JPH06172437A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having an extremely wide molecular weight distribution and excellent moldability and stereoregularity by blending in a molten state olefin polymers prepared by using different specific catalysts. CONSTITUTION:(A) An olefin polymer obtained by (co)polymerizing an olefin in the presence of a catalyst comprising (i) a solid catalytic component composed essentially of Mg, Ti, a halogen and an electron donor, (ii) an organoaluminum compound and (iii) an electron donor of formula I [R<1> is alkyl, cycloalkyl, etc., wherein C adjoining Si (adjoining C) is secondary or tertiary; R<2> is hydrocarbon] is blended in a molten state with (B) an olefin polymer prepared by (co) polymerizing an olefin in the presence of a catalyst comprising the component (i), the component (ii) and (iv) an electron donor of formula II ((n) is 0-4; when (n) is 2, one of R<1> is alkyl or alkenyl wherein adjoining C is primary and the other R<1> is aralkyl wherein adjoining C is primary; when (n) is except 2, R<1> is alkyl or alkenyl wherein adjoining C is primary; R<2> is hydrocarbon).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention provides an olefin polymer having a wide molecular weight distribution, excellent moldability, and a stereoregularity capable of providing a molded product having excellent mechanical properties and transparency in a high yield. And a process for producing such an olefin polymer.

[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 molecular weight distribution is narrow and moldability is not always good, so that it is used in applications. In some cases, an olefin polymer that is easy to flow when melted, that is, has excellent moldability has been desired.

Therefore, conventionally, a plurality of polymerization vessels are used,
Means have been taken such that an olefin polymer having a different molecular weight is produced in each polymerization vessel to obtain a polymer having a wide molecular weight distribution and to improve moldability. However, the above method cannot be adopted in a single polymerization vessel, and there is a problem that it takes time to produce an olefin polymer having a wide molecular weight distribution by a plurality of polymerization vessels.
It has been desired to develop a method for producing an olefin polymer that can obtain 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. An unexpected result that a high molecular weight component was produced was also obtained, and it can be expected that the strength of the olefin polymer is improved by the high molecular weight component. The olefin polymer obtained by this polymerization method has high stereoregularity and high bulk density.

The inventors of the present invention have conducted extensive studies to obtain an olefin polymer having a broader molecular weight distribution and excellent moldability than the olefin polymer obtained by the above-mentioned polymerization method, and a specific solid titanium catalyst component. An olefin polymer (I) obtained by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst formed from a specific organoaluminum compound catalyst component and a specific electron donor catalyst component; Polymerization or copolymerization of olefin in the presence of a solid titanium catalyst component, a specific organoaluminum compound catalyst component, and an olefin polymerization catalyst formed from a specific electron donor catalyst component different from the above electron donor catalyst component. The olefin polymer (I
When I and (I) are melt-kneaded, an olefin polymer having an extremely broad molecular weight distribution and excellent moldability and stereoregularity is obtained, and a molded product made of this olefin polymer has mechanical properties and transparency. It has been found that it has excellent properties, and has completed the present invention.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and has an extremely wide molecular weight distribution, excellent moldability, and excellent mechanical properties and transparency. Moreover, it is an object of the present invention to provide a method for producing an olefin polymer having excellent stereoregularity.

[0009]

SUMMARY OF THE INVENTION A method for producing an olefin polymer 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; [C] Electron donor catalyst component represented by the following general formula [I] R ¹ ₂ Si (OR ² ) ₂ ... [I] [In the formula, R ¹ is a carbon atom adjacent to Si. Is an alkyl group, a cycloalkyl group or a cycloalkenyl group which is a secondary or tertiary carbon, and R ² is a hydrocarbon group], the olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst. The olefin polymer (I) thus obtained, [A] a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor as essential components, and [B] an organoaluminum. Compound catalyst component, and [D] electron donor catalyst component represented by the following general formula [II] R ¹ _n Si (OR ² ) _4-n ... [II] [where n is 2 , One of R ¹ is an alkyl group or an alkenyl group in which the carbon adjacent to Si is a primary carbon, the other R ¹ is an aralkyl group in which the carbon adjacent to Si is a primary carbon, and 0 <N <2 or 2 <n <
4, R ¹ is an alkyl group or an alkenyl group in which the carbon adjacent to Si is a primary carbon, R ² is a hydrocarbon group, and n is 0 <n <4] In the presence of a catalyst for use, olefin polymer (II) obtained by polymerizing or copolymerizing olefin is melt-kneaded.

According to the present invention, an olefin polymer having a very wide molecular weight distribution, excellent moldability, and excellent stereoregularity can be produced in 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.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The method for producing an olefin polymer according to the present invention will be specifically described below. In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" refers to not only homopolymer but also copolymer. May also be used in the sense of including.

In the method for producing an olefin polymer according to the present invention, first, a specific solid titanium catalyst component [A] is used.
And a specific organoaluminum compound catalyst component [B],
An olefin polymer (I) is obtained by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst formed with a specific electron donor catalyst component [C], and a specific solid titanium catalyst component [ A], a specific organoaluminum compound catalyst component [B], and a specific electron donor catalyst component [D], in the presence of an olefin polymerization catalyst, the olefin is polymerized or copolymerized to produce an olefin. A polymer (II) is obtained.

Then, the obtained olefin polymer (I)
And the olefin polymer (II) are melt-kneaded to obtain the olefin polymer of the present invention. FIG. 1 shows an example of a flow chart of a 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
Trihalogenated alkoxytitaniums such as (OC ₂ H ₅ ) Br ₃ and Ti (O-iso-C ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) ₂ Cl ₂
, Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (O-n-C ₄ H ₉ ) ₂ Cl
₂ , di-dihalogenated dialkoxy titanium such as Ti (OC ₂ H ₅ ) ₂ Br ₂ ; Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ C
l, Ti (O-n- C 4 H 9) 3 Cl, Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium and Br; Ti (OC
Examples thereof include tetraalkoxytitanium such as H ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ and Ti (On-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 magnesium compound having a reducing property and a magnesium compound having no reducing property.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such reducing magnesium compounds 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.

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 a compound derived from the above-mentioned reducing magnesium compound or a compound derived during 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 from polysiloxane compounds, halogen-containing silane compounds, halogen-containing aluminum compounds, esters, alcohols, etc. It may be brought into contact with the compound.

In the present invention, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property, the magnesium compound may be a complex compound, a complex compound or another compound of the above-mentioned magnesium compound with another metal. It may be a mixture with a metal compound. Further, it may be a mixture of two or more kinds of the above compounds.

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, when preparing the solid titanium catalyst component [A], it is preferable to use an electron donor. As such an electron donor, specifically,
Oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides; ammonia,
Examples thereof include nitrogen-containing electron donors such as amine, nitrile, and isocyanate.

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,
Methyl anisate, ethyl anisate, ethyl ethoxybenzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, γ-butyrolactone,
δ-valerolactone, coumarin, phthalide, ethylene carbonate and the like, organic acid esters having 2 to 30 carbon atoms, including the below-mentioned esters which are preferably contained in the titanium catalyst component; inorganics such as ethyl silicate and butyl silicate Acid esters; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthalic acid dichloride, and other acid halides having 2 to 15 carbon atoms; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, Ethers having 2 to 20 carbon atoms such as anisole and diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; acid anhydrides such as benzoic anhydride and phthalic anhydride; methylamine, ethylamine, triethylamine , Tributylamine , Amines such as piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile.

As the electron donor, an organosilicon compound represented by the following general formula [III] can be used. R _n Si (OR ′) _4-n [III] [wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Is. Specific examples of the organosilicon compound represented by the above general formula [III] 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, and more preferable examples of the electron donor include an ester having a skeleton represented by the following general formula.

[0028]

[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 isopropyl malonate, diethyl butyl malonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allyl malonate diethyl dibutyl isobutylmalonate, diethyl Normal butyl malonate 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 polycarboxylic acid ester that can be supported in the titanium catalyst component include, in addition to the above compounds, 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 preferred, and more preferred 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 hydrocarbon groups optionally having a substituent, at least one of which is a branched chain. (Including an alicyclic group) or a ring-containing chain group). Specific examples of R and R ′ include (C
_{H 3) 2 CH-, C 2} H 5 CH (CH 3) -, (CH 3) 2 C
_{HCH 2 -, (CH 3)} 3 C-, C 2 H 5 CH, (CH 3) C
H ₂ -,

[0036]

[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 that can be changed to these during the preparation process of the solid titanium catalyst component. it can.

Other electron donors may coexist in the solid titanium catalyst component, but if they coexist in too large an amount, it will have an adverse effect and should be kept to a small amount. 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 of reacting a magnesium compound or a complex compound composed of a magnesium compound and an electron donor with a titanium compound in a liquid phase.

This reaction may be carried out in the presence of a grinding aid and the like. Further, when the reaction is performed as described above, the solid compound may be pulverized. (2) Liquid magnesium compound having no reducing property,
A method of reacting a liquid titanium compound in the presence of an electron donor to deposit a solid titanium complex. (3) A method of further reacting the reaction product obtained in (2) with a titanium compound. (4) A method of further reacting the reaction product obtained in (1) or (2) with an electron donor and a titanium compound. (5) A solid compound obtained by pulverizing a magnesium compound or a complex compound consisting of a magnesium compound and an electron donor in the presence of a titanium compound is treated with halogen, a halogen compound or an aromatic hydrocarbon. how to.

In this method, the magnesium compound or the complex compound consisting of the magnesium compound and the electron donor may be ground in the presence of a grinding aid. Alternatively, the magnesium compound or the complex compound composed of the magnesium compound and the electron donor may be pulverized in the presence of the titanium compound, pretreated with a reaction aid, and then treated with halogen or the like. Examples of the reaction aid include organic aluminum compounds and halogen-containing silicon compounds. (6) A method of treating the compound obtained in (1) to (4) above with halogen or a halogen compound or an aromatic hydrocarbon. (7) A method of bringing a catalytic reaction product of a metal oxide, magnesium dihydrocarbyl and a halogen-containing alcohol into contact with an electron donor and a titanium compound. (8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium, or aryloxy magnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

Among the methods for preparing the solid titanium catalyst component [A] listed in (1) to (8) above, a method using liquid titanium halide during catalyst preparation, or a method 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 electron donor is about 1 mol per 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,
It is preferably about 0.2 to about 6, and the magnesium / titanium (atomic ratio) is about 1 to 100, preferably about 2 to 50.
Is desirable.

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, 51-1366
25, 52-87489, 52-100596, and
52-147688, 52-104593, 53-2580, 53-40093, 53-40094, 53-430
94 publication, 55-135102 publication, 55-135103 publication,
55-152710, 56-811, 56-11908, 56-18606, 58-83006, 58-1387.
05 publication, 58-138706 publication, 58-138707 publication,
58-138708, 58-138709, 58-1387
No. 10, No. 58-138715, No. 60-23404, and No.
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 sesqui chloride, 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 hydride such as diethyl aluminum hydride and dibutyl aluminum hydride; Partially hydrogenated alkyl aluminum such as ethyl aluminum dihydride and alkyl aluminum dihydride such as propyl aluminum dihydride; Ethyl aluminum ethoxy chloride;
Mention may be made of partially alkoxylated and halogenated alkylaluminium, such as butylaluminum butoxycyclolide, ethylaluminum ethoxy bromide. Further, as a compound similar to (i), an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom can be mentioned. Examples of such a compound include (C ₂ H ₅ )
₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C
₄ H ₉ ) ₂ ,

[0054]

[Chemical 3]

Mention may be made of methylaluminoxane and the like. As the compound represented by the formula (ii),
Examples 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 in which two or more kinds of aluminum compounds described above are bound.

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

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

R ² in the above formula [I] is a hydrocarbon group. R ² preferably has 1 to 10 carbon atoms.
5, particularly preferably a hydrocarbon group having 1 to 2 carbon atoms. Specific examples of such an organosilicon compound include diisopropyldimethoxysilane, diisopropyldiethoxysilane, disec-butyldimethoxysilane and diisopropyldimethoxysilane.
t-butyldimethoxysilane, di-t-amyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, diphenyldimethoxysilane,
Bis-o-tolyldimethoxysilane, Bis-m-tolyldimethoxysilane, Bis-p-tolyldimethoxysilane, Bisethylphenyldimethoxysilane, t-butylmethyldimethoxysilane, t-amylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, cumylmethyldimethoxy Silane, isobutylisopropyldimethoxysilane, isobutylpropyldimethoxysilane, cyclohexylethyldimethoxysilane, (ethylphenyl) methyldimethoxysilane, isopropylmethyldimethoxysilane,
Phenylmethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, sec-butylisobutyldimethoxysilane, cyclohexylisobutyldimethoxysilane, 3,3,3-trifluoropropylcyclopentyldimethoxysilane and the like are preferably used.

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. .

Electron Donor Catalyst Component [D] The electron donor catalyst component [D] used in the present invention is an organosilicon compound represented by the following general formula [II].

R ¹ _n Si (OR ² ) _4-n ... [II] In the above formula [II], n is 0 <n <4, and R is
² is a hydrocarbon group, and when n is 2, one of R ¹ is
Si is an alkyl or alkenyl group in which the carbon adjacent to Si is a primary carbon, and another R ¹ is an aralkyl group in which the carbon adjacent to Si is a primary carbon.

When 0 <n <2 or 2 <n <4, R ¹ is an alkyl group or an alkenyl group whose carbon adjacent to Si is a primary carbon. More specifically explaining the above formula [II], when n is 2, R ¹ is specifically an alkyl group such as a methyl group, an ethyl group, an n-propyl group or an n-butyl group. An aralkyl group such as a cumyl group and a benzyl group; an alkenyl group such as a vinyl group. These substituents may contain halogen, silicon, oxygen, nitrogen, sulfur, phosphorus and boron.

In this case, R ² is preferably a hydrocarbon group having 1 to 5 carbon atoms, particularly preferably 1 to 2 carbon atoms. In the above formula [II], specific examples of the organosilicon compound in which n is 2 include diethyldimethoxysilane, dipropyldimethoxysilane, di-n-butyldimethoxysilane, dibenzyldimethoxysilane, divinyldimethoxysilane and diethyldimethoxysilane. Ethoxysilane, bis-3,3,3
-Trifluoropropyldimethoxysilane and the like are preferably used.

In the above formula [II], when 0 <n <2 or 2 <n <4, R ¹ is an alkyl group or an alkenyl group as described above. In this case, R ² is
It is preferably a hydrocarbon group having 1 to 5 carbon atoms, particularly preferably 1 to 2 carbon atoms.

In the above formula [II], the organic silicon compound in which n is 1 or 3 is specifically trimethylmethoxysilane, trimethylethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane. , Methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane,
Phenyltrimethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, amyl Triethoxysilane, isobutyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane and the like are used.

Of these, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, propyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane. Silane, vinyltrimethoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, amyltriethoxysilane, isobutyltriethoxysilane, methyltriethoxysilane, and 3,3,3-trifluoropropyltriethoxysilane are preferably used.

As the above-mentioned organosilicon compound,
As in the case of the electron donor catalyst component [C] described above, a compound capable of inducing these organosilicon compounds under the olefin polymerization conditions or the prepolymerization conditions is added during the olefin polymerization or the prepolymerization, and the olefin polymerization or the prepolymerization is performed. You may use it so that an organosilicon compound may be produced | generated simultaneously with superposition | polymerization.

In the polymerization method of the present invention, the olefin is polymerized in the presence of the above-mentioned catalyst, but the following prepolymerization is carried out before carrying out such polymerization (main polymerization). Is preferred.

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 electron donor catalyst component [C] or the electron donor 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 50 per 1 g of the solid titanium catalyst component [A].
The amount may be 0 g, preferably 0.3 to 300 g of polymer, and is usually about 0.1 to 100 mol, preferably about 100 mol, per 1 mol of titanium atom in the solid titanium catalyst component [A]. It is desirable that the amount is 0.5 to 50 mol.

The prepolymerization is preferably carried out under mild conditions by adding the olefin and the above catalyst component to an inert hydrocarbon medium. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described below.

When such an olefin is used for prepolymerization, α-containing 2 to 10 carbon atoms, preferably 3 to 10 carbon atoms.
Highly crystalline polymers are obtained from olefins. 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 prepolymer to be produced 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.

A molecular weight modifier such as hydrogen may be used in the prepolymerization. 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.
/ G or more, preferably about 0.5 to 10 dl / g.

It is desirable to carry out the prepolymerization so that about 0.1 to 1000 g, preferably about 0.3 to 500 g of a polymer is produced per 1 g of the titanium catalyst component [A], as described above. If the prepolymerization amount is too large, the production efficiency of the olefin polymer in the main polymerization may decrease.

The prepolymerization can be carried out batchwise or continuously. Production of olefin polymer In the method for producing an olefin polymer according to the present invention,
As described above, the solid titanium catalyst component [A], the organoaluminum compound catalyst component [B], and the electron donor catalyst are first prepared after the preliminary polymerization as described above or without the preliminary polymerization. The olefin polymer (I) is obtained by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst formed from the component [C], and the solid titanium catalyst component [A] and the organoaluminum compound catalyst component described above are also obtained. Olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst formed from [B] and an electron donor catalyst component [D] to obtain an olefin polymer (II). Next, the obtained olefin polymer (I) and olefin polymer (II) are melt-kneaded to obtain the olefin polymer of the present invention.

The above olefin polymers (I) and (I
The olefins used in the production of I) include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-
Examples include octene. In the present invention, these olefins may be used alone or in combination. Of these olefins, propylene or 1-butene is preferably used for homopolymerization, or mixed olefins containing propylene or 1-butene as a main component are preferably used for copolymerization. When such a mixed olefin is used, the content of propylene or 1-butene as the main component is usually 50 mol% or more, preferably 70 mol% or more.

When carrying out homopolymerization or copolymerization of these olefins, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used as a polymerization raw material.

The olefin polymerization in the present invention is usually carried out in a gas phase or a liquid phase. When the polymerization takes the reaction form of slurry polymerization, the following inert hydrocarbons can be used as the reaction solvent, and liquid olefins at the reaction temperature can also be used.

Examples of the inert hydrocarbon medium used in this case 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.

In the production of the above olefin polymer (I), the titanium catalyst component [A] is usually about 0.0001 to 5 in terms of Ti atom per liter of polymerization volume.
It is used in an amount of 0 mmol, preferably about 0.01-10 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. It is used in an amount such that it is 1,000 moles, preferably about 2-1,000 moles. Further, the electron donor catalyst component [C] is usually about 0.001 to 10 in terms of Si atom in the electron donor catalyst component [C] per 1 mol of metal atom in the organoaluminum compound catalyst component [B]. It is used in an amount such that it is a molar amount, preferably about 0.01 to 5 mol, particularly preferably about 0.05 to 2 mol.

In the production of the olefin polymer (II), the titanium catalyst component [A] is usually about 0.00 in terms of Ti atom per liter of polymerization volume.
It is used in an amount of 01 to 50 mmol, preferably about 0.01 to 10 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. It is used in an amount such that it is 1,000 moles, preferably about 2-1,000 moles. Further, the electron donor catalyst component [D] is equivalent to Si atom in the electron donor catalyst component [D] per 1 mol of metal atom in the organoaluminum compound catalyst component [B],
Usually about 0.001 to 10 mol, preferably about 0.01
~ 5 mol, particularly preferably about 0.05 to 2 mol.

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.

If hydrogen is used during the polymerization of the olefin,
The molecular weight of the obtained polymer can be adjusted, and a polymer having a high melt flow rate can be obtained. In the production of the olefin polymer (I), 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 10 to 90 minutes, preferably 20 to
80 minutes, more preferably 30 to 70 minutes.

In the production of the olefin polymer (II), the olefin polymerization temperature is usually about 20 to
200 ° C., preferably about 50 to 180 ° C., the pressure is usually atmospheric pressure to 100 kg / cm ² , preferably about 2 to 50.
It is set to kg / cm ² . The polymerization reaction time is usually 10 to 90 minutes, preferably 20 to 80 minutes, and more preferably 30 to 70 minutes.

In the present invention, the olefin polymerization is
It can be carried out by any of a batch system, a semi-continuous system and a continuous system, but from the viewpoint of productivity, a continuous polymerization process is particularly preferred.

The olefin polymer (I) and the olefin polymer (II) thus obtained may be any of a homopolymer, a random copolymer and a block copolymer.

The melt-kneading of the above-mentioned olefin polymer (I) and olefin polymer (II) is carried out using a conventionally known melt-kneading apparatus such as a Banbury mixer or an extruder.

The olefin polymer obtained by the production method of the present invention has a wide molecular weight distribution and is excellent in processability (moldability) during melt molding.

[0093]

EFFECTS OF THE INVENTION According to the present invention, an olefin polymer having a very wide molecular weight distribution, excellent moldability, and excellent stereoregularity capable of providing a molded product having excellent mechanical properties and transparency can be obtained. It can be produced in yield.

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

[0095]

[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. The reaction was carried out to obtain a uniform solution. After that, 1.67 phthalic anhydride was added to this solution.
g (11.3 mmol) was added, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the above homogeneous solution.

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, a solid portion was collected by hot filtration, the solid portion was resuspended in 275 ml of TiCl ₄ , and then the reaction was carried out at 110 ° C. for 2 hours by heating again.

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 solid titanium catalyst component [A] were added.
Was added in an amount of 2 mmol in terms of titanium atom, and then propylene was supplied for 1 hour at a rate of 5.9 Nl / hour to obtain Ti.
2.8 g of propylene was polymerized per 1 g of the catalyst component [A].

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] Two autoclaves having an internal volume of 2 liters were prepared, and one autoclave was charged with 750 ml of purified hexane, and 0.75 mmol of triethylaluminum, 0.038 mmol of propyltriethoxysilane in a propylene atmosphere at room temperature, and To the preliminarily polymerized product of the catalyst component [A], 0.015 mmol in terms of titanium atom (equivalent to 4.46 mg in terms of the catalyst component [A]) was added. In the other autoclave, an aluminum component and a titanium component were added in the same manner as above except that 0.038 mmol of dicyclopentyldimethoxysilane was added instead of propyltriethoxysilane.

Next, after adding 200 Nml of hydrogen to each of these autoclaves, the temperature was raised to 70 ° C. and the pressure was adjusted to 7
While maintaining kg / cm ² G, the polymerization was started at the same time and the polymerization was carried out for 2 hours.

After the completion of the polymerization, the slurry containing the produced polymer was filtered, separated into a white granular polymer and a liquid phase portion, dried, and then melt-kneaded. Extraction residual rate by boiling n-heptane after melt-kneading, MFR, apparent bulk specific gravity, polymerization activity,
II of all polymers is shown in Table 1.

[0103]

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

The results are shown in Table 1.

[0105]

Examples 3 to 4 Polymerization of propylene was carried out in the same manner as in Example 1 except that dit-butyldimethoxysilane was used instead of dicyclopentyldimethoxysilane in the polymerization of Examples 1 and 2. .

The results are shown in Table 1.

[0107]

Comparative Example 1 Polymerization of propylene was carried out in the same manner as in Example 1 except that dicyclopentyldimethoxysilane was used as both of the electron donor catalyst components used in different reactors in the polymerization of Example 1.

The results are shown in Table 1.

[0109]

Comparative Example 2 Polymerization of propylene was carried out in the same manner as in Example 1 except that propyltriethoxysilane was used as both of the electron donor catalyst components used in different reactors in the polymerization of Example 1.

The results are shown in Table 1.

[0111]

Comparative Example 3 Propylene was polymerized in the same manner as in Example 1 except that vinyltriethoxysilane was used instead of dicyclopentyldimethoxysilane in the polymerization of Example 1.

The results are shown in Table 1.

[0113]

Comparative Example 4 [Main Polymerization] 750 ml of purified hexane was charged into an autoclave having an internal volume of 2 liters, and 0.75 mmol of trimethylaluminum, 0.038 mmol of dicyclopentyldimethoxysilane and 0.038 mmol of propyltriethoxysilane were added in a propylene atmosphere at room temperature. 0.038 mmol and the above-mentioned prepolymerized product of the catalyst component [A] were converted to titanium atoms in an amount of 0.
015 mmol (converted into the above catalyst component [A] is 4.4
6 mg) was added. After adding 200 Nml of hydrogen, the temperature was raised to 70 ° C. and propylene polymerization was carried out for 2 hours. The pressure during the polymerization was kept at 7 kg / cm ² G.

After the completion of the polymerization, the slurry containing the produced polymer was filtered to separate it into a white granular polymer and a liquid phase part. Table 1 shows the extraction residual rate by boiling n-heptane after drying, MFR, apparent bulk specific gravity, polymerization activity, and II of all polymers.

[0115]

[Table 1]

[Brief description of drawings]

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

Claims (1)

[Claims] 1. A solid titanium catalyst component containing [A] magnesium, titanium, halogen and an electron donor as essential components, [B] an organoaluminum compound catalyst component, and [C] represented by the following general formula [I]. Electron donor catalyst component R ¹ ₂ Si (OR ² ) ₂ ··· [I] [wherein R ¹ is an alkyl group in which the carbon adjacent to Si is a secondary or tertiary carbon, cyclo An alkyl group or a cycloalkenyl group, and R ² is a hydrocarbon group], and an olefin polymer (I) obtained by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst. A] a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, [B] an organoaluminum compound catalyst component, and [D] the following general formula [ The electron donor catalyst component _{^{R 1 n Si (OR 2)}} 4-n ······ [II] [ wherein represented by I], when n is 2, one R ¹ is adjacent to Si An alkyl group or an alkenyl group whose carbon is a primary carbon, another R ¹ is an aralkyl group whose carbon adjacent to Si is a primary carbon, and when 0 <n <2 or 2 <n <4, R ¹ is S
i is an alkyl or alkenyl group in which the carbon adjacent to i is a primary carbon, R ² is a hydrocarbon group, and n is 0 <n <4] in the presence of a catalyst for olefin polymerization, A method for producing an olefin polymer, which comprises melt-kneading an olefin polymer (II) obtained by polymerizing or copolymerizing an olefin.