JPH06248019A - Catalyst for polymerizing olefin and polymerization of olefin - Google Patents

Abstract

PURPOSE:To (co)polymerize an olefin into a polymer high in stereo-regularity and bulk density and wide in mol. wt. distribution by using a polymerization catalyst comprising a solid titanium catalyst component, an organic aluminum compound catalyst component and a specific organic compound catalyst com pound, etc. CONSTITUTION:An olefin is preliminarily polymerized in the presence of an olefin-copolymerizing catalyst in an inert hydrocarbon medium and subsequently mainly (co)polymerized. The olefin-polymerizing catalyst is formed from (A) 0.01-0.5mmol of a solid titanium catalyst component (preferably titanium tetrachloride) consisting essentially of magnesium, titanium, a halogen and an electron donor, (B) 5-500mol/Al mol of an organic aluminum compound catalyst component (preferably triethyl aluminum), (C) an organic silicon compound catalyst component (preferably t-butylmethyldimethoxysilane), and (D) an organic silicon compound catalyst component, etc., different from the component C (preferably methyltrimethoxysilane, benzyldimethoxysilane) in a (C + D) amount of 0.05-5 moles/mole of B.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst capable of obtaining an olefin polymer having a wide molecular weight distribution in a high yield, and an olefin polymerization method using this catalyst.

[0002]

BACKGROUND OF THE INVENTION There have already been many proposals for a method for producing a solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components. It is also known that a polymer having high stereoregularity can be produced in high yield by using it in the polymerization of olefin.

Generally, an olefin polymer obtained by using a MgCl ₂ -supported high activity catalyst component has excellent mechanical properties, but its moldability is not always good.
This is because the molecular weight distribution of the polymer is not wide enough. Therefore, depending on the application, an olefin polymer that is easy to flow when melted, that is, has excellent moldability has been desired.

As a countermeasure, conventionally, a plurality of polymerization vessels are used, and a polymer having a wide molecular weight distribution is obtained by producing olefin polymers having different molecular weights in each of the polymerization vessels to improve the moldability. Had been taken. However, until now, it was not possible to sufficiently broaden the molecular weight distribution with a single polymerizer, and in order to produce an olefin polymer having a wide molecular weight distribution with multiple polymerizers, the operation management becomes complicated and plant construction costs are low. Therefore, it has been desired to develop a method for producing an olefin polymer capable of obtaining an olefin polymer having a wide molecular weight distribution by a single-stage polymerization operation.

Therefore, the inventors of the present invention have disclosed in Japanese Patent Laid-Open No. 3-770.
In Japanese Patent Publication No. 3, the following olefin polymerization method is disclosed. That is, the polymerization method of this olefin is
[A] A solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components,
[B] Organoaluminum compound catalyst component, and [C]
At least two or more electron donor catalyst components containing an electron donor (a) and an electron donor (b) (provided that the electron donor (a) is the solid titanium catalyst component [A] and the organoaluminum compound catalyst component [a]. And a homopolypropylene MFR (b) obtained by using the electron donor (b) and the electron donor (b) under the same polymerization conditions. log
[MFR (b) / MFR (a)] ≧ 1.5) is a method of polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst.

This olefin polymerization method can produce an olefin polymer having a particularly wide molecular weight distribution in a high yield, and not only widens the molecular weight distribution, but also obtains it by conventional single-stage polymerization. Since the unexpected result that a high molecular weight component that was not produced was also obtained,
This high molecular weight component had the possibility of improving the strength of the olefin polymer. The olefin polymer obtained by this polymerization method is characterized by high stereoregularity and high bulk density.

The inventors of the present invention conducted extensive studies to obtain an olefin polymer having a broader molecular weight distribution and excellent moldability than those of the olefin polymer obtained by the above-mentioned polymerization method. The present invention is completed by finding that an olefin (co) polymer having a wide molecular weight distribution can be obtained by using two or more specific organosilicon compound catalyst components in addition to the aluminum compound catalyst component. Came to.

[0008]

It is an object of the present invention to solve the problems associated with the prior art as described above, and to produce an olefin polymer having a wide molecular weight distribution by a single-stage polymerization operation. It is an object of the present invention to provide an olefin polymerization catalyst and an olefin polymerization method using this catalyst.

[0009]

SUMMARY OF THE INVENTION The catalyst for olefin polymerization according to the present invention is
[A] a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components;
[B] an organoaluminum compound catalyst component, [C] an organosilicon compound catalyst component represented by the following general formula [I], [D] an organosilicon compound catalyst component represented by the following general formula [II], and / or Alternatively, it is formed from an organosilicon compound catalyst component represented by [III].

R ¹ R ² Si (OR ³ ) ₂ ... [I] [In the formula, R ¹ is an alkyl group or an aralkyl group in which the carbon adjacent to Si is a secondary or tertiary carbon, It is a cycloalkyl group or a cycloalkenyl group, R ² is an alkyl group or an alkenyl group in which the carbon adjacent to Si is a primary carbon, and R ³ is a hydrocarbon group. ] R ⁴ Si (OR ³ ) ₃ ··· [II] [In the formula, R ⁴ is an alkyl group, an alkenyl group or an aralkyl group in which the carbon adjacent to Si is a primary carbon,
R ³ is a hydrocarbon group. ] R ⁵ R ⁶ Si (OR ³ ) ₂ ··· [III] [In the formula, R ⁵ is an alkyl group or an alkenyl group whose carbon adjacent to Si is a primary carbon, and R ⁶ is R is an aralkyl group in which the carbon adjacent to Si is a primary carbon;
³ is a hydrocarbon group. Further, the olefin polymerization method according to the present invention comprises: [A] a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, [B] an organoaluminum compound catalyst component, and [C]. The organosilicon compound catalyst component represented by the above general formula [I], and [D] the organosilicon compound catalyst component represented by the above general formula [II] and / or [II]
I] is characterized by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst formed from an organosilicon compound catalyst component.

In the polymerization method of the present invention, as described above, the solid titanium catalyst component [A], the organoaluminum compound catalyst component [B], and at least two or more specific organosilicon compound catalyst components [C] and [D] are used. ], The olefin polymer having a wide molecular weight distribution and excellent stereoregularity can be produced in a high yield. In addition, the above-mentioned catalyst is less likely to lower the polymerization activity, and the melt flow rate of the olefin polymer obtained by using this catalyst can be easily adjusted.

[0012]

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

In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" may refer to not only homopolymer but also copolymer. It may be used in a meaning including a polymer.

In the olefin polymerization method according to the present invention, in the presence of the following olefin polymerization catalyst,
Polymerize or copolymerize olefins. The olefin polymerization catalyst according to the present invention is a solid titanium catalyst component [A].
And an organoaluminum compound catalyst component [B] and at least two specific organosilicon compound catalyst components [C] and [D].

FIG. 1 shows an example of a flow chart of the method for preparing the catalyst used in the present invention. Solid Titanium Catalyst Component [A] The solid titanium catalyst component [A] used in the present invention is a highly active catalyst component containing magnesium, titanium, halogen and an electron donor as essential components.

Such solid titanium catalyst component [A] is
It is prepared by contacting the following magnesium compound, titanium compound and electron donor. In the present invention, examples of the titanium compound used for preparing the solid titanium catalyst component [A] include Ti (OR) _g X _4-g
(R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦ 4)
The tetravalent titanium compound represented by
More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ and Ti (OC
₂ H ₅ ) Cl ₃ , Ti (O-n-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H
_{5) Br 3, Ti (O} -iso-C 4 H 9) trihalide alkoxy titanium Br _{3 such; Ti (OCH 3) 2 Cl} 2, Ti (O
_{C 2 H 5) 2 Cl 2} , Ti (O-n-C 4 H 9) 2 Cl 2, Ti (O
A dihalogenated dialkoxy titanium such as C ₂ H ₅ ) ₂ Br ₂ ;
Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O-n-
_{C 4 H 9) 3 Cl,} Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium and _{Br; Ti (OCH 3) 4,} Ti (O
Examples thereof include tetraalkoxytitanium such as C ₂ H ₅ ) ₄ and Ti (O-n-C ₄ H ₉ ) ₄ .

Of these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferable, and titanium tetrachloride is more preferable. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component [A] include a reducing magnesium compound and a non-reducing magnesium compound.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a magnesium compound having a reducing property include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl. Magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium halide, etc. can be mentioned. These magnesium compounds may be used alone or may form a complex compound with an organic aluminum compound described later. Also,
These magnesium compounds may be liquid or solid, or may be derived by reacting metallic magnesium with a corresponding compound. Furthermore, it can also be derived from metallic magnesium during catalyst preparation using the methods described above.

Specific examples of the non-reducing magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride, magnesium ethoxy chloride, and magnesium isopropoxy chloride. ,
Alkoxy magnesium halides such as butoxy magnesium chloride and octoxy magnesium chloride; Alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium, etc. Alkoxy magnesium; phenoxy magnesium, dimethylphenoxy magnesium, and other allyloxy magnesium; magnesium laurate, magnesium stearate, and other carboxylates of magnesium.

The non-reducing magnesium compound may be the above-mentioned reducing magnesium compound or a compound derived from metallic magnesium, or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducible magnesium compound, for example, a reducible magnesium compound is prepared by using a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an alcohol, an ester or a ketone. It may be contacted with a compound having an active carbon-oxygen bond, such as aldehyde.

In the present invention, in addition to the above-mentioned reducing magnesium compound and non-reducing magnesium compound, the magnesium compound may be a complex compound of the above-mentioned magnesium compound and another metal, a complex compound or another metal. It may be a mixture with a compound. further,
You may use the said compound in combination of 2 or more type.

As the magnesium compound used for the preparation of the solid titanium catalyst component [A], many magnesium compounds other than those mentioned above can be used, but in the finally obtained solid titanium catalyst component [A]. , Preferably in the form of a halogen-containing magnesium compound,
Therefore, when a halogen-free magnesium compound is used, it is preferable to react it with a halogen-containing compound during the preparation.

In the present invention, among these, a magnesium compound having no reducing property is preferable, a halogen-containing magnesium compound is particularly preferable, and among these, magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are preferably used. To be

In the present invention, an electron donor can be used when preparing the solid titanium catalyst component [A]. Specific examples of such electron donors include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides and acid anhydrides; Examples thereof include nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates.

More specifically, carbon atoms of methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms; phenols having 6 to 25 carbon atoms which may have an alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol and naphthol; acetone, 3 to 15 carbon atoms such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone
Ketones; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, and other aldehydes having 2 to 15 carbon atoms; methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, propione Ethyl acetate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate,
Methyl methacrylate, ethyl crotonate, dibutyl maleate, diethyl butylmalonate, diethyl dibutylmalonate, ethyl cyclohexanecarboxylate, diethyl 1,2-cyclohexanedicarboxylate, di2-ethylhexyl 1,2-cyclohexanedicarboxylate, benzoic acid Methyl, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate,
The number of carbon atoms including the ester described below, which is preferably contained in the titanium catalyst component, such as methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate is 2 to 2 30 organic acid esters; inorganic acid esters such as ethyl silicate and butyl silicate; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride and phthalic acid dichloride Ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; anhydrous benzoic acid Acid, phthalic anhydride, etc. Acid anhydrides; amines such as methylamine, ethylamine, triethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine;
Examples thereof include nitriles such as acetonitrile, benzonitrile and trinitrile.

As the electron donor, an organosilicon compound represented by the following general formula [IV] can be used. R _n Si (OR ′) _4-n ... [IV] [wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Is. Specific examples of the organosilicon compound represented by the above general formula [IV] include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, and t-butylmethyldimethoxy. Silane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyl Dimethoxysilane, bis
p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,
Methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltoluethoxysilane,
Ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyl Triisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethyl Phenoxysilane, methyltriallyloxy
Silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, dicyclohexylmethyldimethoxysilane, cyclopentylmethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, di-n-propyldiethoxy Silane, di
-t-Butyldiethoxysilane, cyclopentyltriethoxysilane, etc. are used.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane and diphenyldiethoxysilane are preferred.

Two or more kinds of these electron donors can be used. The electron donor that is preferably contained in the titanium catalyst component is an ester of an organic acid, and more preferable examples of the electron donor include an ester having a skeleton represented by the following general formula.

[0030]

[Chemical 1]

Here, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ , and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are , Hydrogen or a substituted or unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other. Examples of the substituted hydrocarbon group represented by R ^{1 to} R ⁵ include N,
Groups containing heteroatoms such as O and S, for example, C—O—C, C
_{OOR, COOH, OH, SO 3} H, -C-N-C-,
Hydrocarbon groups having groups such as NH ₂ are mentioned.

Of these, a particularly preferred electron donor is R
^At least one of ¹ and R ² is a diester of a dicarboxylic acid having an alkyl group having 2 or more carbon atoms. Specific examples of the polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, α
-Diisobutyl methyl glutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, diethyl isopropylmalonate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate diethyl dibusobutylmalonate diethyl, diethyl N-butylmalonate Diethyl maleate Dimethyl maleate Monooctyl maleate, Dioctyl maleate, Dibutyl maleate, Dibutyl butyl maleate, Diethyl butyl maleate, Diisopropyl β-methyl glutarate, Diallyl ethyl succinate, Di fumarate
-2-Ethylhexyl, diethyl itaconic acid, dibutyl itaconic acid, dioctyl citraconic acid, dimethyl citraconic acid and other aliphatic polycarboxylic acid esters; diethyl 1,2-cyclohexanecarboxylic acid, diisobutyl 1,2-cyclohexanecarboxylic acid, tetrahydrophthalic acid Alicyclic polycarboxylic acid esters such as diethyl and diethyl nadic acid;
Monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, mononormal butyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, ethyl normal butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, Di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate,
Dyneopentyl phthalate, Didecyl phthalate, Benzyl butyl phthalate, Diphenyl phthalate, Diethyl naphthalene dicarboxylate, Dibutyl naphthalene dicarboxylate,
Examples thereof include aromatic polycarboxylic acid esters such as triethyl trimellitate and dibutyl trimellitate; heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

Specific examples of the polyhydric hydroxy compound ester include 1,2-diacetoxybenzene and 1-methyl.
Examples thereof include -2,3-diacetoxybenzene, 2,3-diacetoxynaphthalene, ethylene glycol dipivalate and butanediol pivalate.

Specific examples of the hydroxy-substituted carboxylic acid include benzoylethyl salicylate, acetylisobutyl salicylate and acetylmethyl salicylate.

Examples of the polyvalent carboxylic acid ester that can be supported in the titanium catalyst component include, in addition to the above compounds, specifically, diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di n-sebacate. Butyl, di-n-octyl sebacate, di-2 sebacate
-Esters of long-chain dicarboxylic acids such as ethylhexyl can be used.

Among these polyfunctional esters, compounds having a skeleton of the above-mentioned general formula are preferable, and more preferable are esters of phthalic acid, maleic acid, substituted malonic acid and the like with alcohols having 2 or more carbon atoms. Preferably
Particularly, a diester of phthalic acid and an alcohol having 2 or more carbon atoms is preferable.

Another electron donor component which can be supported on the titanium catalyst component is RCOOR '(R and R'are hydrocarbyl groups which may have a substituent, at least one of which is a branched chain. (Including an alicyclic group) or a ring-containing chain group). As R and R ′, specifically,
_{(CH 3) 2 CH-, C} 2 H 5 CH (CH 3) -, (CH 3)
_{2 CHCH 2 -, (CH 3} ) 3 C-, C 2 H 5 CH, (C
H ₃₎ CH ₂ -,

[0038]

[Chemical 2]

Groups such as If either R or R ′ is a group as described above, the other may be a group as described above, or another group such as a linear group,
It may be a cyclic group.

Specifically, dimethylacetic acid, trimethylacetic acid, α-methylbutyric acid, β-methylbutyric acid, methacrylic acid,
Examples include various monoesters such as benzoyl acetic acid; various monocarboxylic acid esters of alcohols such as isopropanol, isobutyl alcohol, and tert-butyl alcohol.

Carbonates can also be selected as electron donors. Specific examples thereof include diethyl carbonate, ethylene carbonate, diisopropyl carbonate, phenylethyl carbonate, diphenyl carbonate and the like.

When supporting these electron donors in the solid titanium catalyst component, it is not always necessary to use them as starting materials, and it is also possible to use compounds which can be changed to these during the process of preparing the solid titanium catalyst component. it can.

Other electron donors may coexist in the solid titanium catalyst component as long as the object of the present invention is not impaired. In the present invention, the solid titanium catalyst component [A] can be produced by bringing the above-mentioned magnesium compound (or magnesium metal), electron donor and titanium compound into contact with each other. In order to produce the solid titanium catalyst component [A], a known method of preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound and an electron donor can be adopted. The above components may be contacted in the presence of other reaction reagents such as silicon, phosphorus and aluminum.

The production method of these solid titanium catalyst components [A] will be briefly described below with some examples. (1) A method in which a solution containing a magnesium compound, an electron donor and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or while being precipitated, a solution is contacted with a titanium compound. (2) A method in which a complex consisting of a magnesium compound and an electron donor is reacted with an organometallic compound and then a titanium compound is reacted. (3) For the contact product between the inorganic carrier and the organic magnesium compound,
A method of catalytically reacting a titanium compound and preferably an electron donor. At this time, the contact product may be previously contact-reacted with a halogen-containing compound and / or an organometallic compound. (4) A method of obtaining a magnesium compound-supported inorganic or organic carrier from a mixture of a solution containing a magnesium compound, an electron donor, and optionally a hydrocarbon solvent, and an inorganic or organic carrier, and then contacting with a titanium compound . (5) magnesium compound, titanium compound, electron donor,
A method for obtaining a solid titanium catalyst component carrying magnesium and titanium by contacting a solution containing a hydrocarbon solvent with an inorganic or organic carrier, as the case may be. (6) A method of reacting an organomagnesium compound in a liquid state with a halogen-containing titanium compound by catalytic reaction. (7) A method of contacting a titanium compound after a liquid reaction of an organomagnesium compound with a halogen-containing compound. (8) A method in which an alkoxy group-containing magnesium compound is catalytically reacted with a halogen-containing titanium compound. (9) A method in which a complex composed of an alkoxy group-containing magnesium compound and an electron donor is catalytically reacted with a titanium compound. (10) A method in which a complex composed of a magnesium compound containing an alkoxy group and an electron donor is contacted with an organometallic compound and then reacted with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor, and a titanium compound in any order. In this reaction, each component may be pretreated with an electron donor and / or a reaction aid such as an organometallic compound or a halogen-containing silicon compound. In this method, it is preferable to use the electron donor at least once. (12) A method of precipitating a solid magnesium-titanium complex by reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor. (13) A method of further reacting a titanium compound with the reaction product obtained in (12). (14) A method of further reacting the reaction product obtained in (11) or (12) with an electron donor and a titanium compound. (15) A method of treating a solid substance obtained by pulverizing a magnesium compound, preferably an electron donor, and a titanium compound with any of halogen, a halogen compound and an aromatic hydrocarbon. In addition, this method may include a step of pulverizing only the magnesium compound, the complex compound composed of the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after pulverization, pretreatment with a reaction auxiliary agent and then treatment with halogen or the like may be performed. Examples of the reaction aid include organic metal compounds and halogen-containing silicon compounds. (16) A method of pulverizing a magnesium compound and then contacting and reacting with the titanium compound.

At this time, it is preferable to use an electron donor or a reaction aid during pulverization and / or contact / reaction. (17) A method of treating the compound obtained in (11) to (16) above with halogen or a halogen compound or an aromatic hydrocarbon. (18) A method of bringing a contact reaction product of a metal oxide, an organomagnesium and a halogen-containing compound into contact with an electron donor and a titanium compound. (19) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium or aryloxy magnesium with a titanium compound and / or a halogen-containing hydrocarbon and preferably an electron donor. (20) A method of bringing a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium into contact with a titanium compound and / or an electron donor. At this time, it is preferable to coexist with a halogen-containing compound such as a halogen-containing silicon compound. (21) Solid magnesium obtained by reacting a liquid magnesium compound having no reducing ability with an organometallic compound.
A method of depositing a metal (aluminum) complex and then reacting an electron donor and a titanium compound.

Among the methods for preparing the solid titanium catalyst component [A] mentioned in (1) to (21) above, a liquid titanium halide is used at the time of catalyst preparation, or after using a titanium compound, or When using the titanium compound, a method using a halogenated hydrocarbon is preferable.

The amount of each of the above-mentioned components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of the electron donor is about 1 mol of the magnesium compound. 0.01-5
The titanium compound is present in an amount of about 0.01-500 moles, preferably 0.05-3, in an amount of about 0.05-2 moles.
Used in an amount of 00 mol.

The solid titanium catalyst component [A] thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component [A], the halogen / titanium (atomic ratio) is about 4-200, preferably about 5-100,
The electron donor / titanium (molar ratio) is about 0.1-10,
Desirably, it is about 0.2 to about 6, and the magnesium / titanium (atomic ratio) is about 1 to 100, preferably about 2 to 50.

The solid titanium catalyst component [A] contains magnesium halide having a smaller crystal size than that of commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60 to 1000 m.
² / g, more preferably about 100 to 800 m ² / g. Since the solid titanium catalyst component [A] forms the catalyst component integrally with the above components, the composition thereof is not substantially changed by washing with hexane.

Such solid titanium catalyst component [A] is
Although it can be used alone, it can also be used by diluting it with an inorganic compound or an organic compound such as a silicon compound, an aluminum compound or a polyolefin. When a diluent is used, the solid titanium catalyst component [A] shows high catalytic activity even if its specific surface area is smaller than the above-mentioned specific surface area. A method for preparing such a highly active titanium catalyst component is described, for example, in JP-A-50.
-108385, 50-126590, 51-20297, 51-28189, 51-64586, 51-92885
No. 51, No. 51-136625, No. 52-87489, No. 5
2-100596, 52-147688, 52-104593, 53-2580, 53-40093, 53-400
94 publication, 53-43094 publication, 55-135102 publication,
55-135103, 55-152710, 56-811, 56-11908, 56-18606, 58-83006
No. 58, No. 58-138705, No. 58-138706, No. 58-138706
58-138707, 58-138708, 58-138709
No. 58, No. 58-138710, No. 58-138715, No. 58-138715
No. 60-23404, No. 61-21109, No. 61-37802, No. 61-37803.

Organoaluminum Compound Catalyst Component [B] As the organoaluminum compound catalyst component [B] used in the present invention, a compound having at least one aluminum-carbon bond in the molecule can be used. Examples of such compounds include (i) the general formula R ¹ _m Al (OR ² ) _n H _p X _q (wherein R ¹ and R ² are usually 1 to 15 carbon atoms,
It is preferably a hydrocarbon group containing 1 to 4 groups, which may be the same or different from each other. X represents a halogen atom, 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q
Is a number 0 ≦ q <3, and m + n + p + q =
An organic aluminum compound represented by the formula (3), (ii) a Group 1 metal represented by the general formula M ¹ AlR ¹ ₄ (wherein M ¹ is Li, Na and K, and R ¹ is the same as the above). And a complex alkylated product of aluminum with aluminum.

Examples of the organoaluminum compound represented by the above formula (i) include the following compounds. General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably a number of 1.5 ≦ m ≦ 3), general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as described above, X is a halogen atom, m is preferably 0 <m <3), and the general formula R ¹ _m AlH _3-m (wherein R ¹ is the same as the above). The same, m is preferably 2 ≦ m <3
R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as above. X is a halogen atom, 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, m + n +
and a compound represented by q = 3).

Specific examples of the aluminum compound represented by (i) include trialkyl aluminum such as triethyl aluminum and tributyl aluminum; trialkenyl aluminum such as triisoprenyl aluminum; diethyl aluminum ethoxide and dibutyl aluminum butoxide. Aluminium sesquiethoxide, butylaluminum sesquibutoxide, and other alkylaluminum sesquialkoxides; partially alkylated alkylaluminum having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 ; Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; ethyl aluminum Alkyl aluminum sesquihalides such as musesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyls such as ethyl aluminum dichloride, propyl aluminum dichloride, alkyl aluminum dihalides such as butyl aluminum dibromide Aluminum; Dialkyl aluminum hydrides such as diethyl aluminum hydride and dibutyl aluminum hydride; Partially hydrogenated alkyl aluminums such as alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride; Ethyl aluminum ethoxy chloride;
Mention may be made of partially alkoxylated and halogenated alkylaluminium, such as butylaluminum butoxycyclolide, ethylaluminum ethoxy bromide.

Examples of the compound similar to (i) include an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Examples of such a compound include (C ₂ H ₅ ) ₂ AlO
_{Al (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 methylaluminoxane.

Examples of the compound represented by the above formula (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum to which two or more kinds of aluminum compounds described above are bound.

Organosilicon Compound Catalyst Component [C] The organosilicon compound used as the organosilicon compound catalyst component [C] in the present invention is an electron donor and is represented by the following general formula [I].

R ¹ R ² Si (OR ³ ) ₂ ... [I] R ¹ in the above formula [I] is an alkyl group in which the carbon adjacent to Si is a secondary or tertiary carbon, aralkyl Base,
A cycloalkyl group or a cycloalkenyl group, specifically, alkyl groups such as isopropyl group, sec-butyl group, t-butyl group, t-amyl group; aralkyl groups such as cumyl group; cyclopentyl group, cyclohexyl group, etc. And a cycloalkenyl group such as a cyclopentenyl group and a cyclopentadienyl group. These substituents may contain halogen, silicon, oxygen, nitrogen, sulfur, phosphorus and boron. Among these, an alkyl group and a cycloalkyl group are preferable.

R ² in the above formula [I] is Si
Is an alkyl group or an alkenyl group whose carbon adjacent to is a primary carbon, specifically, a methyl group, an ethyl group, n-
Examples thereof include alkyl groups such as propyl group and n-butyl group; alkenyl groups such as vinyl group. These substituents may contain halogen, silicon, oxygen, nitrogen, sulfur, phosphorus and boron.

R ³ in the above formula [I] represents a hydrocarbon group, preferably a hydrocarbon group having 1 to 5 carbon atoms, particularly preferably 1 to 2 carbon atoms. Specific examples of such an organosilicon compound include t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butylethyldiethoxysilane, t-butylvinyldimethoxysilane, and t-butyln-propyldimethoxysilane. Silane, t-butyl n-butyldimethoxysilane, t-butyl n-butyldiethoxysilane, t-butylisobutyldimethoxysilane, t-butyldecyldimethoxysilane, t-amylmethyldimethoxysilane, t-amylmethyldiethoxysilane, t-amylethyldimethoxysilane, t-amylvinyldimethoxysilane, t-amyl n-propyldimethoxysilane, t-amyl n-propyldiethoxysilane, t-amyl n-
Butyldimethoxysilane, t-amylisobutyldimethoxysilane, t-amyldecyldimethoxysilane, cumylmethyldimethoxysilane, cumylethyldimethoxysilane, cumylethyldiethoxysilane, cumylvinyldimethoxysilane, cumyln-propyldimethoxysilane, Cumyl n-butyldimethoxysilane, cumyl n-butyldiethoxysilane, cumylisobutyldimethoxysilane, cumyldecyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylvinyldimethoxysilane, cyclopentyln -Propyldimethoxysilane, cyclopentyl n-butyldimethoxysilane, cyclopentyl n-butyldiethoxysilane, cyclopentylisobutyl Dimethoxysilane, cyclopentyldecyldimethoxysilane, cyclopentenylmethyldimethoxysilane, cyclopentenylethyldimethoxysilane, cyclopentenylethyldiethoxysilane, cyclopentenylvinyldimethoxysilane, cyclopentenyl n-propyldimethoxysilane, cyclopentenyl n-butyldimethoxysilane, cyclo Pentenyl n-butyldiethoxysilane, cyclopentenylisobutyldimethoxysilane, cyclopentenyldecyldimethoxysilane, thexylmethyldimethoxysilane, thexylethyldimethoxysilane, thexylethyldiethoxysilane, thexylvinyldimethoxysilane, thexyl n-propyldimethoxysilane Silane, Thexyl n-butyldimethoxysilane, Thexyl n-butyldiethoxysilane, Thexylyl Butyl dimethoxysilane, etc. thexyldimethylsilyl decyl dimethoxysilane is preferred.

As the above-mentioned organosilicon compound,
Compounds capable of inducing these organosilicon compounds under olefin polymerization conditions or prepolymerization conditions may be added during olefin polymerization or prepolymerization, and may be used so as to produce an organosilicon compound simultaneously with olefin polymerization or prepolymerization. .

Organosilicon Compound Catalyst Component [D] The organosilicon compound used as the organosilicon compound catalyst component [D] in the present invention is an electron donor and is represented by the following general formula [II] or [III]. .

These organosilicon compounds may be used alone or in combination. R ⁴ Si (OR ³ ) ₃ ... [II] R ⁴ in the above formula [II] is an alkyl group, an alkenyl group or an aralkyl group in which the carbon adjacent to Si is a primary carbon. Include an ethyl group, n-propyl group,
Examples thereof include alkyl groups such as n-butyl group; alkenyl groups such as vinyl group; and aralkyl groups such as cumyl group, benzyl group and phenethyl group.

R ³ in the above formula [II] represents a hydrocarbon group, preferably a hydrocarbon group having 1 to 5 carbon atoms, particularly preferably 1 to 2 carbon atoms. Specific examples of such an organosilicon compound include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, and propyl. Trimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, β
-Phenethyltrimethoxysilane, β-phenethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, γ-chloropropyltriethoxysilane, γ-aminopropyltriethoxysilane, ethyltriisopropoxysilane and the like are preferably used.

R ⁵ R ⁶ Si (OR ³ ) ₂ ... [III] R ⁵ in the above formula [III] is an alkyl group or an alkenyl group in which the carbon adjacent to Si is a primary carbon, Specifically, a methyl group, an ethyl group, an n-propyl group,
Examples thereof include alkyl groups such as n-butyl group; alkenyl groups such as vinyl group.

R ⁶ in the above formula [III] is
An aralkyl group in which the carbon adjacent to Si is a primary carbon, and specific examples thereof include an aralkyl group such as a benzyl group and a phenethyl group.

R ³ in the above formula [III] represents a hydrocarbon group, preferably a hydrocarbon group having 1 to 5 carbon atoms, particularly preferably 1 to 2 carbon atoms. As such an organosilicon compound, specifically, benzylmethyldimethoxysilane, benzylmethyldiethoxysilane, benzylethyldimethoxysilane, benzylethyldiethoxysilane, benzylvinyldimethoxysilane, benzyl n-butyldimethoxysilane, β- Phenethylmethyldimethoxysilane, β-phenethylmethyldiethoxysilane, β-phenethylethyldimethoxysilane, β-phenethylethyldiethoxysilane, β-phenethylvinyldimethoxysilane, β-phenethyln-butyldimethoxysilane, δ-phenylbutylmethyldimethoxysilane Silane, δ-phenylbutylmethyldiethoxysilane, δ-phenylbutylethyldimethoxysilane, δ-
Phenylbutylethyldiethoxysilane, δ-phenylbutylvinyldimethoxysilane, δ-phenylbutyl n-
Butyldimethoxysilane, β-methyl-γ-phenylpropylmethyldimethoxysilane, β-methyl-γ-phenylpropylmethyldiethoxysilane, β-methyl-γ-phenylpropylethyldimethoxysilane, β-methyl-γ-
Phenylpropylethyldiethoxysilane, β-methyl
-γ-Phenylpropylvinyldimethoxysilane, β-methyl-γ-phenylpropyl n-butyldimethoxysilane and the like are preferably used.

The above-mentioned general formula [II] or [II]
As the organosilicon compound represented by the formula [I], as in the case of the above-mentioned organosilicon compound catalyst component [C], a compound capable of derivatizing the organosilicon compound under olefin polymerization conditions or prepolymerization conditions is used. In addition to the pre-polymerization, the organosilicon compound may be produced simultaneously with the olefin polymerization or the pre-polymerization.

Olefin Polymerization Method In the polymerization method of the present invention, the olefin is polymerized in the presence of the catalyst as described above. It is preferable to carry out polymerization.

By carrying out such preliminary polymerization,
A powder polymer having a large bulk density can be obtained, and the stereoregularity of the obtained olefin polymer tends to be improved.
Further, if the preliminary polymerization is carried out, the properties of the slurry become excellent in the case of the slurry polymerization. Therefore, according to the polymerization method of the present invention, the obtained polymer powder or polymer slurry can be easily handled.

In the prepolymerization, the solid titanium catalyst component [A] is usually used in combination with at least a part of the organoaluminum compound catalyst component [B]. At this time, part or all of the organosilicon compound catalyst component [C] and the organosilicon compound catalyst component [D] can be allowed to coexist.

In the prepolymerization, a catalyst having a much higher concentration than the catalyst concentration in the system in the main polymerization can be used.
The concentration of the solid titanium catalyst component [A] in the prepolymerization is
It is desirable that the amount is usually about 0.01 to 200 mmol, preferably about 0.05 to 100 mmol, in terms of titanium atom, per liter of an inert hydrocarbon medium described later.

The amount of the organoaluminum compound catalyst component [B] is 0.1 to 10 per 1 g of the solid titanium catalyst component [A].
The amount may be such that 00 g, preferably 0.3 to 500 g of a polymer is produced, and is usually about 0.1 to 100 mol per 1 mol of titanium atom in the solid titanium catalyst component [A],
It is desirable that the amount is preferably about 0.5 to 50 mol. If the prepolymerization amount is too large, the production efficiency of the olefin polymer in the main polymerization may decrease.

The prepolymerization is preferably carried out under mild conditions by adding the olefin and the above-mentioned catalyst component to an inert hydrocarbon medium. Specific examples of such an inert hydrocarbon medium include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane,
Alicyclic hydrocarbons such as methylcyclopentane; benzene,
Examples thereof include aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons.

The olefin used in the prepolymerization may be the same as the olefin used in the main polymerization described below,
May be different. In the present invention, liquid α-olefin can be used in place of part or all of the inert hydrocarbon medium used in the prepolymerization.

The reaction temperature of the prepolymerization may be a temperature at which the produced prepolymer is not substantially dissolved in the inert hydrocarbon medium, and is usually about -20 to + 100 ° C, preferably about -20 to 20 ° C. + 80 ° C, more preferably 0 to +40
It is preferably in the range of ° C.

In the prepolymerization, a molecular weight modifier such as hydrogen can be used. Such a molecular weight modifier has an intrinsic viscosity [η] of a polymer obtained by prepolymerization measured in decalin at 135 ° C. of about 0.2 dl /
It is desirable to use it in an amount of g or more, preferably about 0.5 to 10 dl / g.

The prepolymerization can be carried out batchwise or continuously. In the method for polymerizing an olefin according to the present invention, as described above, the solid titanium catalyst component [A] and the organoaluminum compound are first prepared after the preliminary polymerization as described above or without the preliminary polymerization. Catalyst component [B], organosilicon compound catalyst component [C]
The main polymerization of olefin is carried out in the presence of an olefin polymerization catalyst formed from the organosilicon compound catalyst component [D].

Specific examples of the olefin used in the main polymerization of the above olefins include ethylene, propylene,
Examples thereof include 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene and 1-decene. In the present invention, these olefins may be used alone or in combination.

In the polymerization method of the present invention, particularly 3 carbon atoms are used.
By polymerizing the above α-olefin, a polymer having a high stereoregularity index can be produced with high catalyst efficiency.

When homopolymerizing or copolymerizing these olefins, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene may be used as a polymerization raw material.

In the polymerization method of the present invention, the main polymerization of olefin is usually carried out in the gas phase or the liquid phase. When the main polymerization takes the reaction form of slurry polymerization, the above-mentioned inert hydrocarbon may be used as the reaction solvent, or a liquid olefin at the reaction temperature may be used.

In the polymerization method of the present invention, the titanium catalyst component [A] is usually about 0.005-0.5 mmol, preferably about 0.01, in terms of Ti atoms per liter of polymerization volume. Used in an amount of ~ 0.5 mmol.
In addition, the organoaluminum compound catalyst component [B] generally contains about 1 to 2 metal atoms in the organoaluminum compound catalyst component [B] per 1 mol of titanium atom in the titanium catalyst component [A] in the polymerization system. 1,000 mol, preferably about 5-5
It is used in an amount such that it is 00 mol. Further, the organosilicon compound catalyst component is a total of the organosilicon compound catalyst component [C] and the organosilicon compound catalyst component [D], and the organosilicon compound catalyst component per mole of metal atom in the organoaluminum compound catalyst component [B]. In terms of Si atoms in [C] and [D], it is usually about 0.001 to 20 mol, preferably about 0.01 to 10 mol, particularly preferably about 0.
It is used in an amount such that it is from 05 to 5 mol.

In the polymerization method of the present invention, the titanium catalyst component [A], the organoaluminum compound catalyst component [B],
The contact method and order of the organosilicon compound catalyst component [C] and the organosilicon compound catalyst component [D] are not particularly limited.
Specifically, these catalyst components may be contacted during the main polymerization, or may be contacted before the main polymerization, for example, during the preliminary polymerization. In this contact before the main polymerization, only two arbitrary members may be freely selected and contacted, or a part of each component may be contacted with two or more members.

As the organosilicon compound catalyst components [C] and [D] which are electron donors, both components may be used during the prepolymerization, or one component may be used during the prepolymerization and the other component may be used during the main polymerization. The components may be used, or both components may be used for the first time during the main polymerization.

In the present invention, each catalyst component may be contacted under an inert gas atmosphere or each catalyst component may be contacted under an olefin atmosphere before polymerizing an olefin.

When a part of the organoaluminum compound catalyst component [B], the organosilicon compound catalyst component [C] and the organosilicon compound catalyst component [D] is used in the prepolymerization, the catalyst used in the prepolymerization is used. Is used with the rest of the catalyst. In this case, the catalyst used in the prepolymerization may contain a prepolymerized product.

When hydrogen is used during the main polymerization of olefin, a polymer having a high melt flow rate can be obtained, and the molecular weight of the obtained polymer can be adjusted by adjusting the hydrogenation amount. Even in this case, the polymerization method of the present invention does not reduce the stereoregularity index of the produced polymer or the catalytic activity.

In the present invention, the olefin polymerization temperature is usually about 20 to 200 ° C., preferably about 50 to 18 ° C.
At 0 ° C., the pressure is usually set to atmospheric pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² . The polymerization reaction time is usually 5 minutes to 10 hours, preferably 10 minutes.
Minutes to 7 hours, more preferably 15 minutes to 5 hours.

In the polymerization method of the present invention, the olefin polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The olefin polymer thus obtained may be any of a homopolymer, a random copolymer and a block copolymer. In the present invention, the yield of the polymer having stereoregularity per unit amount of the solid catalyst component is high, so that the catalyst residue, particularly the halogen content in the polymer can be relatively reduced. Therefore, the operation of removing the catalyst in the polymer can be omitted, and rusting of the mold can be effectively prevented when the molded product is molded using the produced olefin polymer.

The olefin polymer obtained by using the catalyst according to the present invention has a wide molecular weight distribution and is excellent in processability (moldability) during melt molding.

[0092]

The olefin polymerization catalyst according to the present invention is
Solid titanium catalyst component [A], organoaluminum compound catalyst component [B], specific organosilicon compound catalyst component [C]
And a specific organosilicon compound catalyst component [D] different from the organosilicon compound catalyst component [C], polymerizing an olefin in the presence of this catalyst results in high stereoregularity and bulk density. In particular, an olefin polymer having a wide molecular weight distribution can be produced in high yield.

Further, the olefin polymerization catalyst according to the present invention can efficiently produce an olefin polymer having the above-mentioned excellent properties, and the catalytic activity is less likely to decrease with the passage of polymerization time.

In the olefin polymerization method according to the present invention,
Since the olefin is polymerized using the above catalyst, the olefin polymer having the above-mentioned excellent properties can be efficiently produced, and moreover, not only the molecular weight distribution is broadened, but also the high molecular weight component is produced. Therefore, it is expected that the strength of the olefin polymer will be improved by the high molecular weight component.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0096]

[Example 1] [Preparation of solid titanium catalyst component [A]] 7.14 g (75 mmol) of anhydrous magnesium chloride, 37.5 ml of decane and 35.1 ml (225 mmol) of 2-ethylhexyl alcohol were heated at 130 ° C for 2 hours. Was performed to obtain a uniform solution. Then, 1.67 g of phthalic anhydride was added to this solution.
(11.3 mmol) and added at 130 ° C.
Stirring and mixing were carried out for a period of time to dissolve phthalic anhydride in the above homogeneous solution.

After cooling the homogeneous solution thus obtained to room temperature, titanium tetrachloride 20 kept at -20 ° C was used.
The total amount was added dropwise to 0 ml (1.8 mol) over 1 hour. After the dropping, the temperature of the obtained solution is 110 for 4 hours.
The temperature was raised to 110 ° C, and when the temperature reached 110 ° C, 5.03 ml (18.8 mmol) of diisobutyl phthalate was added.

The solution was stirred at the above temperature for a further 2 hours. After the completion of the reaction for 2 hours, the solid portion was collected by filtration under heating, the solid portion was resuspended in 275 ml of TiCl ₄ , and then the reaction was again carried out at 110 ° C. for 2 hours by heating.

After completion of the reaction, the solid portion was collected again by hot filtration and washed with decane and hexane at 110 ° C.
This washing was performed until no titanium compound was detected in the washing liquid.

The solid titanium catalyst component [A] synthesized as described above was obtained as a hexane slurry. A part of this catalyst was taken and dried. Analysis of this dried product revealed that the composition of the solid titanium catalyst component [A] obtained as described above was 2.5% by weight of titanium, 58% by weight of chlorine, 18% by weight of magnesium and 13.8% by weight of diisobutyl phthalate. %Met. [Preliminary Polymerization] 200 ml of purified hexane was placed in a glass reactor having a capacity of 400 ml and purged with nitrogen, and 6 mmol of triethylaluminum and the above solid titanium catalyst component [A]
After adding 2 mmol of titanium atom in terms of titanium atom, propylene was fed at a rate of 5.9 Nl / hr for 1 hour to obtain Ti
2.8 g of propylene was polymerized per 1 g of the catalyst component [A] to prepare a prepolymerized catalyst.

After the completion of this preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was dispersed again in decane. [Main polymerization] Purified in an autoclave with an internal volume of 2 liters n-
Charge 750 ml of hexane, and in a propylene atmosphere at 60 ° C., 0.75 mmol of triethylaluminum, 0.038 mmol of t-butylmethyldimethoxysilane, 0.038 mmol of n-propyltriethoxysilane and the above-mentioned prepolymerization catalyst were titanium. 0.015 mmol Ti in terms of atom was charged.

Next, 150 ml of hydrogen was placed in the autoclave.
Was introduced, the temperature was raised to 70 ° C., and this was held for 2 hours to carry out propylene polymerization. Pressure during polymerization is 7 kg / cm ² G
Kept at. After completion of the polymerization, the slurry containing the produced solid was filtered to separate a white powder and a liquid phase part.

The yield of the white powdery polymer after drying was 35.
9.5 g, extraction residual rate with boiling heptane is 99.1%,
MFR is 1.8 dg / min, apparent bulk specific gravity is 0.45
The g / ml and Mw / Mn were 7.63. On the other hand, 0.8 g of a solvent-soluble polymer was obtained by concentrating the liquid phase part.
Therefore, the activity was 24,000 g-PP / mM-Ti, and the total II (t-I.I.) Was 98.9%.

[0104]

Example 2 Polymerization was carried out in the same manner as in Example 1 except that vinyltriethoxysilane was used instead of n-propyltriethoxysilane.

The results are shown in Table 1.

[0106]

Example 3 Polymerization was carried out in the same manner as in Example 1 except that β-phenethyltriethoxysilane was used instead of n-propyltriethoxysilane.

The results are shown in Table 1.

[0108]

Example 4 Polymerization was carried out in the same manner as in Example 1 except that n-pentyltriethoxysilane was used instead of n-propyltriethoxysilane.

The results are shown in Table 1.

[0110]

Example 5 In Example 1, cyclopentylethyldimethoxysilane was used instead of t-butylmethyldimethoxysilane, and β- was used instead of n-propyltriethoxysilane.
Polymerization was performed in the same manner as in Example 1 except that phenethylmethyldimethoxysilane was used.

The results are shown in Table 1.

[0112]

Comparative Example 1 In Example 1, as the silane compound,
Polymerization was carried out in the same manner as in Example 1 except that t-butylmethyldimethoxysilane and n-propyltriethoxysilane were not used and only 0.075 mmol of cyclohexylmethyldimethoxysilane was used.

The results are shown in Table 1.

[0114]

Comparative Example 2 Polymerization was performed in the same manner as in Example 1 except that vinyltriethoxysilane was used instead of cyclohexylmethyldimethoxysilane in Comparative Example 1.

The results are shown in Table 1.

[0116]

[Table 1]

[Brief description of drawings]

FIG. 1 is a flowchart showing an example of a method for preparing a catalyst used in the olefin polymerization method according to the present invention.

Claims (2)

[Claims] 1. A solid titanium catalyst component containing [A] magnesium, titanium, halogen and an electron donor as essential components, and [B] an organoaluminum compound catalyst component.
[C] An organosilicon compound catalyst component represented by the following general formula [I], and [D] An organosilicon compound catalyst component represented by the following general formula [II] and / or [III]
And an organosilicon compound catalyst component represented by: R ¹ R ² Si (OR ³ ) ₂ ··· [I] [wherein R ¹ is Si is an alkyl group, an aralkyl group, a cycloalkyl group or a cycloalkenyl group whose carbon adjacent to Si is a secondary or tertiary carbon, and R ² is an alkyl group or an alkenyl group whose carbon adjacent to Si is a primary carbon. , R ³ is a hydrocarbon group], R ⁴ Si (OR ³ ) ₃ ... [II] [In the formula, R ⁴ is an alkyl group in which the carbon adjacent to Si is a primary carbon, An alkenyl group or an aralkyl group, R ³ is a hydrocarbon group], R ⁵ R ⁶ Si (OR ³ ) ₂ ··· [III] [wherein R ⁵ is a carbon atom adjacent to Si] Is an alkyl or alkenyl group in which primary carbon is ⁶ is an aralkyl group in which the carbon adjacent to Si is a primary carbon, and R ³ is a hydrocarbon group]. 2. A solid titanium catalyst component containing [A] magnesium, titanium, halogen and an electron donor as essential components, and [B] an organoaluminum compound catalyst component.
[C] An organosilicon compound catalyst component represented by the following general formula [I], and [D] An organosilicon compound catalyst component represented by the following general formula [II] and / or [III]
An olefin polymerization method characterized by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst formed with an organosilicon compound catalyst component represented by: R ¹ R ² Si (OR ³ ) ₂ ... [I] [In the formula, R ¹ is an alkyl group, an aralkyl group, a cycloalkyl group or a cycloalkenyl group in which the carbon adjacent to Si is a secondary or tertiary carbon, and R ² is Si is an alkyl group or an alkenyl group whose carbon adjacent to Si is a primary carbon, and R ³ is a hydrocarbon group], R ⁴ Si (OR ³ ) ₃ ... [II] [wherein R is ⁴ is an alkyl group, an alkenyl group or an aralkyl group in which the carbon adjacent to Si is a primary carbon, R ³ is a hydrocarbon group], R ⁵ R ⁶ Si (OR ³ ) ₂ ... [III] [wherein, R ⁵ is, Si An alkyl or alkenyl group having a carbon adjacent are primary carbon, R ⁶ is an aralkyl group wherein the carbon adjacent to Si is a primary carbon, R ³ is a hydrocarbon group.