JP2001089515A - Treatment of catalyst component, olefin polymerization catalyst and polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for the treatment of a catalyst component for the polymerization of an olefin such as ethylene to enable the production of an ethylene polymer having high bulk density and excellent granular state in improved yield per unit volume of polymerizer. SOLUTION: The process for the treatment of a catalyst component comprises the treatment of a catalyst component containing magnesium, titanium, a halogen and a nucleation agent with an alkoxyaluminum or alkoxyaluminum halide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for preparing a solid titanium catalyst component for olefin polymerization having a high bulk density. The present invention also relates to the production of a polymer having a good bulk density and / or particle properties and a good yield per polymerization volume.

[0002]

BACKGROUND OF THE INVENTION Ethylene polymers such as homopolyethylene and linear low-density ethylene polymer (LLDPE) have excellent transparency and mechanical strength, and are widely used as films.

[0003] Various methods for producing such ethylene polymers have been known in the art, but Ziegler-type catalysts containing a titanium catalyst component containing titanium, magnesium, halogen and an optional electron donor as a polymerization catalyst. It is known that the use of a polymer can produce an ethylene polymer with high polymerization activity. In particular, a halogen-containing magnesium compound prepared in a liquid state as a titanium catalyst component,
It is known that a solid titanium catalyst component obtained from a liquid titanium compound and an electron donor exhibits high activity.

[0004] However, the bulk density of the ethylene polymer obtained by such a conventional method is generally 0.20 to 0.2.
It is about 32 g / cm ³ , and it has been urgently desired to improve the yield per polymerization volume by further improving the bulk density.

[0005] The ethylene polymer immediately after polymerization is usually obtained in powder form regardless of the slurry method, the gas phase method, etc., but at this time, it has excellent fluidity and does not contain particles such as fine powder and has a particle size distribution. It is desirable to produce excellent ethylene polymers. Such an ethylene polymer having excellent particle properties has various advantages such that it can be used as it is without pelletizing depending on the use.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and in the polymerization of olefins such as ethylene, a polymer having a high bulk density is obtained and the yield per polymerization volume is obtained. The purpose of the present invention is to make it possible to produce an ethylene polymer having excellent particle properties.

[0007]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to achieve the above-mentioned improvement, and found that at any stage during the preparation of a solid titanium catalyst component conventionally used,
By adding a specific compound to the catalyst preparation system in the presence of the nucleating agent, a solid titanium catalyst component having a high bulk density can be obtained,
Moreover, when olefin polymerization is performed using such a catalyst component, the bulk density of the obtained polymer can be improved, the yield per polymerization volume can be improved, and the particle properties of the polymer can be improved. As a result, the present invention has been completed.

That is, the method for treating a catalyst component according to the present invention is characterized in that a solid catalyst component containing magnesium, titanium, halogen and a crystal nucleating agent is treated with an alkoxyaluminum or an alkoxyaluminum halide.

The catalyst for olefin polymerization according to the present invention comprises:
[I] a solid titanium catalyst component obtained by treating a solid catalyst component containing magnesium, titanium, a halogen and a crystal nucleating agent with an alkoxyaluminum or an alkoxyaluminum halide; and [II] an organometallic compound It is characterized by.

In the olefin polymerization method according to the present invention,
The olefin is (co) polymerized in the presence of such a catalyst.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The method for treating a catalyst component, the catalyst for olefin polymerization and the method for olefin polymerization according to the present invention will be described below.

In the present invention, the term "polymerization" means
The term "polymer" may be used to include not only a homopolymer but also a copolymer, in some cases. Further, when the term “olefin” is simply described, it is used in a meaning including ethylene.

FIG. 1 is an explanatory diagram of a process for treating a catalyst component according to the present invention and a process for preparing an olefin polymerization catalyst including this process. [I] Solid titanium catalyst component The solid titanium catalyst component according to the present invention comprises magnesium,
It is obtained by treating a catalyst component containing titanium, a halogen and a crystal nucleating agent with an alkoxyaluminum or an alkoxyaluminum halide. The catalyst component containing magnesium, titanium, halogen and a nucleating agent is, for example, (a)
A liquid magnesium compound, and (b) a liquid titanium compound,
It is obtained by contacting (c) an organosilicon compound having no active hydrogen with (d) a crystal nucleating agent to prepare a solid catalyst component.

The above catalyst component and alkoxyaluminum or alkoxyaluminum halide (f) are
By directly adding to the reaction system of (a) to (d), or separately after the completion of the reaction of (a) to (d), a catalyst component containing magnesium, titanium, halogen and a crystal nucleating agent, It can be treated with an alkoxyaluminum or an alkoxyaluminum halide.

Hereinafter, each component will be described. (a) Liquid magnesium compound The magnesium compound is used in a liquid state. When the magnesium compound is in a solid state, it is liquefied and used.

As the magnesium compound, a magnesium compound (a-1) having a reducing ability and a magnesium compound (a-2) having no reducing ability can be used. (a-1) Examples of the magnesium compound having a reducing ability include an organic magnesium compound represented by the following formula.

[0017] X _n MgR in _2-n wherein, n = 0 ≦ n <2, R is 1 number of hydrogen or carbon
20 to 20 alkyl groups, aryl groups or cycloalkyl groups, and when n is 0, two Rs may be the same or different. X is a halogen.

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

(A-2) 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, and ethoxymagnesium 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, Aryloxy such as alkoxymagnesium such as 2-ethylhexoxymagnesium, phenoxymagnesium and dimethylphenoxymagnesium It is also possible to use magnesium carboxylate such as simmagnesium, magnesium laurate and magnesium stearate, magnesium metal, magnesium hydride and the like.

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. In order to derive a magnesium compound having no reducing ability (a-2) from a magnesium compound having reducing ability (a-1), for example, a magnesium compound having reducing ability (a-1) is converted into an alcohol, a ketone, Esters, ethers, siloxane compounds, halogen-containing silane compounds, halogen-containing aluminum compounds,
It may be brought into contact with a halogen-containing compound such as an acid halide or a compound having an OH group or an active carbon-oxygen bond.

Further, according to the present invention, an organosilicon compound (c) having no active hydrogen as described later is used to convert a magnesium compound (a-1) having a reducing ability to a compound (a- 2) can also be induced.

The magnesium compounds can be used in combination of two or more kinds. The magnesium compound as described above may form a complex compound with a metal compound other than magnesium such as aluminum, zinc, boron, beryllium, sodium, and potassium, for example, an organoaluminum compound described later, or a complex compound, or It can be used by mixing with other metal compounds.

At the time of preparing the catalyst component, a magnesium compound other than those described above can be used, but it is preferable that the magnesium compound is present in the form of a halogen-containing magnesium compound in the finally obtained solid titanium catalyst component [I]. 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 the catalyst component.

Of the above compounds, 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 preferably used.

In the present invention, when the above-mentioned magnesium compound is a solid, the magnesium compound can be liquefied using an electron donor (e-1). As such an electron donor (e-1), alcohols, carboxylic acids, aldehydes, amines, metal esters, and the like can be used.

Examples of alcohols include methanol, ethanol, propanol, isopropyl alcohol, butanol, pentanol, hexanol, 2-
Fatty alcohols such as methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecyl alcohol, octadecyl alcohol, undecenol, oleyl alcohol, stearyl alcohol, ethylene glycol, cyclohexanol, and methyl Alicyclic alcohols such as cyclohexanol, benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, α-methylbenzyl alcohol,
α, α-dimethylbenzyl alcohol, phenylethyl alcohol, cumyl alcohol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, aromatic alcohols such as naphthol, n-butyl cellosolve, ethyl cellosolve, 1-
Alkoxy group-containing alcohols such as butoxy-2-propanol and methyl carbitol; and halogen-containing alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol.

The carboxylic acids are preferably carboxylic acids having 7 or more carbon atoms, such as caprylic acid, 2-ethylhexanoic acid, nonylic acid and undecylenic acid.

The acetaldehyde is preferably an acetaldehyde having 7 or more carbon atoms, such as capryl aldehyde, 2-ethylhexyl aldehyde, undecyl aldehyde, benzaldehyde, tolualdehyde and naphthaldehyde.

The amines are preferably amines having 6 or more carbon atoms, such as heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine and laurylamine.

Examples of the metal acid esters include tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium. In addition, the metal acid esters do not include a silicate ester described later as (c) an organosilicon compound having no active hydrogen.

These may be used in combination of two or more kinds, and may also be used in combination with an electron donor (e) other than those described above as described later. Among these, alcohols and metal acid esters are preferable, and alcohols having 6 or more carbon atoms are particularly preferably used.

When the magnesium compound is liquefied using the electron donor (e-1) as described above, the electron donor (e-
When using an electron donor having 6 or more carbon atoms as 1),
It is usually used in an amount of about 1 mol or more, preferably 1 to 40 mol, more preferably 1.5 to 12 mol, per 1 mol of the magnesium compound. When an electron donor having 5 or less carbon atoms is used, about 15 mol or more is usually required for 1 mol of the magnesium compound.

A solid magnesium compound and an electron donor (e
At the time of contact with -1), a hydrocarbon solvent can be used. Examples of such hydrocarbon solvents include pentane, hexane, heptane, octane, decane, dodecane, tetradecane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, cyclohexane, and the like.
Alicyclic hydrocarbons such as methylcyclohexane, cyclooctane, and cyclohexene; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, and cymene; halogens such as carbon tetrachloride, dichloroethane, dichloropropane, trichloroethylene, and chlorobenzene Hydrocarbons and the like can be used.

When an aromatic hydrocarbon is used among such solvents, for example, alcohols as the electron donor (e-1) are not limited to the above-mentioned electron having 6 or more carbon atoms regardless of the type (carbon number). The magnesium compound can be dissolved when used in the amount indicated as the amount of the donor used. When an aliphatic hydrocarbon and / or an alicyclic hydrocarbon is used, the alcohol as the electron donor (e-1) is used in an amount corresponding to the number of carbon atoms as described above.

In the present invention, it is preferable to contact the solid magnesium compound with the electron donor (e-1) in a hydrocarbon solvent. The solid magnesium compound is converted to an electron donor (e
In order to dissolve it in -1), a method is generally used in which a solid magnesium compound and an electron donor (e-1) are brought into contact, preferably in the presence of a hydrocarbon solvent, and if necessary, heated. This contact is usually performed at 0 to 300 ° C, preferably 20 to 180 ° C.
More preferably at a temperature of 50 to 150 ° C. for 15 minutes to 5
This is performed for about an hour, preferably about 30 minutes to 2 hours.

(B) Liquid titanium compound In the present invention, a tetravalent titanium compound is particularly preferably used as the liquid 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 , Ti (OC ₂ H ₃ ) C
l 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) 3 Br
Monohalogenated trialkoxy titanium such as Ti (OC
_{H 3) 4, Ti (OC} 2 H 5) 4, Ti (On-C 4 H 9) 4, Ti (O-is
and tetraalkoxy titanium such as o-C ₄ H ₉ ) ₄ and 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.

Further, the magnesium compound (a) may be used after being diluted with a hydrocarbon solvent as shown when liquefying the magnesium compound. (c) Organosilicon Compound Having No Active Hydrogen The organosilicon compound having no active hydrogen used in the present invention is, for example, R ¹ xR ² ySi (OR ³ ) z (R ¹ and R ² are each independently R ³ is a hydrocarbon group or a halogen, and 0 ≦ x <2, 0 ≦ y <2, 0 <z ≦
4. ).

Specific examples of the organosilicon compound represented by the above formula include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrakis (2-ethylhexyloxy) silane, ethyltrimethoxysilane. Silane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-
Methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltrimethylsilane Ethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, decyltriethoxysilane, cyclopentyltriethoxysilane, cyclohexyltriethoxysilane, 2 -Norbornane triethoxysilane,
Phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane,
Trimethylphenoxysilane, methyltriaryloxy (a
llyloxy) silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyldimethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis ( 2,3-dimethylcyclopentyl) dimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-o-
Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bisethylphenyldimethoxysilane, dimethyldiethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclopentyldiethoxysilane , Diphenyldiethoxysilane, bis-p-tolyldiethoxysilane, cyclohexylmethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane,
Examples include dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylethoxysilane, dimethyltetraethoxydisiloxane, and the like.

Of these, tetramethoxysilane, tetraethoxysilane, cyclohexylmethyldimethoxysilane and the like are preferably used. From the viewpoint of catalytic activity, tetraethoxysilane is particularly preferably used.

In the present invention, it suffices that the solid titanium catalyst component finally obtained contains the organosilicon compound (c) having no active hydrogen. Therefore, even when not necessarily using the organic silicon compound having no active hydrogen (c) itself as described above when preparing the catalyst component, an organic silicon compound having no active hydrogen is used in the process of preparing the catalyst component. Other compounds that can be formed can also be used.

(E) Other Electron Donor In the present invention, in preparing the catalyst component, in addition to the above-mentioned organosilicon compound having no active hydrogen (c), the catalyst may optionally have no active hydrogen. Other electron donors (e) may be used.

In the present invention, such other electron donors
(e) includes, for example, organic acid esters, organic acid halides, organic acid anhydrides, ethers, ketones, tertiary amines, phosphites, phosphates, carboxylic amides,
Examples include nitriles, aliphatic carbonates, pyridines and the like. More specifically, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, i-butyl acetate,
T-butyl acetate, octyl acetate, cyclohexyl acetate, methyl chloroacetate, ethyl dichloroacetate, ethyl propionate, ethyl pyruvate, ethyl pivalate, methyl butyrate, ethyl valerate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate , Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate,
Organic acid esters having 2 to 18 carbon atoms such as ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate and ethyl ethoxy benzoate; carbons such as acetyl chloride, benzoyl chloride and toluic acid chloride Acid halides of number 2 to 15, acetic anhydride, phthalic anhydride, maleic anhydride, benzoic anhydride,
Trimellitic anhydride, acid anhydrides such as tetrahydrophthalic anhydride, and 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, ethyl benzyl ether, ethylene glycol dibutyl ether, anisole, and diphenyl ether. Ethers, acetone,
Methyl ethyl ketone, methyl isobutyl ketone, ethyl
C3-C20 ketones such as n-butyl ketone, acetophenone, benzophenone, benzoquinone, and cyclohexanone; tertiary amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, and tetramethylethylenediamine; trimethyl phosphite; Phyte, tri-n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, tri-isobutyl phosphite, diethyl n-
Phosphites such as butyl phosphite and diethyl phenyl phosphite; phosphates such as trimethyl phosphate, triphenyl phosphate and tolyl phosphate; N, N-dimethylamide acetate; N, N-diethylamide benzoate Acid amides such as N, N-dimethylamide, toluic acid, nitriles such as acetonitrile, benzonitrile and tolunitrile, aliphatic carbonates such as dimethyl carbonate, diethyl carbonate and ethylene carbonate, pyridine, methylpyridine, ethylpyridine and dimethylpyridine And the like.

These compounds can be used in combination of two or more kinds. (d) Crystal nucleating agent Examples of the crystal nucleating agent used in the present invention include typical metal oxide fine particles or a solid divalent metal halide having a cadmium chloride type crystal structure.

Examples of the typical metal oxide fine particles include solid compounds whose composition is represented by MO, MO ₂ , M ₂ O, and M ₂ O ₃ (M is a typical metal atom). , Al ₂ O ₃ , Ga ₂ O ₃ , GeO ₂ , SnO ₂ , Na ₂ O, K ₂
O, MgO, CaO and the like can be mentioned. Of these, A
_{l 2 O 3, Ga 2 O} 3, MgO, CaO are preferable, Al ₂ O ₃
Is particularly preferred.

The solid divalent metal halide having a cadmium chloride type crystal structure has a composition of MX
₂ (M is a divalent metal atom, X is Cl, I or Br), specifically, MgCl ₂ , Mn
Cl ₂ , FeCl ₂ , CoCl ₂ , NiCl ₂ , CdCl ₂ , ZnB
r ₂ , NiBr ₂ , CdBr ₂ , NiI _{2 and the} like. Among them, MgCl ₂ , FeCl ₂ , CoCl ₂ , NiCl _{2 and the} like are preferable, MgCl ₂ , FeCl ₂ , and particularly preferably MgCl ₂ .

The cadmium chloride type crystal structure is
Known crystal structures described in various documents, for example, “Chemical Dictionary 1” (Kyoritsu Shuppan Co., Ltd., first edition, February 1962)
28th), "Contemporary Inorganic Chemistry Lectures on Inorganic Chemistry (Part 1)" (Shichiichiro Utsumi, Gihodo Co., Ltd., first edition July 1965)
Issued on March 20).

The above-mentioned nucleating agent used in the present invention has an average particle size of 0.001 to 1000 μm, preferably 0.0.
It is preferably from 02 to 250 μm. More preferably 0.005 to 60 μm, particularly preferably 0.01 to 10 μm.
μm. When a catalyst component is prepared using a typical metal oxide having an average particle diameter within the above range, or a solid divalent metal halide having a cadmium chloride-type crystal structure, when polymerizing olefin, olefin polymerization is performed with high polymerization activity. Coalescence can be obtained.

Usually, the above-mentioned nucleating agent is preferably used in the form of a slurry. The medium used for preparing the crystal nucleating agent slurry is appropriately selected depending on the crystal nucleating agent to be used, and is usually an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane, kerosene; Cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane,
Alicyclic hydrocarbons such as cyclooctane and cyclohexene; halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene and chlorobenzene;
Examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene.

The concentration of the nucleating agent slurry is not particularly limited, but is usually 100 to 1 g / l, preferably 50 to 10 g / l.
It is desirable to be in the range of / l. (f) Alkoxy aluminum or alkoxy aluminum halide As the alkoxy aluminum or alkoxy aluminum halide, specifically, an aluminum compound represented by Al (OR) _a X _3-a is used. In the formula, a is an integer of 1 to 3, and particularly preferably 1 or 2. R is a hydrocarbon group having 1 to 20 carbon atoms, preferably an alkyl group having 2 to 12 carbon atoms, particularly ethyl,
Propyl, isopropyl, butyl, isobutyl, tert-
Butyl, pentyl, hexyl, octyl, 2-ethylhexyl, decyl, dodecyl. X is a halogen, specifically, fluorine, chlorine, bromine, or iodine, and chlorine is particularly preferable.

As such an aluminum compound,
Specifically, monomethoxyaluminum dichloride, monoethoxyaluminum dichloride, monopropoxyaluminum dichloride, monobutoxyaluminum dichloride, monopentoxyaluminum dichloride, monohexoxyaluminum dichloride, mono-2-methylhexoxyaluminum dichloride, mono-2-ethyl Monoalkoxyaluminum dichloride such as hexoxyaluminum dichloride; dimethoxyaluminum chloride, diethoxyaluminum chloride, dipropoxyaluminum chloride, dibutoxyaluminum chloride, dipentoxyaluminum chloride, dihexoxyaluminum chloride, di2-methylhexoxyaluminum chloride , Dialkoxyaluminum such as di-2-ethylhexoxyaluminum chloride Umukurorido; trimethoxy aluminum, triethoxy aluminum, tripropoxy aluminum, tributoxy aluminum, tri-pentoxy aluminum, tri-hexoxyphenyl aluminum, tri
Trialkoxyaluminums such as 2-methylhexoxyaluminum and tri-2-ethylhexoxyaluminum are exemplified.

These compounds can be used in combination of two or more kinds. Preparation of Catalyst Component The solid titanium catalyst component (I) of the present invention comprises magnesium, titanium, halogen and a crystal nucleating agent which can be formed from the components (a) to (d) and (e) if necessary. The catalyst component containing (f) alkoxyaluminum or alkoxyaluminum halide (hereinafter simply referred to as aluminum compound)
(f)).

The order of contact of each component is not particularly limited, and the aluminum compound (f) may be added simultaneously with the preparation of the catalyst component, or may be brought into contact with the catalyst component after the preparation of the catalyst component.

For example, after contacting (a) a liquid magnesium compound with (c) an organosilicon compound having no active hydrogen (hereinafter simply referred to as organosilicon compound (c)), the resulting contact product ( i) in the presence of (d) a crystal nucleating agent,
(b) The liquid titanium compound and (f) may be simultaneously or sequentially contacted with the aluminum compound, and (a) a liquid magnesium compound, (b) a liquid titanium compound, and (c)
After contacting the organosilicon compound with (d) the crystal nucleating agent, the resulting contact product (ii) may be contacted with (f) an aluminum compound.

It is preferable that the titanium compound (b) is used in an amount sufficient to precipitate a solid without contacting a special precipitation means. The amount of the titanium compound (b) used depends on the type, contact conditions, the amount of the organosilicon compound (c) used, etc., but the magnesium compound (a)
Usually, it is preferably about 1 mol or more, more preferably about 5 to about 200 mol, especially about 10 to about 10 mol per mol.
More preferably, it is 0 mol. Also titanium compound
(b) is preferably used in an amount exceeding 1 mol, more preferably 5 mol or more, per 1 mol of the organosilicon compound (c).

The amount of the organosilicon compound (c) to be used also varies depending on the kind and the like, but generally it is 0.01 to 1.0 mol per 1 mol of the magnesium compound (a). Preferably, furthermore, 0.05 to 0.8 mol, especially 0.1.
More preferably, it is 0.5 mol. Further, the organosilicon compound (c) is used in an amount of 1 mol per 1 mol of the titanium compound (b).
Preferably, it is used in an amount of less than 0.2 mole,
More preferably, it is used in an amount of not more than mol.

The amount of the aluminum compound (f) used also varies depending on the kind and the like, but it is generally preferably 0.01 to 0.7 mol per 1 mol of the magnesium compound (a). , And more preferably 0.03 to 0.5 mol, especially 0.5 mol.
More preferably, it is in the range of 0.5 to 0.3 mol.

The liquid magnesium compound (a) and / or the titanium compound (b) used for contacting the liquid magnesium compound (a) with the titanium compound (b) contain the organosilicon compound (c) in advance. Is also good.

In this case, it is not necessary to newly add the organosilicon compound (c) when the magnesium compound (a) and the titanium compound (b) are brought into contact, but they may be added. In any case, the total amount of the organosilicon compound (c) with respect to the magnesium compound (a) may be within the above range.

The nucleating agent (d) is composed of (a), (b) and (a).
When (c) or (a) is brought into contact with (b) and (c), it may be present in the catalyst component. As a nucleating agent, solid 2
When a valent metal halide is used, it is desirable that the solid divalent metal halide is present in the catalyst component so as not to dissolve.

The contact temperature of each component is not particularly limited, but is generally preferably in the range of -70 to 150 ° C.
For example, after contacting (a) a liquid magnesium compound, (c) an organosilicon compound, and (d) a crystal nucleating agent at 20 to 150 ° C., the obtained contact product (i) is converted into (b) liquid It is particularly preferred that the titanium compound and the (f) aluminum compound are contacted simultaneously or sequentially at a temperature of -70 to 50 ° C.

Further, (a) a liquid magnesium compound and (b)
After contacting the liquid titanium compound with the (c) organosilicon compound at -70 to 150 ° C, the obtained contact product (ii)
May be brought into contact with the aluminum compound (f) at a temperature of -20 to 150 ° C.

In the present invention, the liquid magnesium compound (a) and the liquid titanium compound (b) are added in the presence of the organosilicon compound (c).
At a low temperature at which a solid does not rapidly form due to this contact, and specifically at -70 to +5
0 ° C, preferably -50 to + 30 ° C, more preferably -4.
It is desirable to carry out at a temperature of 0 to + 20 ° C. The temperature of each solution used for the contact may be different. In addition, at the beginning of contact, when the contact temperature is too low and solid matter does not precipitate,
The contact at a low temperature can be performed for a long time to precipitate a solid.

By the above operation, the solid catalyst component containing magnesium, titanium, halogen and a crystal nucleating agent is treated with (f) an aluminum compound to obtain granules having a relatively large particle size and a good particle size distribution. A spherical or spherical solid titanium catalyst component can be obtained. And when the olefin such as ethylene is subjected to slurry polymerization using the solid titanium catalyst component having such excellent particle properties, a polymer having a granular or spherical shape with an excellent particle size distribution, a large bulk density and a good fluidity is obtained. be able to.

The solid titanium catalyst component according to the present invention prepared as described above contains magnesium, titanium, halogen, and (c) an organosilicon compound having no active hydrogen.

In this solid titanium catalyst component, the magnesium / titanium (atomic ratio) is about 2 to about 100, preferably about 4 to about 50, and more preferably about 5 to about 30; Ratio) is about 4 to about 100,
Preferably about 5 to about 90, more preferably about 8 to about 5
0, organosilicon compound (c) / titanium (molar ratio)
Is from about 0.01 to about 100, preferably from about 0.2 to about 1
Desirably, it is 0, more preferably about 0.4 to about 6.

The organosilicon compound (c) / magnesium (molar ratio) is about 0.001 to about 0.1, preferably about 0.01.
02 to about 0.08, particularly preferably 0.005 to 0.05.
It is desirable that

The aluminum compound (f) / magnesium (molar ratio) is 0.01 to 0.7, preferably 0.03 to 0.7.
0.5, particularly preferably 0.05 to 0.3. The solid titanium catalyst component may contain other components, such as a carrier, in addition to these components. Specifically, the other component is added in an amount of 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. %, More preferably 20% by weight or less.

The composition of the catalyst component is such that after thoroughly washing the solid titanium catalyst component with a large amount of hexane, the catalyst component is 0.1 to 1 Torr.
After drying at room temperature for 2 hours or more, it can be measured by ICP (atomic absorption spectrometry), gas chromatography or the like.

The shape of the solid titanium catalyst component according to the present invention is desirably granular or substantially spherical, and its specific surface area is about 10 m ² / g or more, preferably about 100 m ² / g.
Desirably, it is １０００1000 m ² / g.

In the present invention, the solid titanium catalyst component is usually used after washing with a hydrocarbon solvent. Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention is formed from the above-mentioned [I] solid titanium catalyst component and [II] an organometallic compound.

The organometallic compound used in the present invention preferably contains a metal selected from Groups I to III of the periodic table.
Examples thereof include complex alkyl compounds of group metal and aluminum, and organometallic compounds of group II metals.

As such an organoaluminum compound, for example, an organoaluminum compound represented by the following formula can be exemplified. 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 organic aluminum compound, a compound represented by the following formula can also be used. R ^a _n AlY _{3-n In the} above formula, R ^a is the same as above, and Y is -OR ^b
Group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -S
iR ^f ₃ or —N (R ^g ) AlR ^h _2;
R ^b , R ^c , R ^d and R ^h are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and ^Re is hydrogen, a methyl group, an ethyl group, an isopropyl group, Examples include a phenyl group and a trimethylsilyl group, and R ^f and R ^g are a methyl group, an ethyl group, and the like.

As such an organoaluminum compound, specifically, the following compounds are used. _{^{(i) R a n Al (}} OR b) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (ii) R a n Al}} (OSiR c) 3-n Et 2 Al (OSiMe 3 ), (Iso-Bu) ₂ Al (OSiMe ₃ ), (iso
Etc. _{-Bu) 2 Al (OSiEt 3)} , (iii) R a n Al (OAlR 4 2) 3-n Et 2 AlOAlEt 2, ( such as _{iso-Bu) 2 AlOAl (iso} -Bu) 2, (iv) R ^a _n Al (NR ^e ₂ ) _3-n Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt,
_{Et 2 AlN (Me 3 Si)} 2, etc. _{(iso-Bu) 2 AlN (} Me 3 Si) 2, (v) such as ^{_{R a n Al (SiR f 3}} ) 3-n (iso-Bu) 2 AlSiMe 3, (vi) such as R ^a _n Al [n (R ^g) -AlR ^b _{2] 3-n Et 2 AlN (Me} ) -AlEt 2 (iso-Bu) 2 AlN (Et) Al (iso-Bu) 2.

Further, there may be mentioned similar compounds, for example, organic aluminum compounds in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. More specifically, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ A
lOAl (C ₄ H ₉ ) ₂ , (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C
₂ H _{5) 2,} etc., may further include aluminoxanes such as methyl aluminoxane.

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

Examples of the organometallic compounds of Group II metals include compounds represented by the following general formula. R ^k R ¹ M ² (R ^k and R ¹ are a hydrocarbon group having 1 to 15 carbon atoms or a halogen, and may be the same or different from each other, except when both are halogen. M ² is Mg , Zn,
Specific examples thereof include diethylzinc, diethylmagnesium, butylethylmagnesium, ethylmagnesium chloride, and butylmagnesium chloride.

[0079] Among the organoaluminum compounds mentioned ^{_{above, R a n AlX 3-n}} , R a n Al (OR b) 3-n, R a n Al
The compound represented by (OAlR ⁴ ₂ ) _{3 -n} , in particular, a trialkylaluminum is preferably used.

These compounds can be used in combination of two or more kinds. In the olefin polymerization catalyst according to the present invention, olefins may be prepolymerized.

The catalyst for olefin polymerization according to the present invention as described above is particularly useful for the polymerization of ethylene or ethylene and other α.
-Useful for copolymerization with olefins, but can also be used for (co) polymerization of olefins other than ethylene.
When the catalyst for olefin polymerization of the present invention is used for (co) polymerization of olefins other than ethylene, an electron donor may be further used as necessary. As such an electron donor, various electron donors as described above can be used without particular limitation. The ethylene polymerization catalyst according to the present invention may contain other components useful for polymerization in addition to the above components.

Next, the method for polymerizing olefins according to the present invention will be described more specifically, taking ethylene polymerization as an example. Ethylene Polymerization Method In the ethylene polymerization method (main polymerization) according to the present invention, ethylene is reacted in the presence of an ethylene polymerization catalyst comprising the solid titanium catalyst component [I] and the organometallic compound [II] as described above. The polymerization is carried out, but ethylene and a small amount of other olefins may be copolymerized.

Specific examples of such olefins include α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-olefin. 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,
Examples include 1-hexadecene, 1-octadecene, and 1-eicosene. Furthermore, vinyl compounds, other unsaturated compounds, polyene compounds and the like can also be copolymerized, for example, styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalenes, substituted vinylnaphthalenes, allylnaphthalenes, Aromatic vinyl compounds such as substituted allylnaphthalenes, vinylcyclopentane, substituted vinylcyclopentanes, vinylcyclohexane, substituted vinylcyclohexanes, alicyclic vinyl compounds such as vinylcycloheptane, substituted vinylcycloheptanes, allylnorbornane, cyclopentene , Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,
Cyclic olefins such as 3,4,4a, 5,8,8a-octahydronaphthalene, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1- Octen, 10
Silane-based unsaturated compounds such as -trimethylsilyl-1-decene can also be copolymerized.

Further, two or more of the above-mentioned copolymerizable monomers can be used to copolymerize with ethylene. In the present invention, in the polymerization of ethylene, the solid titanium catalyst component [I]
The (or pre-polymerization catalyst) is usually desirably used in an amount of about 0.0001 to 1.0 mmol in terms of titanium atoms per liter of polymerization volume. Organometallic compounds [I
I] is such that the metal atom in the catalyst component [II] is usually about 1 to 2000 mol, preferably about 5 to 500 mol, per 1 mol of the titanium atom in the solid titanium catalyst component [I] in the polymerization system. It is desirable to use an amount such that

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, a polymerization-inert organic solvent is usually used as a polymerization solvent. As the organic solvent, specifically, propane,
Aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as ethylene chloride and chlorobenzene can be used. These may be used in combination. Further, a copolymer monomer which is liquid at the reaction temperature together with the organic solvent can be used.

The polymerization conditions vary depending on the type of polymerization or the type of the obtained ethylene polymer.
Usually, at a temperature of about 20 to 300 ° C., preferably about 50 to 150 ° C., at normal pressure to 100 kg / cm ^2, preferably about ² to 50 kg
/ Cm ² pressure.

The molecular weight of the obtained polymer can be controlled by using hydrogen during the polymerization. The polymerization as described above can be performed by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization was carried out by changing the reaction conditions.
It can also be performed in multiple stages.

In the present invention, when polymerizing ethylene,
The catalyst is formed using the specific solid titanium catalyst component as described above, whereby an ethylene polymer having excellent particle properties can be produced with extremely high polymerization activity. For this reason, the resulting ethylene polymer has a low catalyst content, particularly a halogen content, per polymer unit, and does not easily cause mold rust during molding. Further, since an ethylene polymer having a small fine powder content and excellent in particle properties can be obtained, it can be used without particular pelletization.

The bulk specific gravity of such an ethylene polymer obtained by the present invention is 0.20 to 0.60 g / cc, preferably 0.1 to 0.5 g / cc.
It is desirably 25 to 0.60 g / cc. The ethylene polymer melt flow rate MFR (ASTM
D1238E, 190 ° C) is 0.01 to 50.
It is desirably 00 g / 10 minutes.

The ethylene polymer obtained in the present invention as described above may contain, if necessary, a heat stabilizer, a weather stabilizer, an antistatic agent, an antiblocking agent, a lubricant, a nucleating agent, a pigment, a dye, an inorganic or organic material. A filler or the like can be blended.

When the olefin polymerization catalyst according to the present invention is used for the polymerization of olefins other than ethylene, the above-mentioned polymerization conditions can be appropriately adopted.

[0092]

According to the present invention, there is provided a solid titanium catalyst component capable of producing a polymer having a low fine powder content, a high bulk specific gravity, and excellent particle properties in an extremely high yield per polymerization volume. The present invention provides a catalyst for olefin polymerization containing the same and a method for polymerizing olefins using the catalyst.

[0093]

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, the composition, particle size and bulk specific gravity of the solid titanium catalyst component were measured as follows. (1) Al, Mg, Ti content ICP analysis (ICPF 1000TR, Shimadzu Corporation) (2) Cl content Measured by silver nitrate titration. (3) OR Group Content A sufficiently dried catalyst was added to an acetone solution to which 10% by weight of water was added, and ROH obtained by hydrolysis was quantified by gas chromatography. (4) Fine powder content Vibrator (manufactured by Iida Manufacturing Co., Ltd., low tap) and sieve (Bu
nsei Furui, 200 mm inside diameter). (5) Bulk specific gravity: Measured according to JIS K-6721

[0095]

Example 1 "Preparation of solid titanium catalyst component" 4.76 g (50 mmol) of anhydrous magnesium chloride, 28.
1 ml and 16.3 g of 2-ethylhexyl alcohol
(125 mmol) was heated and reacted at 130 ° C. for 3 hours to form a homogeneous solution. Then, 3.1 g (15 mmol) of tetraethoxysilane was added to this solution, and the mixture was further stirred and mixed at 50 ° C. for 2 hours. Tetraethoxysilane was dissolved in the solution.

Further, alumina fine particles (average particle size: 0.037 μm) were used as a nucleating agent, and 2.0 ml of a decane dispersion of the alumina particles (slurry concentration: 25.5 g / l) was used.
Was added to the above solution.

After cooling the whole amount of the homogeneous suspension thus obtained to room temperature, titanium tetrachloride 17 kept at 0 ° C.
0 ml (1.55 mol) was added dropwise with stirring over 1 hour.

After completion of the charging, the temperature of the obtained solution was raised to 110 ° C. over 4 hours, and the solution was stirred for 2 hours while maintaining the same temperature. After the completion of the reaction for 2 hours, a solid (1) was collected by hot filtration, and the solid was resuspended in 70 ml of toluene.

After the suspension was cooled to -20 ° C, 0.962 g (3 mmol) of di-2-ethylhexoxyaluminum chloride dissolved in 4 ml of toluene was separately added with stirring.

Then, while maintaining the temperature at -20 ° C., 30 ml (0.27 mol) of titanium tetrachloride was added dropwise with stirring over 0.5 hours. After completion of the charging, the obtained suspension was heated to 110 ° C. over 3 hours, and stirred for 2 hours while maintaining the same temperature.

After completion of the reaction for 2 hours, a solid (2) was collected by hot filtration, and the solid was sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the washing solution. After that, a hexane suspension of a solid titanium catalyst component was obtained.

The composition of the obtained solid titanium catalyst component is shown in Table 1. [Polymerization] 500 ml of purified n-heptane was charged into an autoclave having a volume of 1 liter under a nitrogen atmosphere, and 0.25 mmol of triethylaluminum and a hexane suspension of the solid titanium catalyst component obtained above were added. After adding 0.015 mmol equivalent in terms of titanium atoms, the temperature was raised to 80 ° C., hydrogen was supplied at 5.0 kg / cm ² G, and then ethylene was added so that the total pressure became 6.0 kg / cm ² G. It was supplied continuously for 1 hour and 30 minutes. The polymerization temperature was kept at 80 ° C.

After completion of the polymerization, the ethylene polymer was separated from the n-heptane solvent and dried. After drying, 131.5 g of a powdery polymer was obtained. The powdery polymer had an MFR of 34 g / 10 min and an apparent bulk specific gravity of 0.35 g / c.
c. Table 2 shows the results.

Table 2 shows the content of the fine powder PE in the powdery polymer.

[0105]

Comparative Example 1 A catalyst component was prepared and polymerized in the same manner as in Example 1 except that fine alumina particles were not used as a nucleating agent. The results are shown in Tables 1 and 2.

[0106]

Comparative Example 2 A catalyst component was prepared and polymerized in the same manner as in Example 1 except that di-2-ethylhexoxyaluminum chloride was not used. The results are shown in Tables 1 and 2.

[0107]

Example 2 In Example 1, the alumina fine particles as a nucleating agent were replaced with solid anhydrous magnesium chloride, and 1.91 ml of a decane dispersion of the solid anhydrous magnesium chloride (slurry concentration: 25.0 g / l). A catalyst component was prepared and polymerized in the same manner as in Example 1 except for using. The results are shown in Tables 1 and 2.

[0108]

[Table 1]

[0109]

[Table 2]

[Brief description of the drawings]

FIG. 1 shows an explanatory view of a process for treating a catalyst component according to the present invention and a process for preparing an olefin polymerization catalyst including the process.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J028 AA01A AB01A AC04A AC05A AC06A AC07A BA01B BA02A BB00A BB01B BC05B BC06B BC09B BC15B BC16B BC17B BC19B BC27B BC28B BC29B BC34A CA02C CA14A CA16A CAEBA EB EB CB CB CB EB10 EB11 EB21 EB26 EC01 EC02 FA01 FA02 FA03 FA04 FA07 FA09 GA07 GA09 GB02 4J100 AA02P AA03P AA04P AA07P AA15P AA16P AA17P AA18P AA19P AA20P AA21P AB00P AB01P AB02P03 AR03P03 AR03P03

Claims (4)

[Claims] 1. A method for treating a catalyst component, comprising treating a solid catalyst component containing magnesium, titanium, halogen and a nucleating agent with an alkoxyaluminum or an alkoxyaluminum halide. 2. A solid titanium catalyst component obtained by treating a solid catalyst component containing magnesium, titanium, a halogen and a nucleating agent with an alkoxyaluminum or an alkoxyaluminum halide. 3. A solid titanium catalyst component obtained by treating [I] a solid catalyst component containing magnesium, titanium, a halogen and a crystal nucleating agent with an alkoxyaluminum or an alkoxyaluminum halide, and [II] an organometallic compound And a catalyst for olefin polymerization. 4. A method for polymerizing an olefin, comprising subjecting the olefin to (co) polymerization in the presence of the catalyst according to claim 3.