JP2001106718A - Method of preparing solid-state titanium catalyst component for olefin polymerization, and solid-state titanium catalyst for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of preparing a solid-state titanium catalyst component capable of producing an olefinic polymer high in melting point and excellent in stereoregularity, and also to provide a catalyst containing the solid- state titanium catalyst component for producing an olefinic polymer. SOLUTION: This method of preparing a solid-state titanium catalyst component comprises the following steps (1) to (3): (1) bringing a liquid magnesium compound (a) and liquid titanium compound (b) into contact with each other, to separate the solid particles 1, (2) removing at least 90 wt.% of the atomic titanium from the solid particles 1 separated in the step (1), and (3) bringing the solid particles 2 obtained in the step (2) into contact with a titanium compound (c) and, as required, electron donor (d).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solid titanium catalyst component capable of producing an olefin polymer having a high melting point and a high stereoregularity, and to an olefin polymerization catalyst containing the solid titanium catalyst component.

[0002]

BACKGROUND OF THE INVENTION Heretofore, solid catalysts comprising a transition metal catalyst component such as titanium and a typical metal catalyst component such as aluminum have been widely known as olefin polymerization catalysts.

[0003] With the advent of a supported catalyst using a magnesium compound as a carrier, the polymerization activity of olefin polymerization catalysts has been drastically increased. Further, by adding an electron donor such as an ester compound, carbon atoms can be reduced. It has become possible to produce a polymer having high stereoregularity from α-olefins of several or more.

In recent years, it has been reported that a high-performance catalyst having high activity, high stereoregularity and uniform particle shape can be obtained by contacting a liquid magnesium compound or titanium compound to precipitate a solid. 58-830
No. 06, for example.

The present inventor has further studied such a high activity and high stereoregularity catalyst, and found that the solid particles precipitated by contacting a liquid magnesium compound and a liquid titanium compound were once used. By removing at least a part of the titanium compound and bringing the solid particles from which the titanium compound has been removed into contact with the titanium compound again, an olefin polymer having a high melting point and excellent stereoregularity is obtained. It has been found that a titanium catalyst component can be obtained.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is capable of polymerizing α-olefins such as ethylene and propylene with a relatively high activity, having a high melting point and a high stericity. It is an object of the present invention to provide a method for preparing a solid titanium catalyst component capable of producing an olefin polymer having excellent regularity and a method for preparing an olefin polymerization catalyst containing the solid titanium catalyst component.

[0007]

SUMMARY OF THE INVENTION A method for preparing a solid titanium catalyst component according to the present invention is characterized by comprising the following steps (1) to (3): (1) Liquid magnesium compound (a) and liquid titanium compound (B) Contacting to precipitate solid particles (1) (2) Step of removing 90% by weight or more of titanium atoms contained in solid particles (1) obtained in step (1) (3) Step ( A step of contacting the solid particles (2) obtained in 2) with the titanium compound (c) and, if necessary, the electron donor (d).

The step (2) is, for example, a step of bringing the solid particles (1) obtained in the step (1) into contact with an organosilicon compound (e) represented by SiCl _n (OR) _4-n .
In the present invention, step (3) may be performed a plurality of times.

The catalyst for olefin polymerization according to the present invention comprises:
(I) a solid titanium catalyst component obtained by the above-mentioned preparation method, (II) an organometallic compound, and if necessary, (III)
And an electron donor.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for preparing the solid titanium catalyst component and the catalyst for olefin polymerization according to the present invention will be specifically described.

The method for preparing a solid titanium catalyst component for olefin polymerization according to the present invention comprises the steps of (I) contacting a liquid magnesium compound (a) with a liquid titanium compound (b) to precipitate solid particles (1). (II) 90% by weight of titanium atoms contained in the solid particles (1) obtained in the step (I)
The method includes a step of removing the above, and a step of bringing the solid particles (2) obtained in the step (II) into contact with the titanium compound (c) and, if necessary, the electron donor (d).

First, each component used for preparing the solid titanium catalyst component will be described. (A) Liquid magnesium compound The liquid magnesium compound (a) used in the present invention may be a liquid magnesium compound itself or a solid magnesium compound prepared as a magnesium compound solution. As a method of converting the solid magnesium compound into a magnesium compound solution, there is a method of dissolving the solid magnesium compound in the electron donor (d-1) as described later.

The magnesium compound itself is a liquid magnesium compound or a solid magnesium compound, (a-1) a magnesium compound having a reducing ability and (a-
2) Magnesium compounds having no reducing ability.

Magnesium compound having reducing ability (a-1)
Is, for example, an organic magnesium represented by the following general formula
System compounds. MgX¹ _nR¹ _2-n Wherein n is 0 ≦ n <2 and R¹Is hydrogen atom, carbon atom
Alkyl group having 1 to 20 carbon atoms, ant having 6 to 20 carbon atoms
Or a cycloalkyl group having 3 to 20 carbon atoms
There are two Rs if n is 0¹Are the same but different
May be. X ¹Is a halogen atom, hydrogen atom or carbon
It is an alkoxy group having 1 to 20 atoms. Where R¹But
X for a hydrogen atom¹Is a halogen atom.

As the organomagnesium compound (a-1) having such a reducing ability, specifically, 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, amyl magnesium chloride Halides; alkylmagnesium alkoxides such as butylethoxymagnesium, ethylbutoxymagnesium, and octylbutoxymagnesium; and butylmagnesium hydride.

The magnesium compound having no reducing ability (a-
Examples of 2) include a magnesium compound represented by the following general formula. Mg (OR ²⁾ in _n X _{^{2 2-n}} wherein, n = 0 ≦ n ≦ ^2, R 2 is 1 to 2 carbon atoms
When it is 0 hydrocarbon group and n is 2, two R ² may be the same or different. X ² is a halogen atom or a hydrogen atom.

Specific examples of the magnesium compound (a-2) having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; methoxymagnesium chloride, ethoxy Alkoxy magnesium halides such as magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, and octoxy magnesium chloride; allyloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy Alkoxy magnesium such as magnesium and 2-ethylhexoxy magnesium; phenoxy magnesium and dimethylphenoxy magnesium , And the like magnesium hydride; Lilo alkoxy magnesium.

The magnesium compound having no reducing ability (a-
2) further includes magnesium carboxylate such as magnesium laurate and magnesium stearate,
Magnesium metal can also be used.

The magnesium compound having no reducing ability (a-2) is a compound derived from the above-mentioned magnesium compound having reducing ability (a-1) or a compound derived at the time of preparing a catalyst component. Is also 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 a polysiloxane compound , A halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, a halogen-containing compound other than the above, or a compound other than the above having an OH group or an active carbon-oxygen bond.

The magnesium compound having reducing ability (a-1) and the magnesium compound having no reducing ability
(a-2) is aluminum, zinc, boron, beryllium,
Metal compounds such as sodium and potassium (for example, organometallic compounds described below as organometallic compounds (II))
May form a complex compound or a complex compound, or may be used as a mixture with these metal compounds.

Among the magnesium compound (a-1) having the reducing ability and the magnesium compound (a-2) having no reducing ability as described above, the solid magnesium compound is the electron donor (d-1) Into a liquid.

As the electron donor (d-1), alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and the like described later are used as the electron donor (d). .

The electron donor (d-1) includes tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, tetraethoxyzirconium and the like. Metal acid esters and the like can also be used.

Of these, alcohols and metal esters are particularly preferably used. In order to dissolve the solid magnesium compound in the electron donor (d-1), a method in which the solid magnesium compound is brought into contact with the electron donor (d-1) and, if necessary, heating is performed. . This contact is usually performed at 0 to 200 ° C, preferably 20 to 180 ° C,
More preferably, it can be performed at a temperature of 50 to 150 ° C.

The above reaction is preferably carried out in the presence 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; alicyclic 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.

As the liquid magnesium compound (a) used for preparing the solid titanium catalyst component, magnesium compounds other than those described above can also be used. The liquid magnesium compound (a) used for preparing the solid titanium catalyst component includes:
It is preferable that the solid titanium catalyst component finally obtained is present in the form of a halogen-containing magnesium compound. Therefore, when a halogen-free liquid magnesium compound is used, a catalytic reaction with the halogen-containing compound occurs during the preparation. Preferably.

As the liquid magnesium compound (a),
Among these, magnesium compounds that have no reducing ability
(a-2) is preferred, and a halogen-containing magnesium compound is particularly preferred. Of these, magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are preferred.

(B) Liquid Titanium Compound As the liquid titanium compound (b) used in the present invention, a tetravalent titanium compound is particularly preferably used. Examples of such a tetravalent titanium compound include compounds represented by the following general formula.

[0029] During _{Ti (OR) g X 4-} g formulas, R is a hydrocarbon group, X is a halogen atom, a 0 ≦ g ≦ 4. As such a titanium compound, specifically, TiCl ₄ , TiBr ₄ , TiCl ₂ Br ₂
A titanium tetrahalide such as Ti (OCH ₃ ) Cl ₃ ,
Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti
Trihalogenated alkoxytitanium such as (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) ₂ C
l ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ C
_{l 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 ) ₃ Br
Monohalogenated trialkoxy titanium such as Ti;
CH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H ₉ ) ₄ , Ti
And tetraalkoxy titanium such as (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, titanium tetrahalides are preferred, and titanium tetrachloride is particularly preferred. These liquid titanium compounds may 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) Titanium Compound The titanium compound used in the present invention includes, for example, the above-mentioned liquid titanium compound (b), preferably a titanium halide, and more preferably titanium tetrachloride. In addition, for example, the following general formula: TiR _m Cl _n (OR ′) _4-mn (R and R ′ are alkyl groups and may be the same or different; m is an integer of 1 to 4; Is an integer of 0 to 3 and m + n ≦ 4) or an electron donor selected from an electron donor (d) described later and halogenation such as titanium tetrachloride or titanium tetrabromide. A complex with titanium is exemplified.

These compounds may be used alone or in combination of two or more, and may be used after being diluted with a hydrocarbon solvent or the like. (D) Electron Donor Examples of the electron donor (d) used in the present invention include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, and ethers. Acid amide, acid anhydride, ammonia, amine, nitrile, hydroxy ether, isocyanate, nitrogen-containing cyclic compound, oxygen-containing cyclic compound, and the like.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol; 1 to 1 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol
8 halogen-containing alcohols; 6 to 6 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol;
20 phenols; acetone, methyl ethyl ketone,
C3 to C15 ketones such as methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; C2 to C15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; 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, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxy benzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate, carbonic acid Organic acid esters having 2 to 30 carbon atoms such as dimethyl; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride; methyl ether, ethyl ether, isopropyl Ether, butyl ether,
Ethers having 2 to 20 carbon atoms such as amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide and toluic acid N, N-dimethylamide; Methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine,
Amines such as tributylamine, tribenzylamine, tetramethylenediamine, hexamethylenediamine;
Nitriles such as acetonitrile, benzonitrile and trinitrile; hydroxyethers such as 1-butoxyethanol, 2-butoxyethanol and 2-butoxypropanol; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride; pyrrole, methyl Pyrroles such as pyrrole and dimethylpyrrole; pyrroline; pyrrolidine; indole; pyridines such as pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine and pyridine chloride; piperidine , Quinolines, isoquinolines and other nitrogen-containing cyclic compounds; tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, Zofran, coumaran, phthalan, tetrahydropyran, pyran, and the like cyclic oxygen-containing compound such as Jitedoropiran.

As the above-mentioned organic acid ester, a polycarboxylic acid ester having a skeleton represented by the following general formula can be mentioned as a particularly preferred example.

[0035]

Embedded image

In the above formula, R¹Is a substituted or unsubstituted carbonized
R represents a hydrogen group;^Two, R^FiveAnd R ⁶Are identical to each other
May be different, a hydrogen atom or a substituted or unsubstituted
Represents a substituted hydrocarbon group;^ThreeAnd R^FourAre the same as each other
May be one or different, hydrogen or substituted or
Represents an unsubstituted hydrocarbon group, preferably at least
One is a substituted or unsubstituted hydrocarbon group. Also
R^ThreeAnd R^FourAre connected to each other to form a ring structure
You may. Hydrocarbon group R¹~ R⁶Is replaced
Has a heteroatom such as N, O, S, etc., for example,
COC, COOR, COOH, OH, SO_ThreeH,-
C—N—C—, NH_TwoAnd the like.

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

Other examples of the polycarboxylic acid ester 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.

As the electron donor (d), a polyether compound having two or more ether bonds existing through a plurality of atoms can be used. In this polyether, the atoms existing between the ether bonds are carbon,
Examples thereof include silicon, oxygen, nitrogen, phosphorus, boron, sulfur, and two or more compounds selected from these. Among these, a compound in which a relatively bulky substituent is bonded to an atom between ether bonds and a plurality of carbon atoms are contained in an atom existing between two or more ether bonds is preferable, for example, represented by the following formula: Polyethers are preferred.

[0040]

Embedded image

(Where n is an integer of 2 ≦ n ≦ 10,
R ^{1 to} R ²⁶ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and arbitrary R ^{1 to} R ²⁶ ,
Preferably, R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and atoms other than carbon may be contained in the main chain. Among them, 1,3-diethers are preferably used, and in particular, 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.

Further, as the electron donor (d), an electron donor (III) as described later, water, or an anionic, cationic or nonionic surfactant can be used.

These electron donors (d) can be used in combination of two or more. In the present invention, as the electron donor (d), among the above, carboxylic acid esters, particularly polyvalent carboxylic acid esters, particularly phthalic acid esters, and polyethers are preferably used.

(E) Organosilicon Compound The organosilicon compound used in the present invention includes compounds represented by the following general formula.

[0045] (in R, having 1 to 20 carbon atoms, preferably an 1-8 alkyl radical, n is an integer of _{0~4.) SiCl n (OR)} 4-n such organosilicon compounds Specifically, for example, tetrachlorosilane, SiCl ₃ (OMe), SiC
l ₃ (OEt), SiCl ₃ (On-Pr), SiCl ₃ (O i-
Pr), SiCl ₃ (On-Bu), SiCl ₃ (O i-B
u), trichloroalkoxysilanes such as SiCl ₃ (Ot-Bu); SiCl ₂ (OMe) ₂ , SiCl ₂ (OE
t) ₂ , SiCl ₂ (On-Pr) ₂ , SiCl ₂ (O i-P
r) ₂ , SiCl ₂ (On-Bu) ₂ , SiCl ₂ (O i-B
u) ₂ , dichlorodialkoxysilanes such as SiCl ₂ (Ot-Bu) ₂ ; SiCl (OMe) ₃ , SiCl (OE
t) ₃ , SiCl (On-Pr) ₃ , SiCl (O i-Pr) ₃ ,
SiCl (O n-Bu) ₃ , SiCl (O i-Bu) ₃ , SiC
Monochlorotrialkoxysilanes such as l (Ot-Bu) ₃ ; Si (OMe) ₄ , Si (OEt) ₄ , Si (On-P
r) ₄ , Si (O i -Pr) ₄ , Si (On-Bu) ₄ , Si (O
Tetraalkoxysilanes such as i-Bu) ₄ and Si (Ot-Bu) ₄ .

Among these organosilicon compounds, tetraalkoxysilanes are preferable, and particularly, Si (OEt)
₄ is preferred. Preparation of Solid Titanium Catalyst Component The method for preparing the solid titanium catalyst component according to the present invention from the above components is as follows.

Step (I) To prepare the solid titanium catalyst component according to the present invention, first, a liquid magnesium compound (a) and a liquid titanium compound (b) are brought into contact. The contacting method is not particularly limited, but a method is generally selected in which the liquid magnesium compound (a) is dropped into the liquid titanium compound (b) and then heated.

When the liquid magnesium compound (a) is brought into contact with the liquid titanium compound (b), for example, the liquid titanium compound (b) is preferably used in an amount of 0.01 to 1000 mol per mol of the liquid magnesium compound (a). Is 0.1 ~
It can be used in an amount of 200 mol. The temperature at the time of dropping is preferably in the range of -70 to 100 ° C, particularly -70 to 50 ° C, and the dropping time is preferably 5 to 300 minutes, particularly preferably 30 to 180 minutes.

Next, by heating the solution obtained as described above, the solid particles (1) are obtained in a state of being suspended in the liquid. The heating temperature at this time is usually -40 to 20
The heating temperature is preferably in the range of 0 ° C, particularly −40 to 50 ° C., and the heating time is preferably 10 to 360 minutes, particularly preferably 30 to 300 minutes. Solid particles obtained here (1)
Usually contains about 10% by weight of a titanium atom or a compound containing titanium in terms of a titanium atom.

In the present invention, when the liquid magnesium compound (a) is brought into contact with the liquid titanium compound (b),
Complexes of metals other than titanium and magnesium, such as lithium acetylacetonate and potassium acetylacetonate, may coexist. Such a metal complex is usually used in an amount of 0.0001 to 1 per mol of the liquid magnesium compound (a).
It is preferred to use it in an amount of from 0.001 to 0.1 mol, especially from 0.001 to 0.1 mol. When the above-described complex is present in the preparation of the solid particles (1), a solid titanium catalyst component having excellent polymerization activity tends to be obtained.

Step (II) Next, from the solid particles (1) obtained in the step (I), 90% by weight or more, preferably 90 to 100% by weight, of titanium atoms contained in the solid particles (1) is added. Preferably 92 to 1
00% by weight, more preferably 95 to 100% by weight. As a method therefor, a method of contacting the solid particles (1) with the organosilicon compound (e) is preferably used.

Specifically, the solid particles (1) are separated from the suspension containing the solid particles (1) obtained in the step (I) by, for example, filtration, and reslurried with a hydrocarbon solvent. A suspension is prepared and the solid particles (1) are brought into contact with the organosilicon compound (e) in the suspension.

Specific examples of the hydrocarbon solvent used herein include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane and the like. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these, aromatic hydrocarbons are preferred, and toluene is particularly preferred.

Solid particles (1) and organosilicon compound (e)
When contacting with, the organosilicon compound (e) is preferably used in an amount of usually 0.01 to 100 mmol, particularly 0.1 to 10 mmol, per 1 g of the solid particles (1). The contact temperature is usually 20 to 300 ° C, especially 50
The contact time is preferably in the range of from to 150 ° C, and the contact time is usually from 10 to 360 minutes, preferably from 30 to 300 minutes.

Solid particles (1) and organosilicon compound (e)
After contacting the solid particles (2), the solid particles (2) are separated by, for example, hot filtration, and the solid particles (2) are separated from a hydrocarbon solvent,
For example, it is preferable to wash with an aliphatic or aromatic hydrocarbon such as decane and hexane. This washing is preferably performed until no free titanium is detected.

The solid particles thus obtained (2)
Is that the content of the compound containing magnesium is usually 80% by weight or more, the content of the titanium atom or the compound containing the titanium atom is usually 0.5% by weight or less in terms of the titanium atom, and the organosilicon compound (e) Is usually less than 0.01 mol per 1 mol of magnesium atom.

Step (III) In the present invention, the solid particles (2) obtained in the step (II) are
It is further contacted with the titanium compound (c) and, if necessary, the electron donor (d) to obtain a solid titanium catalyst component.
Specifically, for example, the solid particles (2) are reslurried with a titanium compound (c), preferably a titanium halide,
Usually at a temperature in the range of 20 to 300 ° C, preferably 50 to 150 ° C, usually for 1 to 1000 minutes, preferably 5 to 60 minutes.
The titanium halide is brought into contact with the solid particles (2) for 0 minutes. At this time, the electron donor (d) may be allowed to coexist.

When the solid particles (2) are brought into contact with the titanium compound (c) and, if necessary, the electron donor (d), the titanium compound (c) is usually added in an amount of 0 to 1 g of the solid particles (2). 0.0001 to 10 mol, preferably 0.0005 to 1
The electron donor (d) is optionally used in an amount of usually 0.01 to 100 mmol, preferably 0.1 to 10 mmol, per 1 g of the solid particles (2).

The contact between the solid particles (2) and the titanium compound (c) and, if necessary, the electron donor (d) as described above,
Can be performed multiple times. After bringing the solid particles (2) into contact with the titanium compound (c) and, if necessary, the electron donor (d), the solid titanium catalyst component is separated by, for example, hot filtration, and the solid titanium catalyst component is separated. Is preferably washed with a hydrocarbon solvent, for example, an aliphatic hydrocarbon such as hexane. This washing is preferably performed until no free titanium is detected.

The solid titanium catalyst component thus obtained contains 0.1 to 5% by weight, preferably 0.1 to 2% by weight of titanium atoms and usually 1 to 50% by weight of magnesium atoms.
%, Preferably 10 to 40% by weight, and 30% by weight of halogen.
-80% by weight, preferably 40-80% by weight, and the electron donor in a proportion of 0.1-30% by weight, preferably 1-20% by weight.

When the solid titanium catalyst component obtained as described above is used as a catalyst component for olefin polymerization,
An olefin polymer having a relatively high polymerization activity and a high melting point can be produced, and when an α-olefin having 3 or more carbon atoms is polymerized, an olefin polymer having extremely high stereoregularity can be obtained.

Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention comprises (I) a solid titanium catalyst component obtained by the above-mentioned method, (II) an organometallic compound, and (III) And a donor.

(II) Organometallic Compound (II) Organometallic Compound Forming Catalyst for Olefin Polymerization
Specific examples include organic aluminum compounds and complex alkyl compounds of a Group 1 metal with aluminum.

Such an organoaluminum compound is represented by the following formula, for example. R ^a _n AlX _3-n (wherein, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen atom, n represents a 1 to 3.) R ^a is carbon A hydrocarbon group having 1 to 12 atoms, such as an alkyl group, a cycloalkyl group or an aryl group,
Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group,
Octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and the like. Specific examples of such organoaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminums such as isoprenylaluminum; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide Alkylaluminum sesquihalide such as; methyl aluminum dichloride, ethyl aluminum dichloride,
Alkyl aluminum dihalides such as isopropyl aluminum dichloride and ethyl aluminum dibromide; and alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound, the following
Compounds represented by the general formula can also be mentioned. R^a _nAlY_3-n In the above general formula, R^aIs the same as above, and Y is-
OR^bGroup, -OSiR ^c _ThreeGroup, -OAlR^d _TwoGroup, -NR
^e _TwoGroup, -SiR^f _ThreeGroup or -N (R_g) AlR ^h _TwoBased on
And n is 1-2, R^b, R^c, R^dAnd R^h
Is methyl, ethyl, isopropyl, isobutyl
Group, cyclohexyl group, phenyl group, etc.^eIs
Hydrogen, methyl group, ethyl group, isopropyl group, phenyl
Group, trimethylsilyl group, etc.^fAnd R^gIs
Examples include a methyl group and an ethyl group.

Specific examples of such an organoaluminum compound include the following compounds. represented by _{^{(ii) R a n Al (}} OSiR c) 3-n; (i) R a n Al (OR b) compound dimethyl aluminum methoxide represented by _3-n, diethylaluminum ethoxide and diisobutylaluminum methoxide Compounds Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiMe
_{3), (iso-Bu)} 2 Al (OSiEt 3) , _{^{etc.; (iii) R a n Al}} (OAlR d 2) a compound represented by _{3-n Et 2 AlOAlEt 2,} (iso-Bu) 2 AlOAl (iso- B
u) ₂ etc. (iv) Compound represented by R ^a _n Al (NR ^e ₂ ) _3-n Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNH
Et, Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN
Such as _{(Me 3 Si) 2, (} v) R a n Al (SiR f 3) a compound represented by _3-n such as _{(iso-Bu) 2 AlSiMe 3} , (vi) R a n Al [N (R ^g) -AlR ^h ₂ ] A compound represented by _3-n Et ₂ AlN (Me) -AlEt ₂ , (iso-Bu) ₂ AlN (E
t) Al (iso-Bu) ₂ etc.

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

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

Among the above-mentioned organometallic compounds,
R ^a ₃ Al, R ^a _n Al (OR ^b ) _3-n , R ^a _n Al (OAl
An organic aluminum compound represented by R ^d ₂ ) _3-n is preferably used.

The above organometallic compounds (II) can be used alone or in combination of two or more. (III) Electron Donor The olefin polymerization catalyst according to the present invention comprises the solid titanium catalyst component (I) and the organoaluminum compound (II)
In addition to the above, an electron donor (III) can be used if necessary. As the electron donor (III), an organic silane compound having at least one alkoxy group represented by the following general formula (i) is preferably used.

R _n Si (OR ') _4-n (i) (wherein R and R' are carbon atoms such as an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, an alkylaryl group and an alkenyl group) Examples thereof include a hydrogen group, 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 general formula (i) is particularly preferably represented by the following general 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 3, when 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 C 1 -C 4 carbon atom; When (4-n) is 2 or 3 in the case of a hydrogen group, OR ^b
May be the same or different. In the organosilane compound having a bulky group represented by the general formula (ii), the secondary or tertiary hydrocarbon group may be a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, or a substituent. And a hydrocarbon group in which carbon adjacent to Si 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-
Dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group, 2,3,4-triethylcyclopentyl group, A cyclopentyl group having an alkyl group such as a tetramethylcyclopentyl group and a tetraethylcyclopentyl group is exemplified.

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.

The substituted cyclopentadienyl group includes 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, s-butyl, s-amyl, α-methylbenzyl and the like. Examples of the hydrocarbon group in which carbon is a tertiary carbon include t-
Butyl group, t-amyl group, α, α′-dimethylbenzyl group,
Admantyl groups and the like can be mentioned.

When n is 1, the organic silane compound represented by the general formula (ii) may be cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane. Silane, cyclopentyltriethoxysilane, is
trialkoxysilanes such as o-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane and 2-norbornanetriethoxysilane; In the case of, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, And dialkoxysilanes such as 2-norbornanemethyldimethoxysilane.

When n is 2 among the organic silane compounds represented by the general formula (ii), particularly preferred are dimethoxysilane compounds represented by the following general formula (iii).

[0079]

Embedded image

In the formula, R ^a and R ^c may be the same or different from each other, and may be a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group. Or the carbon adjacent to Si is a secondary carbon or 3
It is a hydrocarbon group that is a grade carbon.

Examples of the dimethoxysilane compound represented by the general formula (iii) include, for example, 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, (2,3-diethylcyclopentyl) dimethoxysilane, di (2,3,4-trimethylcyclopentyl)
Dimethoxysilane, di (2,3,5-trimethylcyclopentyl) dimethoxysilane, di (2,3,4-triethylcyclopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane, di (tetraethylcyclopentyl) dimethoxysilane, di ( 2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclopentenyl) 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) dimethoxy Run, di (2,3,4-
Triethylcyclopentenyl) dimethoxysilane, di (tetramethylcyclopentenyl) dimethoxysilane,
Di (tetraethylcyclopentenyl) dimethoxysilane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxysilane, di ( 2-n-butylcyclopentenyl) dimethoxysilane, di (2,3-dimethylcyclopentadienyl) dimethoxysilane, di (2,4-dimethylcyclopentadienyl) dimethoxysilane, di (2,5-dimethylcyclopenta Dienyl) 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-butyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, dis-butyldimethoxysilane, dis-amyldimethoxysilane, Isopropyl-s-butyldimethoxysilane and the like.

Further, when n is 3 as the organosilane compound represented by the general formula (ii), tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentyl Monoalkoxysilanes such as methylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane are exemplified.

Among them, 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 general formula (iii) The dimethoxysilane compounds shown are preferred. Particularly, a dimethoxysilane compound represented by the general formula (iii) is preferable, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) Dimethoxysilane, di-t-amyldimethoxysilane and the like are preferred.

In the present invention, 2,6-substituted piperidines and 2,5-substituted piperidines are further used as the electron donor (III);
N, N, N ', N'-tetramethylmethylenediamine, N, N, N', N'-
Substituted methylenediamines such as tetraethylmethylenediamine; nitrogen-containing compounds such as substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine; triethylphosphite, tri-n-propyl Phosphorus-containing compounds such as phosphites such as phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite; 2,6-substituted tetrahydropyran And oxygen-containing compounds such as 2,5-substituted tetrahydropyrans; and the above-described electron donor (d), particularly, a polyether compound.

The above electron donors (III) can be used alone or in combination of two or more. The olefin polymerization catalyst according to the present invention is formed from the above (I) solid titanium catalyst component, (II) an organometallic compound, and, if necessary, (III) an electron donor.

The olefin polymerization catalyst according to the present invention may be a prepolymerization catalyst obtained by prepolymerizing an olefin with the olefin polymerization catalyst as described above. Examples of the olefin 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 Α-olefins having 2 or more carbon atoms, such as -1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Further, other vinyl compounds and polyene compounds as described later can also be used at the time of preliminary polymerization. These can be used alone or in combination of two or more.

The olefin used in the prepolymerization may be the same as the olefin used in the main polymerization described later,
It may be different. In the present invention, there is no particular limitation on the method of performing the prepolymerization.For example, the prepolymerization can be performed in a state where the olefins and the polyene compound are in a liquid state, or can be performed in the coexistence of an inert solvent. It is also possible to carry out under conditions. Of these, in the presence of an inert solvent,
Add olefins and each catalyst component to the inert solvent,
Preliminary polymerization is preferably performed 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 may be carried out under a condition in which the prepolymer is not dissolved, but it is preferably carried out under a condition in which the prepolymer is not dissolved.

The prepolymerization is usually carried out at about -20 to + 100 ° C.
Preferably about -20 to + 80 ° C, more preferably -1.
It is desirable to carry out at 0 to + 40 ° C. The pre-polymerization is
It can be performed in any of a batch system, a semi-continuous system, and a continuous system.

In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. Although the concentration of the catalyst component in the prepolymerization varies depending on the catalyst component used, the concentration of the solid titanium catalyst component (I) is expressed in terms of titanium atoms per liter of polymerization volume.
Usually about 0.001 to 5000 mmol, preferably about 0.005 mmol.
01-1000 mmol, particularly preferably 0.1-50
Desirably, it is 0 mmol.

The organometallic compound (II) is used in an amount of 0.01 to 2000 g, preferably 0.03 to 1000 g, more preferably 0.05 to 2 g per 1 g of the solid titanium catalyst component (I).
It is used in an amount such that 00 g of the preliminary (co) polymer is produced, and usually about 0.1 to 1000 mol, preferably about 0.5, per mol of titanium in the solid titanium catalyst component (I).
It is used in an amount of ５００500 mol, particularly preferably 1-100 mol.

At the time of prepolymerization, the electron donor (III)
Is usually 0.01 to 50 mol, preferably 0.05 to 30 mol, per 1 mol of titanium atom in the solid titanium catalyst component (I).
Moles, more preferably 0.1 to 10 moles, if necessary.

In the prepolymerization, a molecular weight regulator such as hydrogen may be used. When the prepolymerized catalyst is obtained in a suspended state, in the next step (main) polymerization, the prepolymerized catalyst can be used in a suspended state,
The prepolymerized catalyst formed from the suspension can be used separately.

As the above prepolymerized catalyst, for example, the prepolymerized catalyst obtained in a suspension state can be used as it is as a catalyst for olefin polymerization, and together with the prepolymerized catalyst, if necessary, the organometallic compound (II) And / or an electron donor (III) can be used. When polymerizing an α-olefin having 3 or more carbon atoms, it is desirable to use an electron donor (III). When the electron donor (III) is not used during prepolymerization, the electron donor (III) is used together with a prepolymerization catalyst. ) May be used to form an olefin polymerization catalyst.

The olefin polymerization catalyst according to the present invention may contain other components useful for olefin polymerization in addition to the above components. In the olefin polymerization method according to the present invention, the olefin polymerization catalyst comprising the solid titanium catalyst component (I) and the organometallic compound catalyst component (II), and if necessary, the electron donor (III), or the prepolymerization The olefin is polymerized or copolymerized in the presence of a catalyst and, if necessary, a catalyst comprising an organometallic compound (II) and / or an electron donor (III).

Specific examples of the olefin used in the polymerization include those having 2 carbon atoms similar to those used in the preliminary polymerization.
The above α-olefins can be used, and cyclopentene, cycloheptene, norbornene, 5-ethyl
2-norbornene, tetracyclododecene, 2-ethyl-1,
Cycloolefins such as 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; styrene, dimethylstyrenes, allylnaphthalene, allylnorbornane, vinylnaphthalenes, allyltoluene And vinyl compounds such as allylbenzene, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, and allyltrialkylsilanes.

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. Specific examples of such a diene compound include 1,3-butadiene, 1,3-pentadiene,
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. These diene compounds can be used alone or in combination of two or more.

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

In the polymerization, the solid titanium catalyst component (I) or the prepolymerized catalyst is usually used in an amount of about 0.001 to 100 mmol, preferably about 0.005 to 100 mmol, in terms of titanium atom per liter of polymerization volume. Used in an amount of 20 mmol.

The organometallic compound (II) is generally used in an amount of about 1 to 2000 mol, preferably about 2 to 50 mol, per 1 mol of the titanium atom in the polymerization system.
It is used in an amount such that it becomes 0 mol.

The electron donor (III) is an organometallic compound (I
Usually about 0.001 mol to 1 mol of the metal atom in I).
It is optionally used in an amount such that it becomes 10 mol, preferably 0.01 mol to 5 mol.

As described above, when a prepolymerization catalyst is used in this polymerization, neither the organometallic compound (II) nor the electron donor (III) may be used in some cases. When an olefin polymerization catalyst is formed from the organometallic compound (II) and / or the electron donor (III) together with the prepolymerization catalyst, these components (II) and (III) are used in the above amounts. be able to.

When hydrogen is used at the time of polymerization, the molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained. The polymerization conditions in the olefin polymerization method according to the present invention vary depending on the type of olefin, the form of polymerization, and the like.
00 ° C., preferably about 50 to 150 ° C., and the polymerization pressure is normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / c.
m ² .

The polymerization can be carried out by any of batch, semi-continuous and continuous methods. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

[0105]

By using the olefin polymerization catalyst containing the solid titanium catalyst component obtained in the present invention, α-olefins such as ethylene and propylene can be polymerized with relatively high activity, and the number of carbon atoms can be increased. When three or more α-olefins are polymerized, an olefin polymer having a high melting point and extremely high stereoregularity can be obtained.

[0106]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In this example, the boiling heptane extraction residual ratio, the 23.degree. C. n-decane soluble component amount and the melting point were determined as follows. Boiling heptane extraction residual ratio (t-II) 200 ml of n-heptane was added to 3 g of a polymer sample, and the mixture was subjected to Soxhlet extraction for 3 hours. The remaining sample was dried for 1 hour, weighed, and determined from the amount of polymerization reduction.

23 ° C. n-decane soluble component (DS) In a 1 liter flask equipped with a stirrer, 3 g of a polymer sample was placed.
2,6-ditert-butyl-4-methylphenol 20 mg, n-
500 ml of decane is added and dissolved by heating on an oil bath at 145 ° C. After the polymer has dissolved, it is cooled to room temperature over about 8 hours and subsequently kept on a 23 ° C. water bath for 8 hours. The precipitated copolymer and the n-decane suspension containing the dissolved polymer are separated by filtration through a glass filter. The resulting solution is
The mixture is dried at 0 mmHg and 150 ° C. until a quantitative amount is obtained, the weight is measured, and the amount is calculated as the amount of the soluble component of the polymer in the mixed solvent and calculated as a percentage based on the weight of the polymer.

Melting point (Tm) The endothermic curve of the differential scanning calorimeter is determined, and the temperature at the maximum peak position is defined as Tm. For measurement, pack the sample in an aluminum pan,
The temperature was raised to 200 ° C. at 100 ° C./min, held at 200 ° C. for 5 minutes, then decreased to −150 ° C. at 10 ° C./min, and then determined from an endothermic curve at 10 ° C./min.

[0110]

Example 1 Preparation of solid particles (1) 95.22 g of anhydrous magnesium chloride, 485 ml of decane
And 390.4 g of 2-ethylhexyl alcohol in 14
After heating at 0 ° C. for 4 hours to form a homogeneous solution, 22.2 g of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.
After cooling the homogeneous solution thus obtained to room temperature,
30 ml of this homogeneous solution was dropped into 80 ml of titanium tetrachloride kept at -20 ° C over 45 minutes. After dropping, the temperature of the solution was raised to 20 ° C. over 3 hours,
When it reached 20 ° C., it was filtered. After the solid portion was washed with decane, a part of the obtained solid particles (1) was dried, and the composition was examined. As a result, the titanium content was 9.0% by weight, the magnesium content was 10.0% by weight, The 2-ethylhexoxy group content was 22.4% by weight.

Preparation of Solid Particles (2) 7.3 g of the solid particles (1) obtained above were resuspended in 110 ml of toluene, and the resulting suspension was heated to 110 ° C. and heated to 110 ° C. Immediately before reaching, 2.8 ml of tetraethoxysilane was added and heated at 110 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

A part of the solid particles (2) prepared by the above operation was dried, and the composition was examined. As a result, the titanium content was 0.2% by weight, the magnesium content was 23.0% by weight, and the chlorine content was 2% by weight. Was 66.0% by weight, and the ethoxy group content was 0.4% by weight.

Preparation of Solid Titanium Catalyst Component After resuspending 3.2 g of the solid particles (2) obtained above in 110 ml of titanium tetrachloride, the obtained suspension was added to 11 parts.
Heat at 0 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

The solid titanium catalyst component prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component is such that the titanium content is 0.5% by weight, the magnesium content is 23.0% by weight, the diethyl phthalate content is 0.9% by weight, and the ethyl-2-ethylhexyl phthalate content is 2.7% by weight and bis (2-ethylhexyl) phthalate content of 0.2% by weight.

[0115] purified polymerization 1-liter autoclave heptane 40
0 ml was charged, and 0.4 mmol of triethylaluminum, 0.04 mmol of dicyclopentyldimethoxysilane prepared in advance, and the solid titanium catalyst component obtained as described above were added in an amount of 0.1 mmol in terms of titanium atoms.
5 ml of a decane slurry containing 008 mmol was charged in a propylene atmosphere at 40 ° C. After the temperature was raised to 60 ° C., 100 ml of hydrogen was introduced. After the temperature was further raised to 70 ° C., the temperature was maintained for 1 hour to carry out propylene polymerization. The pressure during the polymerization was kept at 5 kg / cm ² G. After completion of the polymerization, the slurry containing the produced solid was filtered to separate into a white powder and a liquid phase.

The polymer obtained in the form of a white powder after drying was
The yield was 228.9 g, and the boiling heptane extraction residual ratio was 9
The amount of the decane-soluble component was 9.4% by weight and 0.22% by weight. The melting point of the polymer measured by DSC is 16
4.6 ° C. By concentrating the liquid phase, 0.2 g of a solvent-soluble polymer was obtained. Therefore, the activity is 28600 g-PP / mmol-Ti, 3000 g-P
It was a P / g-catalyst. Table 1 shows the results.

[0117]

Example 2 A catalyst was prepared in the same manner as in Example 1 except that the reaction temperature of the solid particles (2) and titanium tetrachloride was changed to 90 ° C. in “Preparation of solid titanium catalyst component” in Example 1. Prepared and polymerized propylene. Table 1 shows the results.

[0118]

Example 3 In "Preparation of a solid titanium catalyst component" in Example 1, after the solid particles (2) were resuspended in titanium tetrachloride, the temperature was raised to 110 ° C., and diisobutyl phthalate was added to 0.1%. A catalyst was prepared in the same manner as in Example 1 except that 21 ml was added, and propylene was polymerized. Table 1 shows the results.

[0119]

Example 4 In Example 1, "Preparation of solid titanium catalyst component", 3.1 g of a complex of titanium tetrachloride and diisobutyl phthalate (1: 1) was used instead of titanium tetrachloride.
Solid particles using 110ml of toluene slurry containing (2)
A catalyst was prepared in the same manner as in Example 1 except that was resuspended, and propylene was polymerized. Table 1 shows the results.

[0120]

Example 5 In "Preparation of a solid titanium catalyst component" in Example 1, 110 ml of a toluene slurry containing 1.3 g of cyclopentadienyltitanium trichloride was used instead of titanium tetrachloride to obtain solid particles (2). A catalyst was prepared in the same manner as in Example 1 except for resuspension, and propylene was polymerized. Table 1 shows the results.

[0121]

Example 6 110 g of 3.2 g of solid particles (2) obtained in the same manner as in "Preparation of solid particles (2)" in Example 1
After resuspension in 1% titanium tetrachloride,
Heated at 10 ° C. for 2 hours. Next, solid particles were collected by hot filtration, and the obtained solid portion was resuspended in 110 ml of titanium tetrachloride and reacted again at 110 ° C. for 2 hours.

After completion of the reaction, a solid portion was collected by hot filtration.
The solid was washed with decane and hexane at 110 ° C. to obtain a solid titanium catalyst component. Propylene was polymerized in the same manner as in Example 1 using the obtained solid titanium catalyst component.
Table 1 shows the results.

[0123]

Example 7 3.2 g of solid particles (2) obtained in the same manner as in “Preparation of solid particles (2)” in Example 1 was mixed with a complex of titanium tetrachloride and diisobutyl phthalate (1: 1). After resuspension with 110 ml of a toluene slurry containing 3.1 g, the resulting suspension was heated at 110 ° C. for 2 hours. Next, solid particles were collected by hot filtration, and the obtained solid portion was resuspended in 110 ml of titanium tetrachloride and reacted again at 110 ° C. for 2 hours.

After completion of the reaction, a solid portion was collected by hot filtration.
The solid was washed with decane and hexane at 110 ° C. to obtain a solid titanium catalyst component. Propylene was polymerized in the same manner as in Example 1 using the obtained solid titanium catalyst component.
Table 1 shows the results.

[0125]

Example 8 3.2 g of solid particles (2) obtained in the same manner as in "Preparation of solid particles (2)" in Example 1 were resuspended in titanium tetrachloride and then heated to 110 ° C. At the time of warming, 0.21 ml of diisobutyl phthalate was added.
Heated for hours. Next, solid particles were collected by hot filtration, and the obtained solid portion was resuspended in 110 ml of titanium tetrachloride and reacted again at 110 ° C. for 2 hours.

After completion of the reaction, a solid portion was collected by hot filtration.
The solid was washed with decane and hexane at 110 ° C. to obtain a solid titanium catalyst component. Propylene was polymerized in the same manner as in Example 1 using the obtained solid titanium catalyst component.
Table 1 shows the results.

[0127]

Example 9 In Example 1, "Preparation of solid particles (2)", the amount of tetraethoxysilane added was 5.6 ml.
Propylene was polymerized in the same manner as in Example 1 except that Table 1 shows the results.

[0128]

Example 10 In "Preparation of solid particles (1)" in Example 1, a homogeneous solution of magnesium chloride was dropped into titanium tetrachloride, and then a solution of lithium acetylacetonate in 2-ethylhexyl alcohol (lithium acetylacetonate) was added. Concentration = 0.05005 mol / l)
A solid titanium catalyst component was prepared in the same manner as in Example 1 except that 1 was added dropwise, and propylene was polymerized. Table 1 shows the results.

[0129]

Example 11 Instead of lithium acetylacetonate,
A solid titanium catalyst component was prepared in the same manner as in Example 10 except that potassium acetylacetonate was used, and propylene polymerization was performed. Table 1 shows the results.

[0130]

Comparative Example 1 Preparation of solid titanium catalyst component 95.22 g of anhydrous magnesium chloride, 485 ml of decane
And 390.4 g of 2-ethylhexyl alcohol in 14
After heating at 0 ° C. for 4 hours to form a homogeneous solution, 22.2 g of phthalic anhydride was added to the solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.
After cooling the homogeneous solution thus obtained to room temperature,
30 ml of this homogeneous solution was added dropwise over 45 minutes to 80 ml of titanium tetrachloride kept at -20 ° C. The temperature of the liquid was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 2.0 ml of diisobutyl phthalate was added and heated at 110 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution. When a part of the solid prepared by the above operation was dried and the composition was examined, the titanium content was 5.1.
% By weight, magnesium content was 14.0% by weight, chlorine content was 56.0% by weight, and diisobutyl phthalate content was 17.5% by weight.

5.2 g of the solid thus obtained was added to 1
After resuspension in 10 ml of titanium tetrachloride, the resulting suspension was heated at 110 ° C. for 2 hours. After the completion of the reaction, a solid portion was collected by hot filtration, and sufficiently washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution.

The solid titanium catalyst component prepared by the above operation was stored as a decane slurry, and a part thereof was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component thus obtained has a titanium content of 2.3% by weight, a magnesium content of 19.0% by weight,
The diisobutyl phthalate content was 11.8% by weight.

Using the solid titanium catalyst component thus obtained, propylene was polymerized in the same manner as in Example 1. Table 1 shows the results.

[0134]

【table 1】

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J028 AA02A AB02A AC05A BA00A BA01B BB00A BB01B BC15B CA16C EB01 EB02 EB03 EB04 EC01 FA02 GA12 GA19 4J100 AA02P AA03P AA04P AA07P AA15P AA16A AAP AAP AAP AAP AAA A

Claims (4)

[Claims] 1. A method for preparing a solid titanium catalyst component for olefin polymerization, comprising the following steps (1) to (3): (1) a liquid magnesium compound (a) and a liquid titanium compound (b) (2) a step of removing 90% by weight or more of titanium atoms contained in the solid particles (1) obtained in the step (1). (3) In the step (2), A step of bringing the obtained solid particles (2) into contact with the titanium compound (c) and, if necessary, the electron donor (d). 2. The step (2) is a step of bringing the granular solid (1) obtained in the step (1) into contact with an organosilicon compound (e) represented by SiCl _n (OR) _4-n. Item 4. A method for preparing a solid titanium catalyst component for olefin polymerization according to Item 1. 3. The method for preparing a solid titanium catalyst component for olefin polymerization according to claim 1, wherein the step (3) is performed a plurality of times. 4. A solid titanium catalyst component obtained by the method for preparing a solid titanium catalyst component according to any one of claims 1 to 3, and (II) an organometallic compound, if necessary. (III) An olefin polymerization catalyst comprising an electron donor.