JPH10218932A - Olefin polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst which has high polymerization activity and high hydrogen-resistant activity can give a highly stereoregular polymer having a broad molecular weight distribution in high yields. SOLUTION: This catalyst comprises a solid catalyst component (A) containing magnesium, titanium, an electron-donating compound and a halogen and obtained by the contact among an Mg compound, a Ti compound and an electron-donating compound, an organoaluminum compound (B) represented by the formula: R<1> n AlX3-x (wherein R<1> is a 1-4C alkyl; X is H or a halogen; and m is a real number in the range: 0<m<=3); a halogen-containing organosilicon compound (C) represented by the formula: Si(OR<2> )4-n Y (wherein R<2> is a 1-4C alkyl, a cycloalkyl, phenyl, vinyl, allyl or an aralkyl; Y is a halogen; and n is an integer of 1-3) and an organosilicon compound represented by the formula: R<3> p Si(OR<4> )4-p (wherein R<3> is a 1-12C alkyl; the other groups are each R2 ; and R4 is R<2> ).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for the polymerization of olefins, which has a high stereoregularity, shows a high hydrogen activity and can obtain an olefin polymer having a wide molecular weight distribution in a high yield. It is.

[0002]

2. Description of the Related Art Conventionally, olefins are polymerized by a solid catalyst component containing magnesium, titanium, an electron donating compound and a halogen as essential components, an organoaluminum compound and an organosilicon compound. Many methods have been proposed for polymerizing or copolymerizing olefins in the presence.

For example, JP-A-57-63310 and JP-A-57-63311 disclose a solid catalyst component containing a magnesium compound, a titanium compound and an electron donor, an organoaluminum compound, and a Si-OC bond. There has been proposed a method of polymerizing an olefin having 3 or more carbon atoms using a catalyst comprising a combination with an organosilicon compound. However, these methods are not always satisfactory for obtaining a high stereoregular polymer in a high yield, and further improvement has been desired.

On the other hand, JP-A-63-3010 discloses that a product obtained by contacting a dialkoxymagnesium, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon and a titanium halide is heat-treated in a powder state. Thus, there has been proposed a olefin polymerization catalyst comprising a solid catalyst component, an organoaluminum compound and an organosilicon compound, and a method for polymerizing olefins.

In Japanese Patent Application Laid-Open No. Hei 1-315406, a suspension formed of diethoxymagnesium and alkylbenzene is brought into contact with titanium tetrachloride, and then phthalic acid dichloride is added to cause a reaction. And a solid catalyst component prepared by further reacting the solid product with titanium tetrachloride in the presence of alkylbenzene, a catalyst for polymerization of olefins comprising an organoaluminum compound and an organosilicon compound, and a catalyst for the catalyst. Methods for polymerizing olefins in the presence have been proposed.

Further, JP-A-2-84404 discloses a solid titanium catalyst component, an organoaluminum compound catalyst component containing magnesium, titanium and halogen as essential components formed by contacting a magnesium compound and a titanium compound. And an olefin polymerization catalyst formed from an organosilicon compound catalyst component containing a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a derivative thereof, and an olefin polymerizing or copolymerizing the olefin in the presence of the catalyst. Polymerization methods have been proposed.

The above prior arts have a high activity enough to eliminate a so-called demineralization step for removing catalyst residues such as chlorine and titanium remaining in a produced polymer, and also have a stereoregularity. It focuses on improving the yield of the polymer and increasing the sustainability of the catalytic activity during the polymerization, and has each produced excellent results.

[0008]

However, when olefins are polymerized using the olefin polymerization catalysts in the prior art described above, hydrogen is usually added as a molecular weight regulator of the polymer. As we improve,
There is a problem that the activity of the catalyst with respect to hydrogen during the polymerization is reduced, and as a result, the productivity of the polymer is reduced. Further, in recent years, a polymer obtained by a polymerization reaction using an olefin polymerization catalyst comprising such a highly active catalyst component and an organoaluminum compound and an organosilicon compound has a conventional titanium trichloride-type catalyst component as an organoaluminum compound. The molecular weight distribution is narrower than the polyolefin obtained by the polymerization reaction using an olefin polymerization catalyst in combination with an electron-donating compound used as a third component, if necessary. There is a problem that its use is restricted, such as impairing the moldability of a certain polyolefin.

As one of means for solving such a problem,
For example, various attempts have been made to adopt a multi-stage polymerization method to obtain a polyolefin having a wide molecular weight distribution. However, the multi-stage polymerization method is not preferable in terms of cost, such as performing complicated polymerization operations in duplicate and recovering a chelating agent used in polymerization.

[0010] Accordingly, an object of the present invention is to provide a method for polymerizing olefins using hydrogen as a molecular weight regulator of a produced polymer while maintaining a high polymerization activity and a yield of a highly stereoregular polymer while maintaining a high stereoregular polymer yield. An object of the present invention is to provide an olefin polymerization catalyst capable of obtaining a polymer having a very high activity and a broad molecular weight distribution.

[0011]

Under such circumstances, the present inventors have conducted intensive studies and as a result, have found that a solid catalyst component, an organoaluminum compound and a specific catalyst obtained by bringing a magnesium compound, a titanium compound and an electron donating compound into contact with each other. It has been found that the above problems can be solved by polymerizing an olefin using a catalyst comprising a combination of the above organosilicon compounds, and the present invention has been completed. That is, the present invention includes the following components (A) to (D): (A) magnesium, titanium, an electron donating compound and a halogen atom obtained by contacting a magnesium compound, a titanium compound and an electron donating compound. (B) the following general formula (1): R ¹ _m AlX _{3 -m} (1) (wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms, X represents a hydrogen atom, chlorine An atom, a bromine atom or an iodine atom, and m represents a real number of 0 <m ≦ 3); (C) the following general formula (2): Si (OR ² ) _4-n Y _n (2) (wherein R ² is the same or different and has an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group,
Y represents a halogen atom; n represents an integer of 1 to 3; (D) the following general formula (3): R ³ _p Si (OR ⁴ ) _4-p (3) wherein R ³ is the same or different and has 1 carbon atom 12 alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, R ⁴ are the same or different, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group , An allyl group or an aralkyl group, and p represents 0 or an integer of 1 to 3).

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The solid catalyst component (A) of the catalyst for olefin polymerization according to the present invention (hereinafter referred to as "solid catalyst component")
Or, it may be referred to as “component (A)”. ) Is one containing magnesium, titanium, an electron-donating compound and a halogen atom as essential components prepared by contacting a magnesium compound, a titanium compound and an electron-donating compound.

In the present invention, the magnesium compound used for preparing the solid catalyst component (A) includes magnesium halide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium, diaryloxymagnesium, alkoxymagnesium halide and fatty acid magnesium. And the like.

Specific examples of the magnesium halide include magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride.

Specific examples of the dialkyl magnesium include dimethyl magnesium, diethyl magnesium, ethyl methyl magnesium, dipropyl magnesium, methyl propyl magnesium, ethyl propyl magnesium, dibutyl magnesium, butyl methyl magnesium and butyl ethyl magnesium. These dialkylmagnesiums can also be obtained by reacting metallic magnesium with an alcohol in the presence of a halogen-containing compound.

Specific examples of the alkyl magnesium halide include ethyl magnesium chloride, propyl magnesium chloride and butyl magnesium chloride. These alkyl magnesium halides are obtained by reacting metal magnesium with a halogenated hydrocarbon or alcohol. Can also be obtained.

Specific examples of dialkoxy magnesium or diaryloxy magnesium include dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, diphenoxy magnesium, ethoxy methoxy magnesium, ethoxy propoxy magnesium and butoxy ethoxy magnesium. Can be.

Specific examples of the alkoxymagnesium halide include methoxymagnesium chloride, ethoxymagnesium chloride, propoxymagnesium chloride and butoxymagnesium chloride.

Specific examples of the fatty acid magnesium include magnesium laurate, magnesium stearate, magnesium octoate and magnesium decanoate.

The magnesium compound is preferably a magnesium halide or a dialkoxymagnesium, particularly preferably magnesium chloride,
Diethoxymagnesium or dipropoxymagnesium.

The magnesium compound may be used alone or in combination of two or more when preparing the solid catalyst component (A).

The dialkoxymagnesium or diaryloxymagnesium is a solid catalyst component (A)
In the preparation of the solid catalyst component (A), for example, it is not necessary to use a product obtained by reacting a metal magnesium and an alcohol in the presence of a catalyst such as iodine. Is also good.

The titanium compound used for preparing the solid catalyst component (A) is a tetravalent halogen-containing titanium compound, such as titanium tetrahalide or alkoxytitanium halide. Specifically, as titanium tetrahalides, TiCl ₄ , TiBr ₄ , TiI ₄ , and alkoxytitanium halides, Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₃
H ₇ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl
₂ , Ti (OC ₃ H ₇ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ , Ti (OCH ₃ ) ₃ Cl
_{, Ti (OC 2 H 5)} 3 Cl, Ti (OC 3 H 7) 3 Cl, Ti (On-C 4 H 9) 3 Cl , and the like. Among them, titanium tetrahalide is preferable, and TiCl ₄ is particularly preferable. One or more of the above titanium compounds can be used. Further, the above titanium compound may be dissolved and used in an organic solvent such as an aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as hexane or heptane.

Further, a tetraalkoxytitanium compound can be used for preparing a solid catalyst component in combination with the above tetravalent halogen-containing titanium compound. Examples of the tetraalkoxytitanium compound include tetraethoxytitanium and tetrabutoxytitanium.

The electron donating compound used for preparing the solid catalyst component (A) is an organic compound containing an oxygen atom or a nitrogen atom.
For example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, Si-O
Examples thereof include an organosilicon compound containing a -C bond and a silicon halide compound.

Examples of alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol and dodecanol. Examples of phenols include phenol and cresol. Is exemplified by methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, and the like.Examples of esters include methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, and butyric acid. Ethyl, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, p-
Monocarboxylic esters such as methyl toluate, ethyl p-toluate, methyl anisate and ethyl anisate;
Examples are dicarboxylic acid esters such as diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dimethyl adipate, diisodecyl adipate, dioctyl adipate, diester phthalate and diester terephthalate. And ketones include acetone,
Examples include methyl ethyl ketone, methyl butyl ketone, acetophenone and benzophenone, and the aldehydes include acid halides such as phthalic acid dichloride and terephthalic acid dichloride, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, and the like. Examples thereof include methylamine, ethylamine, tributylamine, piperidine, aniline, and pyridine, and examples of the nitriles include acetonitrile, benzonitrile, and tolunitrile.

Examples of the organosilicon compound containing a Si-OC bond include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri-n-butylmethoxysilane, Isobutylmethoxysilane, tri-t
-Butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-
Propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2- Ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane , Cyclohexyl (isopropyl) dimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethyl Kishishiran, cyclopentylethyl diethoxysilane, cyclopentyl (isopropyl)
Dimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclopentyl (isobutyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, Phenylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldimethylethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclohexyl (n-pentyl ) Diethoxysilane, Lopentylethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (n-butyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (n-butyl) diethoxysilane, Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane,
Isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane , Cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane,
Chlorotriethoxysilane, dichlorodiethoxysilane and the like can be mentioned.

Further, as the silicon halide compound,
Examples include SiCl ₄ , SiBr ₄ , SiI ₄ , SiF ₄ and HSiCl ₃ .

As the electron donating compound used for preparing the solid catalyst component (A) of the present invention, esters of the above compounds are preferably used, and diester of phthalic acid is particularly preferable. Particularly preferred is a linear or branched alkyl diester of phthalic acid having 1 to 12 carbon atoms. Specific examples of the diester include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethyl methyl phthalate, butyl ethyl phthalate, methyl (isopropyl) phthalate, and ethyl- n-propyl phthalate, ethyl-n-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dihexyl phthalate, di-n-
Heptyl phthalate, di-n-octyl phthalate, bis (2-methylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate,
Di-isodecyl phthalate, bis (2,2-dimethylheptyl) phthalate, n-butyl (isohexyl) phthalate, ethyl (isooctyl) phthalate, n-butyl (isooctyl) phthalate, n-pentylhexyl phthalate, n-pentyl (isohexyl) ) Phthalate, isopentyl (heptyl) phthalate, n-pentyl (isooctyl) phthalate, n-pentyl (isononyl) phthalate, isopentyl (n-decyl) phthalate, n-pentyl (undecyl) phthalate, isopentyl (isohexyl) phthalate, n-hexyl (Isooctyl) phthalate, n-hexyl (isononyl)
Phthalate, n-hexyl (n-decyl) phthalate,
Examples include n-heptyl (isooctyl) phthalate, n-heptyl (isononyl) phthalate, n-heptyl (neodecyl) phthalate, isooctyl (isononyl) phthalate, dibenzyl phthalate, n-butyl benzyl phthalate, ethyl benzyl phthalate, and dicyclohexyl phthalate. Of these, diethyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate and bis (2-ethylhexyl) phthalate are particularly preferred. The electron donating compounds may be used alone or in combination of two or more.

The solid catalyst component (A) can be prepared by bringing a magnesium compound, a titanium compound, and an electron donating compound into contact with each other as described above.
A known method can be adopted as such a preparation method. These methods are described, for example, in JP-A-63-308.
No. 004, No. 63-314111, No. 64-
Nos. 6006, 64-14210, 64-
No. 43506, No. 63-3010, No. 62-
No. 158704.

Specifically, this contact can be carried out in the absence of an inert organic solvent, but it is preferable to carry out the treatment in the presence of the solvent in view of the ease of operation. As the inert organic solvent used, hexane, heptane and saturated hydrocarbon compounds such as cyclohexane,
Benzene, toluene, xylene and aromatic hydrocarbon compounds such as ethylbenzene, orthodichlorobenzene, methylene chloride, halogenated hydrocarbon compounds such as carbon tetrachloride and dichloroethane, and the like,
Aromatic hydrocarbon compounds in a liquid state at a normal temperature of about 90 to 150 ° C., specifically, toluene, xylene or
Ethylbenzene is preferably used.

The solid catalyst component (A) may be prepared by dissolving the above magnesium compound in an alcohol or a titanium compound and then depositing a solid to obtain a solid catalyst component. A method of obtaining a solid catalyst component by suspending in a compound or an inert hydrocarbon solvent or the like may be used. Among them, the particles of the solid catalyst component obtained by the former method are almost spherical,
The particle size distribution is also sharp. Also, in the latter method, a spherical and sharp particle size distribution of the solid catalyst component can be obtained by using a spherical magnesium compound. Is formed, a solid catalyst component having a similar spherical shape and a sharp particle size distribution can be obtained.

The contact of each component is carried out in an inert gas atmosphere, while removing water and the like, while stirring in a vessel equipped with a stirrer. The contact temperature may be in a relatively low temperature range around room temperature when the mixture is simply brought into contact and agitated or mixed or dispersed or suspended for denaturation, but when the reaction is carried out after contact to obtain a product. 40 to 1
A temperature range of 30 ° C. is preferred. When the temperature during the reaction is lower than 40 ° C., sufficient reaction does not proceed, and the performance of the solid catalyst component prepared as a result becomes insufficient. When the temperature exceeds 130 ° C., evaporation of the used solvent becomes remarkable. As a result, the control of the reaction becomes unstable. The reaction time is at least 1 minute, preferably at least 10 minutes, more preferably at least 30 minutes.

The method for preparing the solid catalyst component (A) is described below. (1) Dissolve magnesium chloride in tetraalkoxytitanium and contact with polysiloxane to obtain a solid component.
A method in which titanium tetrachloride is reacted with the solid component, then phthalic chloride is contact-reacted, and titanium tetrachloride is reacted again to prepare a solid catalyst component. In the method for preparing the solid catalyst component, a method for preparing the solid catalyst component by polymerizing the solid catalyst component with an organic aluminum compound, an organic silicon compound and an olefin.

(2) After reacting anhydrous magnesium chloride and 2-ethylhexyl alcohol to form a homogeneous solution, phthalic anhydride is brought into contact with this solution. Then, titanium tetrachloride and phthalic acid diester are contact-reacted with this solution to obtain a solid component, and the solid component is further contacted with titanium tetrachloride to prepare a solid catalyst component.

(3) Metal magnesium, butyl chloride and dibutyl ether are reacted to synthesize an organic magnesium compound. The organomagnesium compound is contacted with tetrabutoxytitanium and tetraethoxysilane to obtain a solid product. A method of preparing a solid catalyst component by contacting phthalic acid diester, dibutyl ether and titanium tetrachloride with the solid product. In the method for preparing the solid catalyst component, a method for preparing the solid catalyst component by polymerizing the solid catalyst component with an organic aluminum compound, an organic silicon compound and an olefin.

(4) An organomagnesium compound such as dibutylmagnesium and an organoaluminum compound are brought into contact with an alcohol such as butanol or 2-ethylhexyl alcohol in the presence of a hydrocarbon solvent to form a uniform solution. In this solution, for example, SiCl ₄ , HSiC
l ₃ , a silicon compound such as polysiloxane is contacted to obtain a solid component. Then, in the presence of an aromatic hydrocarbon solvent, the solid component is contact-reacted with titanium tetrachloride and phthalic acid diester, and further contacted with titanium tetrachloride to obtain a solid catalyst component.

(5) Magnesium chloride, tetraalkoxytitanium and an aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon compound to form a homogeneous solution, and titanium tetrachloride is added to the solution. Precipitate the components. Contacting the solid component with a phthalic acid diester;
A method of preparing a solid catalyst component by further reacting with titanium tetrachloride.

(6) A metal magnesium powder, an alkyl monohalide and an iodine are contact-reacted, and then a tetraalkoxytitanium, an acid halide and an aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon,
A homogeneous solution is prepared, and titanium tetrachloride is added to the solution, and then the temperature is raised to precipitate a solid component. A method of preparing a solid catalyst component by bringing a phthalic acid diester into contact with the solid component and further reacting the solid component with titanium tetrachloride.

(7) Diethoxymagnesium is suspended in an alkylbenzene or halogenated hydrocarbon solvent, contacted with titanium tetrachloride, heated, and then contacted with phthalic diester to obtain a solid component. A method in which the solid component is washed with alkylbenzene, and then contacted again with titanium tetrachloride in the presence of alkylbenzene to prepare a solid catalyst component. A method of obtaining a solid catalyst component by subjecting the solid catalyst component to a heat treatment in the presence or absence of a hydrocarbon solvent.

(8) Diethoxymagnesium is suspended in alkylbenzene, and titanium tetrachloride and phthalic chloride are contacted to obtain a solid component. A method in which the solid component is washed with alkylbenzene, and then contacted again with titanium tetrachloride in the presence of alkylbenzene to prepare a solid catalyst component. Also, the solid catalyst component and titanium tetrachloride were added in 2 parts.
A method of obtaining a solid catalyst component by contacting at least twice.

(9) Diethoxymagnesium, calcium chloride and a silicon compound represented by the formula Si (OR ⁵ ) ₄ (wherein R ⁵ represents an alkyl group or an aryl group) are co-pulverized, and the pulverized solid is obtained. Is suspended in an aromatic hydrocarbon, contact-reacted with titanium tetrachloride and a diester of an aromatic dicarboxylic acid, and further contacted with titanium tetrachloride to prepare a solid catalyst component.

(10) Diethoxymagnesium and phthalic acid diester are suspended in alkylbenzene, and the suspension is added to titanium tetrachloride and reacted to obtain a solid component. After washing the solid component with alkylbenzene,
A method in which titanium tetrachloride is brought into contact again in the presence of alkylbenzene to prepare a solid catalyst component.

(11) A solid catalyst component is prepared by contacting an aliphatic magnesium such as calcium halide and magnesium stearate with titanium tetrachloride and a diester of an aromatic dicarboxylic acid, and further contacting titanium tetrachloride. how to.

(12) Diethoxymagnesium is suspended in an alkylbenzene or halogenated hydrocarbon solvent, contacted with titanium tetrachloride, heated, and then contacted with phthalic diester to obtain a solid component. After washing the solid component with alkylbenzene, in the method of preparing a solid catalyst component by again contacting titanium tetrachloride in the presence of alkylbenzene, in any of the contacting steps, contacting aluminum chloride to remove the solid catalyst component How to prepare.

(13) Diethoxymagnesium is suspended in an alkylbenzene or halogenated hydrocarbon solvent,
Titanium tetrachloride is brought into contact, the temperature is raised, and then a phthalic acid diester having two or more alkyl groups having different carbon numbers is brought into contact to obtain a solid component. A method in which the solid component is washed with alkylbenzene, and then contacted again with titanium tetrachloride in the presence of alkylbenzene to prepare a solid catalyst component. In the preparation of the solid catalyst component, a phthalic acid diester having two or more alkyl groups having different carbon numbers is brought into contact again with titanium tetrachloride for the second time. A method in which the above-mentioned electron-donating compound other than the phthalic acid diester is used in combination with the phthalic acid diester.

(14) Diethoxymagnesium, titanium tetrachloride and phthalic acid diester are contact-reacted in the presence of chlorobenzene, then titanium tetrachloride and phthalic dichloride are contacted, and titanium tetrachloride is further reacted. A method for preparing a solid catalyst component. The method for preparing the solid catalyst component, wherein the solid catalyst component is contacted again with titanium tetrachloride. Further, a method of using a silicon compound in any of the contacting steps.

(15) Diethoxymagnesium, 2-ethylhexyl alcohol and carbon dioxide are contact-reacted in the presence of toluene to form a homogeneous solution. This solution is contacted with titanium tetrachloride and phthalic acid diester,
A solid component is obtained, and the solid component is dissolved in tetrahydrofuran to further precipitate the solid component. Then
A method of preparing a solid catalyst component by contacting titanium tetrachloride with the solid component, and optionally repeating the contact reaction with titanium tetrachloride. In any of the contacting steps, for example, a method using a silicon compound such as tetrabutoxysilane.

(16) Magnesium chloride, an organic epoxy compound and an organic phosphoric acid compound are suspended in a hydrocarbon solvent such as toluene, and heated to form a homogeneous solution. The solution is contacted with phthalic anhydride and titanium tetrachloride to obtain a solid component, and further reacted with phthalic acid diester. Then, the reaction product is washed with an alkylbenzene, and then titanium tetrachloride is contacted again in the presence of the alkylbenzene to prepare a solid catalyst component.

As a preferred method for preparing the solid catalyst component (A) used in the present invention, for example, a dialkoxymagnesium is suspended in a liquid aromatic hydrocarbon compound at room temperature, and then the suspension is added to the suspension. The catalytic reaction of a divalent titanium halide is carried out. At this time, a phthalic acid diester is contacted before or after contacting the suspension with the titanium halide to obtain a solid reaction product. A method in which the solid reaction product is washed with a liquid aromatic hydrocarbon compound at room temperature, and then a tetravalent titanium halide is contact-reacted in the presence of the aromatic hydrocarbon compound to obtain a solid catalyst component.
Further, a method using an aluminum halide compound such as aluminum trichloride in any of the contacting steps can be mentioned.

In preparing the solid catalyst component (A) of the present invention, the amounts of the magnesium compound, the titanium compound and the electron-donating compound used vary depending on the preparation method and cannot be specified unconditionally.
Per mole, the titanium compound is 0.5 to 100 mol, preferably 1 to 10 mol, and the electron donating compound is 0.01 to 3 mol.
Mole, preferably 0.02 to 1 mole.

The solid catalyst component (A) of the present invention prepared as described above is preferably washed with an inert organic solvent such as heptane to remove unreacted substances. Alternatively, the catalyst for polymerization of olefins of the present invention is formed as it is after washing, in combination with the components (B) and (C) or (D) described below.

Next, the organoaluminum compound (B) (hereinafter sometimes referred to as “component (B)”) used in the present invention is not particularly limited as long as it is represented by the general formula (1). However, in the formula, R ¹ includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group, and among them, an ethyl group or an isobutyl group is preferable. X is a hydrogen atom,
A chlorine atom and a bromine atom are preferred. Examples of the component (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and ethylaluminum hydride. Of these, triethylaluminum and triisobutylaluminum are preferable.
In addition, the organoaluminum compound of the component (B) is 1
Species or a combination of two or more can be used.

As the halogen-containing organosilicon compound (C) (hereinafter sometimes referred to as “component (C)”) used in the present invention, if it is represented by the general formula (2), There is no particular limitation, and in the formula, a preferred group of R ² is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group or a phenyl group, and the cycloalkyl group is preferably a cycloalkyl group having 3 to 6 carbon atoms. And particularly preferably a cyclopentyl group or a cyclohexyl group. Further, as the halogen atom of Y, chlorine, bromine, iodine,
Examples include atoms such as boron, and among them, chlorine, bromine and iodine are preferred.

As such a halogen-containing organosilicon compound (C), for example, chlorotrimethoxysilane,
Chlorotriethoxysilane, chlorotripropoxysilane, chlorotriisopropoxysilane, chlorotributoxysilane, chlorotriisobutoxysilane, chlorotricyclopropoxysilane, chlorotricyclohexyloxysilane, chlorotriphenoxysilane, dichlorodimethoxysilane, dichlorodi Ethoxysilane, dichlorodipropoxysilane, dichlorodiisopropoxysilane, dichlorodibutoxysilane, dichlorodiisobutoxysilane, dichlorodicyclopropoxysilane, dichlorodicyclohexyloxysilane, dichlorodiphenoxysilane, trichloromethoxysilane, trichloroethoxysilane, trichloro Propoxysilane, trichloroisopropoxysilane, trichlorobutoxysilane, trichloroisobutoxy Run, trichloroacetic cyclopropoxy, trichlorosilane cyclohexyloxy silane and trichloro phenoxy silane and the like, preferably chloro trimethoxysilane, chloro triethoxy silane, dichlorosilane dimethoxy silane or dichlorosilane diethoxy silane. The organosilicon compound (C) can be used alone or in combination of two or more.

The organosilicon compound (D) (hereinafter sometimes referred to as “component (D)”) used in the present invention is not particularly limited as long as it is represented by the general formula (3). In the formula (3), a preferable group of R ³ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group or a phenyl group, and the cycloalkyl group is preferably a cycloalkyl group having 3 to 6 carbon atoms. . Also, R
⁴ Preferred groups are alkyl groups of 1 to 4 carbon atoms, a cycloalkyl group or a phenyl group, preferably a cycloalkyl group having 3 to 6 carbon atoms as the cycloalkyl group, especially cyclopentyl or cyclohexyl preferred .

Examples of the organosilicon compound (D) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, and alkoxysilane. For example, trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylmethoxysilane, tri-t-butylmethoxysilane, tri-t-butylmethoxysilane -N
-Butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n
-Propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane Silane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyl Dimethoxysilane,
Cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexyl (isopropyl) dimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane,
Cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (isopropyl) dimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, cyclopentyl (isobutyl)
Dimethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (isopropyl) diethoxysilane, cyclohexyl (n-butyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (Isobutyl) dimethoxysilane,
Diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldimethylethoxysilane, cyclohexyldiethylmethoxysilane,
Cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane,
n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-
Butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane,
Cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetra Methoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-
Methylcyclohexylcyclohexyldimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 3,5-dimethoxycyclohexylcyclohexyldimethoxysilane and bis (3,5- Dimethylcyclohexyl) dimethoxysilane and the like.

Of the above, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyldimethoxysilane Butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxy Silane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclo Pentyl dimethoxy silane,
Cyclohexylcyclopentyldiethoxysilane, 3-
Methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound (D) may be used alone or in combination of two or more. it can.

To polymerize olefins using the olefin polymerization catalyst of the present invention, the solid catalyst component (A), organoaluminum compound (B), halogen-containing organosilicon compound (C) and organosilicon compound (C) D)
Polymerization or copolymerization of olefins is carried out in the presence of a catalyst consisting of, but the ratio of each component used is arbitrary and is not particularly limited as long as it does not affect the effects of the present invention. Usually, the organoaluminum compound (B) is used in a molar ratio of 1 to 1,000, preferably 50 to 500, per mol of titanium atom in the solid catalyst component (A). The halogen-containing organosilicon compound (C) is
0.0020 to 1 in molar ratio per mole of component (B)
0, preferably 0.01 to 2, particularly preferably 0.01
It is used in the range of 0.5 to 0.5. The organosilicon compound (D) is present in a molar ratio of 0.00 per mole of the component (B).
It is used in the range of 20 to 10, preferably 0.01 to 2, particularly preferably 0.01 to 0.5.

The ratio of the halogen-containing organosilicon compound (C) to the organosilicon compound (D) used in the polymerization is not limited, but is usually from 1:99 to 99:
1, preferably from 10:90 to 90:10, particularly preferably from 30:70 to 70:30.

The order of contact of each component is arbitrary, but first, an organoaluminum compound (B) is charged into a polymerization system, and then a halogen-containing organosilicon compound (C) and an organosilicon compound (D) are contacted. And the solid catalyst component (A)
Is preferably contacted. At this time, the halogen-containing organosilicon compound (C) and the organosilicon compound (D) can be mixed in advance, and the mixture can be charged into the polymerization system.

The olefins homopolymerized or copolymerized using the catalyst of the present invention include ethylene, propylene,
-Butene or 4-methyl-1-pentene, which is particularly suitable for the polymerization of propylene. The catalyst of the present invention is also effective in random copolymerization or block copolymerization of propylene with other olefins such as ethylene and 1-butene.

Further, in the polymerization of olefins (also referred to as main polymerization) using the olefin polymerization catalyst of the present invention, in order to further improve the catalytic activity, stereoregularity, and particle properties of the resulting polymer. It is preferable to carry out preliminary polymerization prior to polymerization. As monomers for the prepolymerization, not only ethylene and propylene but also monomers such as styrene and vinylcyclohexane can be used.

In carrying out the prepolymerization, the order of contact of each component and the monomer is arbitrary. Preferably, the organoaluminum compound (B) is first placed in the prepolymerization system in an inert gas atmosphere or an olefin gas atmosphere for polymerization. )
, And then contacted with the solid catalyst component (A).
Contacting one or more olefins. When the prepolymerization is carried out by combining the halogen-containing organosilicon compound (C) and / or the organosilicon compound (D), the organoaluminum is first placed in the prepolymerization system in an inert gas atmosphere or an olefin gas atmosphere for polymerization. After the compound (B) is charged, the halogen-containing organosilicon compound (C) and / or the organosilicon compound (D) are brought into contact with each other, and the solid catalyst component (A) is brought into contact therewith.
It is preferred to contact one or more olefins.

The polymerization is carried out by slurry polymerization, liquefaction polymerization or gas phase polymerization, and it is possible to use hydrogen as a molecular weight regulator during the polymerization. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower,
It is preferably at most 5 MPa, more preferably at most 2.5 MPa.

[0066]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but this is merely an example, and the present invention is not limited thereto.

Example 1 <Preparation of a solid catalyst component> 20 g of diethoxymagnesium and 160 ml of toluene were put into a 500 ml round bottom flask which was sufficiently substituted with nitrogen gas and equipped with a stirrer, to be in a suspended state. After stirring at room temperature for 15 minutes, 40 ml of room temperature titanium tetrachloride was added thereto, the temperature was raised to 80 ° C. with stirring, 5.7 ml of di-n-butylphthalate was added, and the temperature in the system was further increased. Was heated to 110 ° C. and reacted for 2 hours. After the reaction, the supernatant was removed, and toluene 200
Washed 3 times at 90 ° C. with ml. Then, toluene 1
60 ml and 40 ml of titanium tetrachloride are newly added,
For 1 hour and 30 minutes while stirring, and then washed seven times with 200 ml of n-heptane at 40 ° C. to obtain a solid catalyst component (A). The Ti content in the solid catalyst component was measured and found to be 2.72%.

<Formation and Polymerization of Polymerization Catalyst> In a 2.0-liter autoclave with a stirrer completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum as the component (B) and dichlorodichloromethane as the component (C) were added. 0.066 mmol of ethoxysilane, 0.066 mmol of cyclohexylmethyldimethoxysilane as the component (D), and 0.0066 mmol of the solid catalyst component as a titanium atom.
mmol was charged to form an olefin polymerization catalyst.
Thereafter, 3.0 l of hydrogen gas and 1.4 l of liquefied propylene were charged and a polymerization reaction was carried out at 70 ° C. for 1 hour.

The olefin polymerization catalyst was evaluated by determining the polymerization activity (polymerization activity), the yield of the whole crystalline polymer and the molecular weight distribution per solid catalyst component used in the following formula (4).
To (6). The results are shown in Table 1 together with the melt index (MI) of the produced polymer.

Polymerization activity = (a) g / solid catalyst component g (4) Yield of fully crystalline polymer (wt%) = (b) × 100 / (a) (5) Molecular weight distribution = weight average molecular weight ( Mw) / number average molecular weight (Mn) (6)

In the above equations (4) and (5),
(A) is the weight (g) of the produced polymer after the completion of the polymerization reaction.
(B) shows the weight (g) of the n-heptane-insoluble component extracted from boiling n-heptane for 6 hours.

Example 2 The same experiment as in Example 1 was performed except that chlorotriethoxysilane was used instead of dichlorodiethoxysilane. Table 1 shows the obtained results.

COMPARATIVE EXAMPLE 1 Dichlorodiethoxysilane was not used, and the amount of cyclohexylmethyldimethoxysilane used was 0.066 mm.
The same experiment as in Example 1 was performed except that ol was changed to 0.132 mmol. Table 1 shows the obtained results.

Example 3 The same experiment as in Example 1 was carried out except that cyclohexylcyclopentyldimethoxysilane was used instead of cyclohexylmethyldimethoxysilane. Table 1 shows the obtained results.

Example 4 The same experiment as in Example 2 was performed except that cyclohexylcyclopentyldimethoxysilane was used instead of cyclohexylmethyldimethoxysilane. Table 1 shows the obtained results.

COMPARATIVE EXAMPLE 2 Dichlorodiethoxysilane was not used, and the amount of cyclohexylcyclopentyldimethoxysilane used was 0.
The same experiment as in Example 3 was performed except that 066 mmol was changed to 0.132 mmol. Table 1 shows the obtained results.

[0077]

[Table 1]

[0078]

According to the olefin polymerization catalyst of the present invention, a high polymerization activity and a high stereoregular polymer yield can be obtained in the polymerization of olefins using hydrogen as a molecular weight regulator of the produced polymer. A polymer having an extremely high hydrogen activity while maintaining the effect and having a wide molecular weight distribution can be obtained.

[Brief description of the drawings]

FIG. 1 is a flowchart schematically showing an olefin polymerization catalyst of the present invention.

Claims (1)

[Claims] 1. The following components (A) to (D): (A) containing magnesium, titanium, an electron donating compound and a halogen atom obtained by contacting a magnesium compound, a titanium compound and an electron donating compound. Solid catalyst component, (B) the following general formula (1); R ¹ _m AlX _3-m (1) (wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms, X represents a hydrogen atom, a chlorine atom , A bromine atom or an iodine atom, and m represents a real number of 0 <m ≤ 3.) (C) the following general formula (2): Si (OR ² ) _4-n Y _n (2) (wherein, R ² is the same or different and has an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group,
Y represents a halogen atom; n represents an integer of 1 to 3; (D) the following general formula (3): R ³ _p Si (OR ⁴ ) _4-p (3) wherein R ³ is the same or different and has 1 carbon atom 12 alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, R ⁴ are the same or different, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group , An allyl group or an aralkyl group, and p represents 0 or an integer of 1 to 3).