or may not be used, but is usually about 0.001 mol-10 mol, preferably 0.01 mol, per 1 mol of the metal atom of the organometallic compound (B). It is optionally used in an amount of up to 5 moles.

When a prepolymerization catalyst is used during this polymerization, the organometallic compound (B) and the organosilane compound (C) are used.
It may not be necessary to use any of the above. When an olefin polymerization catalyst is formed from the component (B) and / or (C) together with the prepolymerization catalyst, these components (B) and (C) can be used in the amounts described above.

If hydrogen is used during the 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 method for polymerizing olefins according to the present invention, the polymerization is usually carried out at a temperature of usually about 20 to 300 ° C., preferably about 50 to 150 ° C., and normal pressure to 100 kg / l, although it depends on the type of the olefin, the form of the polymerization, and the like.
It is carried out under a pressure of about ² to 50 kg / cm ² , preferably about ² to 50 kg / cm ² .

In the polymerization method of the present invention, the polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further, the polymerization was carried out by changing the reaction conditions.
It can also be divided into more than one step.

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 kinds of olefins.

[0104]

When the olefin polymerization catalyst containing the solid titanium catalyst component according to the present invention as described above is used, the olefin can be polymerized with extremely high activity, and the α-olefin having 3 or more carbon atoms can be produced. When polymerized, a polyolefin having high stereoregularity can be produced.

[0105]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.
In the following Examples and Comparative Examples, the bulk specific gravity of polyolefin was measured according to JIS K6721. The boiling heptane extraction residual rate of the polyolefin; the powder content after completion of the polymerization was determined by Soxhlet extraction with boiling heptane until the extraction residual became a constant weight.

[0106]

[Example 1] [Preparation of solid titanium catalyst component (A-1)] 7.14 g (75 mmol) of anhydrous magnesium chloride and 37.5 ml of decane.
And 2-ethylhexyl alcohol 35.1 ml (22
(5 mmol) was mixed and heated at 130 ° C. for 2 hours to form a uniform solution. In this homogeneous solution, 2,2-diisopropyl-
2.12 g (11.27 mmol) of 1,3-dimethoxypropane was added, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to be dissolved.

Then, FeCl ₂ was added to this solution at 0.9.
5 g (7.5 mmol) was added, and the mixture was stirred and mixed at 130 ° C. for 1 hour to be dissolved. The homogeneous solution thus obtained was cooled to room temperature and then added dropwise to 200 ml (1.8 mol) of titanium tetrachloride kept at -20 ° C over 1 hour. After the dropping, the temperature of the obtained solution was raised to 110 ° C. over 4 hours and stirred at 110 ° C. for 2 hours.

After the completion of the reaction for 2 hours, the solid portion was collected by hot filtration, resuspended in 275 ml of TiCl _{4, and} then 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 washing solution.

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

The solid titanium catalyst component (A-1) comprises 3.0% by weight of Ti, 15.9% by weight of Mg, 52.5% by weight of Cl, 2.8% by weight of Fe and 2,2% by weight. It contained 19.0% by weight of diisopropyl-1,3-dimethoxypropane.

[Main Polymerization] 400 ml of purified heptane was charged into an autoclave having an internal volume of 1 liter, and 0.4 mmol of triethylaluminum, 0.4 mmol of dicyclopentyldimethoxysilane and the above-obtained product were obtained at 60 ° C. in a propylene atmosphere. After adding 0.004 mmol of the solid titanium catalyst component (A-1) in terms of titanium atom, 75 ml of hydrogen was added, the temperature was raised to 70 ° C., and this was kept for 1 hour to polymerize propylene. It was During the polymerization, the pressure is 5 kg /
It was kept at cm ² G. After the completion of the polymerization, the slurry containing the produced polymer was filtered to separate it into a white granular polymer (powder) and a liquid phase part. The results are shown in Table 1. In the table, the polymer recovered from the liquid phase part is shown as a solvent-soluble polymer.

[0112]

Example 2 [Preparation of Solid Titanium Catalyst Component (A-2)] FeCl ₂
Instead of 0.95 g (7.5 mmol), CoCl ₂
A solid titanium catalyst component (A-2) was prepared in the same manner as in Example 1 except that 0.97 g (7.5 mmol) was used. The composition of this catalyst component was analyzed in the same manner as in Example 1.

The solid titanium catalyst component (A-2) is composed of 3.4% by weight of Ti, 15.7% by weight of Mg, 54.0% by weight of Cl, 2.5% by weight of Co and 2.2% of Co. It contained 18.5% by weight of diisopropyl-1,3-dimethoxypropane.

[Main Polymerization] Propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-1) was replaced with the solid titanium catalyst component (A-2). The results are shown in Table 1.

[0115]

Example 3 [Preparation of solid titanium catalyst component (A-3)] Solid titanium catalyst was prepared in the same manner as in Example 1 except that the amount of FeCl ₂ added was 0.095 g (0.75 mmol). Component (A-3) was prepared. The composition of this catalyst component was analyzed in the same manner as in Example 1.

The solid titanium catalyst component (A-3) is composed of 2.9% by weight of Ti, 17.5% by weight of Mg, 55.0% by weight of Cl, 0.3% by weight of Fe and 2,2%. It contained 18.5% by weight of diisopropyl-1,3-dimethoxypropane.

[Main Polymerization] Propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-1) was replaced with the solid titanium catalyst component (A-3). The results are shown in Table 1.

[0118]

Example 4 [Preparation of solid titanium catalyst component (A-4)] The solid titanium catalyst component (A) was prepared in the same manner as in Example 1 except that the amount of FeCl ₂ added was 1.90 g (15 mmol). A-3) was prepared. The composition of this catalyst component was analyzed in the same manner as in Example 1.

The solid titanium catalyst component (A-4) comprises 2.7% by weight of Ti, 15.5% by weight of Mg, 53.0% by weight of Cl, 5.1% by weight of Fe and 2,2% by weight. It contained 17.3% by weight of diisopropyl-1,3-dimethoxypropane.

[Main Polymerization] Propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-4) was used in place of the solid titanium catalyst component (A-1). The results are shown in Table 1.

[0121]

[Comparative Example 1] [Preparation of solid titanium catalyst component (A-5)] A solid titanium catalyst component (A-5) was prepared in the same manner as in Example 1 except that FeCl ₂ was not used. Prepared. The composition of this catalyst component was analyzed in the same manner as in Example 1.

The solid titanium catalyst component (A-5) is composed of 3.0% by weight of Ti, 17.0% by weight of Mg, 55.0% by weight of Cl, and 2,2-diisopropyl-1,3-dimethoxy. It contained 19.1% by weight of propane.

[Main Polymerization] Propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-1) was replaced with the solid titanium catalyst component (A-5). The results are shown in Table 1.

[0124]

[Comparative Example 2] [Preparation of solid titanium catalyst component (A-6)] 7.14 g (75 mmol) of anhydrous magnesium chloride and 37.5 ml of decane.
And 2-ethylhexyl alcohol 35.1 ml (22
(5 mmol) was mixed and heated at 130 ° C. for 2 hours to form a uniform solution. Then add 1.6% phthalic anhydride to this solution.
7 g (11.5 mmol) was added, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the above homogeneous solution.

Then, FeCl ₂ was added to this solution at 0.9.
3 g was added, and the mixture was stirred and mixed at 130 ° C. for 1 hour to be dissolved. After cooling the homogeneous solution thus obtained to room temperature, 200 ml of titanium tetrachloride kept at -20 ° C.
The whole amount was dripped into (1.8 mol) over 1 hour. After the dropping, the temperature of the obtained solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.03 ml (18.8 mmol) of diisobutyl phthalate was added. It was further stirred for 2 hours at the above temperature.

After the completion of the reaction for 2 hours, a solid portion was collected by hot filtration, the solid portion was resuspended in 275 ml of TiCl _{4 and} then 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 washing solution. Example 1
The composition of this catalyst component was analyzed in the same manner as in.

The solid titanium catalyst component (A-6) comprises 2.2% by weight of Ti, 19.0% by weight of Mg, 57.5% by weight of Cl, 2.7% by weight of Fe and diisobutyl phthalate. The content was 13.3% by weight.

[Main Polymerization] Propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-1) was replaced with the solid titanium catalyst component (A-6). The results are shown in Table 1.

[0129]

Comparative Example 3 [Preparation of Solid Titanium Catalyst Component (A-7)] Anhydrous magnesium chloride 20 g (210 mmol), FeCl ₂ 3.80
g (30 mmol), di-n-butyl phthalate 4.45 g
(16 mmol) was placed in a container for a vibrating ball mill (a stainless steel cylindrical type, an internal volume of 1 l, a magnetic ball having a diameter of 10 mm was filled with an apparent volume of about 50%). This was attached to a vibrating ball mill having an amplitude of 6 mm and a frequency of 30 Hz, and co-pulverized for 20 hours to obtain a co-pulverized solid. 5 g of the obtained co-ground product is 50 ml of titanium tetrachloride.
It was suspended in (0.45 mmol) and reacted at 120 ° C. for 2 hours. The solid product is collected by filtration, 60 ° C
It was washed 10 times with toluene (80 ml). This is 4
It was dried under reduced pressure at 0 ° C. to obtain the desired solid catalyst component.
The composition of this catalyst component was analyzed in the same manner as in Example 1.

The solid titanium catalyst component (A-7) is composed of 2.8% by weight of Ti, 16.0% by weight of Mg, 56.0% by weight of Cl, 2.7% by weight of Fe and diphthalic acid. n-butyl 1
It contained 5.7% by weight.

[Main Polymerization] Propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-1) was replaced with the solid titanium catalyst component (A-7). The results are shown in Table 1.

[0132]

[Comparative Example 4] [Preparation of solid titanium catalyst component (A-8)] Di-n-phthalate
Solid titanium catalyst component in the same manner as in Comparative Example 3 except that 6.48 g (30 mmol) of 2,2-diisopropyl-1,3-dimethoxypropane was used instead of 4.45 g (16 mmol) of butyl. (A-8) was prepared.

The solid titanium catalyst component (A-8) comprises 1.5% by weight of Ti, 18.5% by weight of Mg, 50.0% by weight of Cl, 2.0% by weight of Fe and 2,2%. It contained 14.6% by weight of diisopropyl-1,3-dimethoxypropane.

[Main Polymerization] Propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (A-8) was used in place of the solid titanium catalyst component (A-1). The results are shown in Table 1.

[0135]

[Table 1]

[0136]

[Comparative Example 5] [Preparation of solid titanium catalyst component (A-9)] 7.14 g (75 mmol) of anhydrous magnesium chloride and 37.5 ml of decane.
And 2-ethylhexyl alcohol 35.1 ml (22
(5 mmol) was mixed and heated at 130 ° C. for 2 hours to form a uniform solution. To this homogeneous solution, 1.47 ml (11.25 mmol) of 2-butoxyethanol was added and the mixture was heated to 130 ° C.
Then, the mixture was stirred and mixed for 1 hour to dissolve it.

Then, FeCl ₂ was added to this solution at 0.9.
5 g (7.5 mmol) was added, and the mixture was stirred and mixed at 130 ° C. for 1 hour to be dissolved. The homogeneous solution thus obtained was cooled to room temperature and then added dropwise to 200 ml (1.8 mol) of titanium tetrachloride kept at -20 ° C over 1 hour. After the dropping, the temperature of the resulting solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.03 ml (18.8 mmol) of diisobutyl phthalate.
Was added and the mixture was stirred at the above temperature for additional 2 hours.

After the completion of the reaction for 2 hours, a solid portion was collected by hot filtration, the solid portion was resuspended in 275 ml of 1,2,4-trichlorobenzene, and then heated at 130 ° C. for 1 hour. . After the reaction is completed, the solid part is collected by hot filtration and the temperature is 130 ° C.
Wash with decane and hexane. This washing,
The procedure was repeated until no titanium compound was detected in the cleaning solution.

As described above, the solid titanium catalyst component (A
-4) Hexane slurry was obtained. A part of the solid titanium catalyst component (A-9) (hexane slurry) was collected and dried, and the composition of this catalyst component was analyzed.

The solid titanium catalyst component (A-9) comprises 1.5% by weight of Ti, 17.0% by weight of Mg, 56.0% by weight of Cl, 2.1% by weight of Fe and diisobutyl phthalate. The content was 17.3% by weight.

[Preparation of Prepolymerization Catalyst] Nitrogen-substituted 2
In a 00 ml glass reactor, 100 ml of purified hexane
Then, 2 mmol of triethylaluminum, 0.4 mmol of dicyclopentyldimethoxysilane and 0.2 mmol of the solid titanium catalyst component (A-9) obtained above in terms of titanium atom were charged, and then 1.0 liter was charged. Propylene was fed in the amount of / hour for 1 hour.

After the completion of the propylene supply, the solid portion obtained by filtration was washed twice with purified hexane, and the obtained prepolymerized catalyst was resuspended in decane and the whole amount was transferred to a catalyst bottle. The amount of preliminary polymerization per 1 g of the solid titanium catalyst component (A-9) was 3 g. In this prepolymerized catalyst, 12.3 mg of Ti remained per 1 g of the solid titanium catalyst component (A-9).

[Main Polymerization] 400 ml of purified heptane was charged into an autoclave having an internal volume of 1 liter, and 0.4 mmol of triethylaluminum, 0.4 mmol of dicyclopentyldimethoxysilane and the above-obtained product were obtained at 60 ° C. in a propylene atmosphere. After the preliminary polymerization catalyst was charged in an amount of 0.008 mmol in terms of titanium atom, 100 ml of hydrogen was added, the temperature was raised to 70 ° C., and this was kept for 1 hour to polymerize propylene. 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. The results are shown in Table 1.

[Brief description of drawings]

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

Claims (6)

[Claims] 1. A liquid magnesium compound, (b) a liquid titanium compound, (c) a metal salt of Group VIII of the periodic table, and (d).
A method for preparing a solid titanium catalyst component, which comprises bringing into contact a polyether having two or more ether bonds existing through a plurality of atoms. 2. The method for preparing a solid titanium catalyst component according to claim 1, wherein (c) a metal salt of Group VIII of the periodic table is brought into contact with the liquid. 3. A solid titanium catalyst component (A) obtained in claim 1 or 2, (B) an organometallic compound, and (C) an organosilane compound having at least one alkoxy group if necessary. An olefin polymerization catalyst comprising: 4. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 3. 5. A solid titanium catalyst component (A) obtained in claim 1 or 2, (B) an organometallic compound, and (C) an organosilane compound having at least one alkoxy group if necessary. A prepolymerization catalyst characterized in that the olefin is prepolymerized. 6. A catalyst for olefin polymerization, which comprises the prepolymerization catalyst according to claim 5 and optionally (B) an organometallic compound and / or (C) an organosilane compound having at least one alkoxy group. An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of olefin.