JPH06220116A - Production of olefin polymer - Google Patents

Abstract

PURPOSE:To obtain the subject polymer having broad molecular weight distribution and excellent moldability, mechanical properties, transparency and stereoregularity in high yield by (co)polymerizing an olefin in the presence of a catalyst composed of a specific solid Ti component, an organic Al compound and an electron donor. CONSTITUTION:The objective olefin polymer is produced by polymerizing or copolymerizing an olefin in the presence of an olefinpolymerization catalyst composed of (A) a solid Ti catalyst component containing Mg, Ti, halogen and an electron donor as essential components, (B) an organic Al compound catalyst component and (C) an electron donative catalyst component expressed by formula I (R<1> is alkyl, cycloalkyl, cycloalkenyl or aryl wherein the carbon atom adjacent to Si is secondary or tertiary carbon; R<2> is hydrocarbon group), adding (D) an electron-donative catalyst component expressed by formula II (0<n<4; when n is 2, one of R<1> is alkyl wherein the carbon atom adjacent to Si is primary carbon and the other R<1> is aralkyl; when n is not 2, R<1> is alkyl, etc., wherein the carbon atom adjacent to Si is primary carbon) to the (co)polymer and polymerizing or copolymerizing an olefin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymer having a wide molecular weight distribution, excellent moldability, and high yield of an olefin polymer having excellent stereoregularity, and having an easily controlled molecular weight distribution. The present invention relates to a method for manufacturing a united body.

[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.

Conventionally, a plurality of polymerization vessels are used, and olefin polymers having different molecular weights are produced in the respective polymerization vessels to obtain a polymer having a wide molecular weight distribution and to improve the moldability. It was However, the above method cannot be adopted in a single-stage polymerization vessel, and there is a problem that it takes time to produce an olefin polymer having a wide molecular weight distribution by a multi-stage polymerization vessel. 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 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. With the olefin polymer produced by the above-mentioned polymerization method, an olefin polymer having a molecular weight distribution (Mw / Mn) of about 6 to 8 can be obtained, and an olefin polymer having a wider molecular weight distribution is desired.

The present inventors have obtained an olefin polymer having a broader molecular weight distribution and excellent moldability than the olefin polymer obtained by the above-mentioned polymerization method, and further, controlling the molecular weight distribution easily. As a result of earnest research to obtain a method for producing a polymer, as a result of the presence of an olefin polymerization catalyst formed from a specific solid titanium catalyst component, a specific organoaluminum compound catalyst component, and a specific electron donor catalyst component, Was polymerized or copolymerized, and then a specific electron-donor catalyst component different from the above-mentioned electron-donor catalyst component was added to polymerize or copolymerize the olefin. An olefin polymer having excellent stereoregularity can be obtained, and a molded product made of this polymer has mechanical properties and transparency. It is excellent in, and the method,
The inventors have found that it is easy to control the molecular weight distribution of the obtained olefin polymer, and have completed the present invention.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made under the above circumstances, and has a very wide molecular weight distribution, excellent moldability, excellent mechanical properties and transparency, and stereoregularity. It is an object of the present invention to provide a method for producing an olefin polymer, which is capable of obtaining the above-mentioned excellent olefin polymer and whose molecular weight distribution can be easily controlled.

[0009]

SUMMARY OF THE INVENTION A first method for producing an olefin polymer according to the present invention is [A] a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, and [B] an organoaluminum compound catalyst. Component, and [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 secondary carbon atom adjacent to Si. Or an alkyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group which is a tertiary carbon, and R ² is a hydrocarbon group], the olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst. And then
[D] Electron donor catalyst component represented by the following general formula [II] R ¹ _n Si (OR ² ) _4-n ... [II] (where n is 0 <n <4 and 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 <
When 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, and R ² is a hydrocarbon group) is added to polymerize the olefin. Alternatively, it is characterized by being copolymerized.

The second method for producing an olefin polymer according to the present invention is a solid titanium catalyst component containing [A] magnesium, titanium, halogen and an electron donor as essential components, and [B] an organoaluminum compound catalyst. component,
And [D] the electron donor catalyst component represented by the following general formula [II] R ¹ _n Si (OR ² ) _4-n ... [II] (where n is 0 <n <4 and n is When 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 <
When 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, and R ² is a hydrocarbon group) In the presence of the olefin, the olefin is polymerized or copolymerized, and then [C] the electron donor catalyst component represented by the following general formula [I] R ¹ ₂ Si (OR ² ) ₂ [I] (wherein R ¹ is an alkyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group in which the carbon adjacent to Si is a secondary or tertiary carbon, and R ² is a hydrocarbon group. It is characterized by being polymerized or copolymerized.

According to the present invention, an olefin polymer having an extremely wide molecular weight distribution, excellent moldability, and excellent stereoregularity can be produced in high yield. Moreover, the above-mentioned catalyst is less likely to lower the polymerization activity, and the melt flow rate of the olefin polymer obtained by the method of the present invention using this catalyst can be easily adjusted.

According to the method of the present invention, it is easy to control the molecular weight distribution of the obtained olefin polymer.

[0013]

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 first method for producing an olefin polymer according to the present invention, first, a specific solid titanium catalyst component [A], a specific organoaluminum compound catalyst component [B], and a specific electron donor. Olefin is polymerized or copolymerized by using an olefin polymerization catalyst formed from the catalyst component [C]. Next, the specific electron donor catalyst component [D] is added to this reaction system to further polymerize or copolymerize the olefin.

In the second method for producing an olefin polymer according to the present invention, first, a specific solid titanium catalyst component [A], a specific organoaluminum compound catalyst component [B], and a specific electron. The olefin is polymerized or copolymerized by using the olefin polymerization catalyst formed from the donor catalyst component [D]. Next, the specific electron donor catalyst component [C] is added to this reaction system to further polymerize or copolymerize the olefin. Here, the polymerization may be performed in a single stage or in multiple stages.

FIG. 1 shows an example of a flow chart of the method for preparing the catalyst used in the present invention. First, each catalyst component used in the present invention will be described. 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 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 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; aryloxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium Alkyloxymagnesium such as phenoxymagnesium, dimethylphenoxymagnesium and the like aryloxymagnesium; magnesium laurate,
Examples thereof include carboxylates of magnesium such as magnesium stearate.

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 magnesium compound having a reducing property and the magnesium compound having no reducing property, the magnesium compound may be a complex compound, a compound compound or a complex compound of the above magnesium compound and 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, an electron donor is used when preparing the solid titanium catalyst component [A].
Specific examples of such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids,
Esters of organic or inorganic acids, ethers, acid amides,
Oxygenated electron donors such as acid anhydrides; ammonia, amines,
Examples thereof include nitrogen-containing electron donors such as 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,
Organic acid esters having 2 to 30 carbon atoms, including esters such as δ-valerolactone, coumarin, phthalide, and ethylene carbonate, and polyvalent carboxylic acid esters described below; inorganic acids such as ethyl silicate and butyl silicate 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, anisole , Ethers having 2 to 20 carbon atoms such as 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, Examples include amines such as piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile and trinitrile.

Further, 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, methyltriethoxysilane,
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
Examples include -t-butyldiethoxysilane and cyclopentyltriethoxysilane.

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 a polycarboxylic acid 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 such polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methylsuccinate, diisobutyl α-methylglutarate, dibutylmethyl malonate, diethyl malonate, diethyl ethylmalonate, isopropyl. Diethyl malonate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl allylmalonate, diethyl dibuisobutylmalonate, diethyl dinormal butylmalonate, dimethyl maleate, monooctyl maleate, dioctyl maleate, malein Acid dibutyl, butyl maleate dibutyl, butyl maleate diethyl, β-methyl glutarate diisopropyl, ethyl succinate diallyl, di-2-ethylhexyl fumarate, diethyl itaconate, itaconic acid di Alicyclic polycarboxylic acid esters such as chill, dioctyl citraconic acid, dimethyl citraconic acid; alicyclic polycarboxylic acids such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate Carboxylic acid ester; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate,
Mono-n-butyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate,
Di-n-butyl phthalate, Di-isobutyl phthalate, Di-n-heptyl phthalate, Di-2-ethylhexyl phthalate, Di-n-octyl phthalate, Dineopentyl phthalate, Didecyl phthalate, Benzyl butyl phthalate, Diphenyl phthalate, Aromatic polycarboxylic acid esters such as diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate and dibutyl trimellitate;
Examples include heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

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

Specific examples of the hydroxy-substituted carboxylic acid ester 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.

In addition to the above, other electron donor components that can be supported on the titanium catalyst component include RCOOR '.
(R and R'are hydrocarbon groups which may have a substituent, at least one of which is branched (including alicyclic)
Or a monocarboxylic acid ester represented by 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
_{-, (CH 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.

Carbonate ester can be selected as the electron donor. 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, 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 or 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, 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 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 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,
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, 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, K, and R ¹ is the same as the above). And a complex alkylated product of aluminum with aluminum.

The following compounds can be exemplified as the organoaluminum compound represented by the above formula (i). 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.

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,

[0057]

[Chemical 3]

Examples thereof include methylaluminoxane. Examples of the compound represented by the above formula (ii) include Li
Examples include Al (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 the above-mentioned aluminum compounds 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, a cycloalkyl group or a cycloalkenyl group in which the carbon adjacent to Si is a secondary or tertiary carbon. Or an aryl group,
Preferably, it is an alkyl group, a cycloalkyl group or a cycloalkenyl group in which the carbon adjacent to Si is a secondary or tertiary carbon.

Specifically, alkyl groups such as isopropyl group, sec-butyl group, t-butyl group and t-amyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; cyclopentenyl group, cyclopentadienyl group And a cycloalkenyl group; and aryl groups such as a phenyl group and a tolyl group.

These substituents may contain halogen, silicon, oxygen, nitrogen, sulfur, phosphorus or boron.
Among 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 ²
Is a hydrocarbon group, and when n is 2, one of R ¹ is S
i is an alkyl or alkenyl group in which the carbon adjacent to i 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. The formula [II] will be described more specifically. When n is 2, R ¹ is specifically a methyl group, an ethyl group, an n-propyl group,
Examples thereof include alkyl groups such as n-butyl group; aralkyl groups such as cumyl group and benzyl group; alkenyl groups such as 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], as the organic silicon compound in which n is 2, specifically, diethyldimethoxysilane,
Dipropyldimethoxysilane, di-n-butyldimethoxysilane, dibenzyldimethoxysilane, divinyldimethoxysilane, diethyldiethoxysilane, 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 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, amyltriethoxysilane, isobutyltriethoxysilane, 3 For example, 3,3,3-trifluoropropyltrimethoxysilane and 3,3,3-trifluoropropyltriethoxysilane are used.

Among 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 pre-polymerization is carried out before 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 for the prepolymerization may be a temperature at which the produced prepolymer does not substantially dissolve 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 that the prepolymerization is carried out 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 First, the first method for producing an olefin polymer according to the present invention will be described.

In the present invention, first, in the presence of an olefin polymerization catalyst formed from the solid titanium catalyst component [A], the organoaluminum compound catalyst component [B], and the electron donor catalyst component [C]. The olefin is (co) polymerized, and then the electron donor catalyst component [D] is added to the polymerization system to carry out (co) polymerization of the olefin. In addition, preliminary polymerization may be performed prior to (main) polymerization of the olefin.

As the olefin used in the present invention,
Examples thereof include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-octene and the like. In the present invention,
These olefins can be used alone or in combination. Of these olefins,
Homopolymerization using propylene or 1-butene,
Alternatively, it is preferable to carry out the copolymerization using a mixed olefin containing propylene or 1-butene as a main component. 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 homopolymerizing or copolymerizing these olefins, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used as a raw material for polymerization.

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 may be used as the reaction solvent, and liquid olefins at the reaction temperature may 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 first method for producing an olefin polymer according to the present invention, the titanium catalyst component [A] is usually about 0.
0001 to 50 mmol, preferably about 0.01 to 10
Used in millimolar amounts. In the organoaluminum compound catalyst component [B], the metal atom in the organoaluminum compound catalyst component [B] is usually about 1 to 2,000 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 a mole, preferably about 2-1,000 moles. The electron donor catalyst component [C] is usually about 0.001 to 10 mol in terms of Si atom in the electron donor catalyst component [C] per mol of the metal atom in the organoaluminum compound catalyst component [B]. It is preferably used in an amount of about 0.01 to 5 mol, particularly preferably about 0.05 to 2 mol. The electron donor catalyst component [D] added later is the organoaluminum compound catalyst component [B].
The amount of Si atom in the electron donor catalyst component [D] is usually about 0.001 to 10 mol, preferably about 0.01 to 5 mol, and particularly preferably about 0.05 per 1 mol of metal atom therein.
It is used in an amount such that it is ˜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. Further, when hydrogen is used during the polymerization of 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 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 .

In the first method for producing an olefin according to the present invention, the electron donor catalyst component [D] contains an olefin polymer in an amount of 10 to 90% by weight, preferably 20 to 80% by weight, based on the whole olefin polymer. More preferably 30 to 7
When 0% by weight is produced, it is added to the reaction system. And
As the subsequent olefin polymerization conditions, the polymerization temperature is
Usually about 20 to 200 ° C, preferably about 50 to 180
° C., the pressure is usually normal pressure to 100 kg / cm ^2, is preferably set to approximately to 50 kg / cm ^2. The reaction time is usually 30 to 600 minutes, preferably 40 to 480.
Minutes, more preferably 60 to 360 minutes.

Next, the method for producing the second olefin polymer according to the present invention will be described. In the present invention, first, an olefin is added in the presence of an olefin polymerization catalyst formed from the solid titanium catalyst component [A], the organoaluminum compound catalyst component [B], and the electron donor catalyst component [D]. (Co) polymerization, and then the electron donor catalyst component [C] is added to carry out (co) polymerization of the olefin.
In addition, preliminary polymerization may be performed prior to (main) polymerization of the olefin.

As the olefin used in the present invention,
The same olefins as mentioned above can be mentioned. 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 homopolymerizing or copolymerizing these olefins, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used as a raw material for polymerization.

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 above-mentioned inert hydrocarbon may be used as the reaction solvent, or a liquid olefin at the reaction temperature may be used.

In the second method for producing an olefin polymer according to the present invention, the titanium catalyst component [A] is usually about 0.
0001 to 50 mmol, preferably about 0.01 to 10
Used in millimolar amounts. The organoaluminum compound catalyst component [B] is generally about 1 to 1 mol of titanium atom in the titanium catalyst component [A] in the polymerization system in terms of metal atom in the organoaluminum compound catalyst component [B]. 2,0
It is used in an amount such that it is 00 mol, preferably about 2-1,000 mol. The electron donor catalyst component [D] is usually about 0.001 to 10 mol in terms of Si atom in the electron donor catalyst component [D] per 1 mol of metal atom in the organoaluminum compound catalyst component [B]. Preferably from about 0.01
It is used in an amount of 5 mol, particularly preferably about 0.05 to 2 mol. In addition, the electron donor catalyst component [C] added later is usually approximately in terms of Si atom in the electron donor catalyst component [C] per mol of metal atom in the organoaluminum compound catalyst component [B]. 0.001-10
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 present invention, each catalyst component may be contacted in an inert gas atmosphere or each catalyst component may be contacted in an olefin atmosphere before polymerizing an olefin. Further, when hydrogen is used during the polymerization of olefin, the molecular weight of the obtained polymer can be adjusted,
A polymer having a high melt flow rate can be obtained.

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 .

In the second method for producing an olefin according to the present invention, in the electron donor catalyst component [C], the olefin polymer is 10 to 90% by weight, preferably 20 to 80% by weight of the whole olefin polymer. More preferably 30 to 7
When 0% by weight is produced, it is added to the reaction system. And
As the subsequent olefin polymerization conditions, the polymerization temperature is
Usually about 20 to 200 ° C, preferably about 50 to 180
° C., the pressure is usually normal pressure to 100 kg / cm ^2, is preferably set to approximately to 50 kg / cm ^2. The reaction time is usually 30 to 600 minutes, preferably 40 to 480.
Minutes, more preferably 60 to 360 minutes.

In the present invention, 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 thus obtained may be any of a homopolymer, a random copolymer and a block copolymer. The olefin polymer obtained by the production method of the present invention has a wide molecular weight distribution,
Therefore, it is excellent in workability (moldability) during melt molding. From the olefin polymer obtained by the method of the present invention, a molded article having excellent mechanical properties and transparency can be produced.

In the production method of the present invention, an olefin polymer having a very wide molecular weight distribution, for example, Mw / Mn of 7 to 1 is used.
0, preferably 8 to 10 olefin polymers are obtained,
Moreover, it is easy to control the molecular weight distribution.

[0105]

According to the present invention, an olefin polymer having a very wide molecular weight distribution, excellent moldability and high stereoregularity can be produced in a high yield. Further, according to the method for producing an olefin polymer of the present invention, it is easy to control the molecular weight distribution of the obtained olefin polymer.

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

[0107]

[Example 1] [Preparation of solid titanium catalyst component [A]] 7.14 g (75 mmol) of anhydrous magnesium chloride and 37.5 ml of decane
And 2-ethylhexyl alcohol 35.1 ml (22
(5 mmol) was heated and reacted at 130 ° C. for 2 hours to form a uniform solution. Then, phthalic anhydride 1.
67 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 dropped into 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 it 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 part was collected by hot filtration, the solid part was resuspended in 275 ml of TiCl ₄ , and then the reaction was again carried out at 110 ° C. for 2 hours.

After the reaction was completed, the solid portion was collected again by hot filtration and washed with decane at 110 ° C. and hexane.
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, which was replaced with nitrogen, and 6 mmol of triethylaluminum and 2 mmol of the solid titanium catalyst component [A] were added in terms of titanium atom.
Propylene was fed at a rate of 9 Nl / hr for 1 hour to polymerize 2.8 g of propylene per 1 g of Ti catalyst component [A].

After the completion of this preliminary polymerization, the liquid part was removed by filtration, and the separated solid part was dispersed again in decane. [Main Polymerization] An autoclave having an internal volume of 2 liters was charged with 750 ml of purified hexane, and 0.75 mmol of triethylaluminum, 0.038 mmol of propyltriethoxysilane and the preliminary charge of the catalyst component [A] were charged in a propylene atmosphere at room temperature. The polymerized product is converted to titanium atoms 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 while the pressure was kept at 7 kg / cm ² G by supplying propylene, polymerization was first carried out for 20 minutes, and 0.038 mmol of dicyclopentyldimethoxysilane was added to this system. Was added to carry out polymerization for a total of 2 hours.

After the completion of the polymerization, the slurry containing each of the produced polymers was filtered to separate it into a white granular polymer and a liquid phase part. Extraction residual rate by boiling n-heptane after drying, MFR, apparent bulk density (BD), polymerization activity, II (tI.I.) of all polymers
Is shown in Table 1.

[0114]

Example 2 Polymerization of propylene was carried out in the same manner as in Example 1 except that the polymerization time before the addition of dicyclopentyldimethoxysilane was 30 minutes in the polymerization of Example 1. The results are shown in Table 1.

[0115]

Example 3 Polymerization of propylene was carried out in the same manner as in Example 1 except that the polymerization time before the addition of dicyclopentyldimethoxysilane was changed to 45 minutes in the polymerization of Example 1. The results are shown in Table 1.

[0116]

Example 4 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.

[0117]

Example 5 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 Example 1. The results are shown in Table 1.

[0118]

Example 6 Polymerization of propylene was carried out in the same manner as in Example 1 except that β-phenethylmethyldiethoxysilane was used instead of propyltriethoxysilane in the polymerization of Example 1. The results are shown in Table 1.

[0119]

Example 7 Polymerization of propylene was carried out in the same manner as in Example 1 except that triethylmethoxysilane was used instead of propyltriethoxysilane in the polymerization of Example 1. The results are shown in Table 1.

[0120]

Example 8 Into an autoclave having an internal volume of 2 liters, 750 ml of purified hexane was charged, and 0.75 mmol of triethylaluminum, 0.038 mmol of dicyclopentyldimethoxysilane and the catalyst component (A) were added in a propylene atmosphere at room temperature. To the prepolymerized product, 0.015 mmole in terms of titanium atom (equivalent to 4.46 mg in terms of the catalyst component (A)) was added. Hydrogen 200 Nm
After adding 1 liter, the temperature was raised to 70 ° C. and the pressure was 7 kg / cm.
Polymerization was first carried out for 60 minutes while maintaining ^2- G, 0.038 mmol of propyltriethoxysilane was added to this system, and polymerization was carried out for a total of 2 hours.

After the completion of the polymerization, the slurry containing the produced polymer was filtered to separate the white granular polymer into a liquid phase part. The results are shown in Table 1.

[0122]

Example 9 Propylene was polymerized in the same manner as in Example 8 except that diethylvinylmethoxysilane was used instead of propyltriethoxysilane in the polymerization of Example 8. The results are shown in Table 1.

[0123]

Example 10 Propylene was polymerized in the same manner as in Example 8 except that triethylmethoxysilane was used instead of propyltriethoxysilane in the polymerization of Example 8. The results are shown in Table 1.

[0124]

[Example 11] [Preparation of solid titanium catalyst component (B)] A high-speed stirrer (made by Tokushu Kika Kogyo Co., Ltd.) having an internal volume of 2 liters was sufficiently replaced with nitrogen, 700 ml of purified decane and 1 ml of commercially available MgCl ₂ were added.
0 g and 3 g of sorbitan distearate were added, the system was heated with stirring, and the temperature was maintained at 120 ° C. for 30 minutes while stirring at 800 rpm. Then, under stirring, a Teflon tube having an inner diameter of 5 mm was used to transfer the solution to a glass flask equipped with a stirrer containing 1 liter of purified decane precooled to -10 ° C. The purified suspension was filtered and washed thoroughly with hexane to obtain a spherical solid (carrier).

[0125] Ti in a 400 ml glass container equipped with a stirrer.
Cl _{4 (} 150 ml) was charged, and the above carrier was added and suspended at room temperature. After the addition was completed, the temperature was raised to 40 ° C. and 5.2 mmol of diisobutyl phthalate was added. Then 100 ℃
The temperature was raised to and held for 2 hours.

Next, the solid part and the liquid part were separated by hot filtration, and the solid part was suspended again in 150 ml of TiCl ₄ and reacted under stirring at 120 ° C. for 2 hours. The mixture was hot filtered and washed with a sufficient amount of purified hexane until chlorine ions were not detected in the filtrate to obtain a solid titanium catalyst component (B). The solid titanium catalyst component (B) obtained as described above contains 3.1% by weight of titanium and 1% of magnesium.
7% by weight, chlorine 58% by weight, diisobutyl phthalate 1
It was 7.3% by weight.

[Preliminary Polymerization] Propylene was preliminarily polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (B) was used.

[Main Polymerization] Polymerization of propylene was carried out in the same manner as in Example 1 except that the prepolymerized solid titanium catalyst component (B) was used. The results are shown in Table 1.

[0129]

Comparative Example 1 In the polymerization of Example 1, dicyclopentyldimethoxysilane 0.0 was used instead of two kinds of silane compounds.
Polymerization of propylene was carried out in the same manner as in Example 1 except that only 75 mmol was used. The results are shown in Table 1.

[0130]

Comparative Example 2 Polymerization of propylene was carried out in the same manner as in Example 1 except that 0.075 mmol of propyltriethoxysilane was used instead of two kinds of silane compounds in the polymerization of Example 1. The results are shown in Table 1.

[0131]

Comparative Example 3 Polymerization of propylene was carried out 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.

[0132]

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 0.015 mmol of the above-mentioned prepolymerized catalyst component [A] in terms of titanium atom (equivalent to 4.46 mg in terms of the above catalyst component [A]) were added at the same time. Hydrogen 200N
After adding ml, 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 by supplying propylene.

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. The results are shown in Table 1.

[0134]

[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 (2)

[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, a cycloalkyl group, a cycloalkenyl group in which the carbon adjacent to Si is a secondary or tertiary carbon). Group or an aryl group and R ² is a hydrocarbon group), the olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst, and then [D] is represented by the following general formula [II]. Represented electron donor catalyst component R ¹ _n Si (OR ² ) _4-n ... [II] (where n is 0 <n <4, and when n is 2, one of R ¹ is Si). Alkyl groups in which adjacent carbons are primary carbons Other is an alkenyl group, other R ¹ is an aralkyl group wherein the carbon adjacent to Si is a primary carbon, also when 0 <n <2 or 2 <n <4, R ¹ is S
a carbon atom adjacent to i is an alkyl group or an alkenyl group having a primary carbon atom, and R ² is a hydrocarbon group), and the olefin is polymerized or copolymerized to produce an olefin polymer. . 2. A solid titanium catalyst component containing [A] magnesium, titanium, halogen and an electron donor as essential components, [B] an organoaluminum compound catalyst component, and [D] represented by the following general formula [II]. Electron donor catalyst component R ¹ _n Si (OR ² ) _4-n ... [II] (where n is 0 <n <4, and when n is 2, one of R ¹ is adjacent to Si Is a primary carbon-containing alkyl or alkenyl group, and R ¹ is an aralkyl group in which the 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 group or an alkenyl group whose carbon adjacent to i is a primary carbon, R ² is a hydrocarbon group, and olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst formed from [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 secondary or tertiary carbon atom adjacent to Si. An olefin polymer characterized by polymerizing or copolymerizing an olefin by adding an alkyl group which is carbon, a cycloalkyl group, a cycloalkenyl group or an aryl group, and R ² is a hydrocarbon group) Method.