JP3478352B2 - Olefin polymerization catalyst and polymerization method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for polymerization of olefins and a method for polymerizing olefins using the same, and more particularly to a catalyst for olefins having a high stereoregularity and a wide molecular weight distribution. The present invention relates to a catalyst for polymerizing olefins which can be obtained in a yield and a method for polymerizing olefins in the presence of the catalyst.

[0002]

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

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 Si- A method has been proposed in which an olefin having 3 or more carbon atoms is polymerized using a catalyst composed of a combination with an organosilicon compound having an OC bond. However, these methods
In order to obtain a highly stereoregular polymer in a high yield, it is not always sufficiently satisfactory, and further improvement has been desired.

On the other hand, in Japanese Patent Laid-Open No. 63-3010,
Solid catalyst component prepared by heating the product obtained by contacting dialkoxymagnesium, aromatic dicarboxylic acid diester, aromatic hydrocarbon and titanium halogen compound in a powder state, an organoaluminum compound and an organosilicon compound And a method for polymerizing olefins in the presence of the catalyst have been proposed.

Further, in JP-A-1-315406, titanium tetrachloride is brought into contact with a suspension formed of diethoxymagnesium and alkylbenzene, and then phthalic acid dichloride is added to cause a reaction to produce a solid. A solid catalyst component prepared by further catalytically reacting the solid product with titanium tetrachloride in the presence of alkylbenzene, a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound, and the catalyst A method for polymerizing olefins in the presence of is proposed.

Further, in Japanese Patent Laid-Open No. 84404/1990, a solid titanium catalyst component containing magnesium, titanium and halogen produced by contacting a magnesium compound with a titanium compound as an essential component, and an organoaluminum compound catalyst component. And a catalyst for olefin polymerization formed from an organosilicon compound catalyst component containing a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or derivatives thereof, and polymerization of an olefin for polymerizing or copolymerizing an olefin in the presence of the catalyst. A method has been proposed.

The above-mentioned respective prior arts have a high activity for the purpose of removing catalyst residues such as chlorine and titanium remaining in the produced polymer, that is, a so-called deashing step can be omitted, and at the same time, three-dimensional It focuses on improving the yield of regular polymers and enhancing the sustainability of catalytic activity during polymerization.
Each has excellent results.

[0008]

However, in recent years, an olefin polymer obtained by a polymerization reaction using such a highly active catalyst component and an olefin polymerization catalyst composed of an organoaluminum compound and an organosilicon compound has been known as a conventional olefin polymer. Compared to an olefin polymer obtained by a polymerization reaction using a catalyst for olefin polymerization in which a titanium chloride type catalyst component is used as an organoaluminum compound and, if necessary, an electron donating compound as a third component, Its molecular weight distribution is narrow, which impairs the moldability of the final product, polyolefin, and limits its use to some extent.

As one of means for solving such a problem, various attempts have been made, for example, by adopting a multistage 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 collecting the chelating agent used during polymerization.

Therefore, in JP-A-3-7703, a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor as essential components, an organoaluminum compound and at least two or more electron donors (organic silicon). A method of polymerizing an olefin in the presence of a catalyst for polymerizing an olefin formed from a compound) has been proposed.

According to the above-mentioned polymerization method, it is said that a desired polyolefin having a wide molecular weight distribution can be obtained without complicated multi-step polymerization, but electron donation during polymerization of two or more kinds of organosilicon compounds. Since its use as a body is an essential requirement, its operation is complicated.

The present inventors have solved the problems associated with the above-mentioned prior art, and have a high molecular weight distribution while maintaining a high polymerization activity and a high stereoregular polymer yield by a simpler operation. As a result of extensive studies for the purpose of providing a catalyst and a method for polymerizing olefins from which a polymer is obtained, magnesium and titanium formed by bringing a magnesium compound, a titanium compound and an electron donating compound into contact with each other. By polymerizing olefins using a catalyst composed of a solid catalyst component containing an electron-donating compound and halogen as essential components, an organoaluminum compound, and an organosilicon compound having a specific structure, high stereoregularity can be obtained. It was found that an olefin polymer having a high molecular weight distribution and a high molecular weight distribution can be obtained in high yield, leading to the completion of the present invention. It was.

[0013]

That is, the catalyst for olefin polymerization provided by the present invention comprises the following (A):
The structural feature is that it is formed from the components (B) and (C). (A) Dissolve dialkoxymagnesium in alkylbenzene
The suspension is suspended in a medium to form a suspension , and titanium tetrachloride is brought into contact with the suspension, followed by heating to bring it into contact with a phthalic acid diester, followed by reaction to obtain a solid component. Is washed with alkylbenzene and then contacted with titanium tetrachloride again in the presence of alkylbenzene (B) Organoaluminum compound (C) 3-methylcyclohexylcyclohexyldimethoate
Kishishiran, bis (3-Mechirushi Kurohekishiru) dimethoxysilane, and one or more organic silicon compound selected from 4-methylcyclohexyl cyclohexyl dimethoxysilane. The olefin polymerization catalyst provided by the present invention is characterized in that it is formed from the following components (A), (B) and (C). (A) Dissolve dialkoxymagnesium in alkylbenzene
After contacting the titanium tetrachloride to form made suspension by suspending in medium causes then contacting the different phthalic acid diester having a carbon number of heating of two or more alkyl groups, is reacted To obtain a solid component, which is washed with alkylbenzene, and then contacted with titanium tetrachloride again in the presence of alkylbenzene to prepare a solid catalyst component (B) organoaluminum compound (C) 3-methylcyclohexylcyclohexyldiene Met
Xysilane

Solid catalyst component (A): The solid catalyst component (hereinafter referred to as "solid catalyst component (A)"), which is one component forming the catalyst for polymerizing olefins of the present invention, is a magnesium compound, a titanium compound and an electron donor. It contains magnesium, titanium, an electron-donating compound and a halogen, which are prepared by bringing a hydrophilic compound into contact with each other, as essential components.

Examples of the magnesium compound used for preparing the solid catalyst component (A) include metal magnesium, magnesium halide, dialkyl magnesium, alkyl magnesium halide, dialkoxy magnesium, and alkoxy magnesium halide.

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

Specific examples of dialkyl magnesium include dimethyl magnesium, diethyl magnesium, ethyl methyl magnesium, dipropyl magnesium, methyl propyl magnesium, ethyl propyl magnesium, dibutyl magnesium, butyl methyl magnesium, butyl ethyl magnesium, and the like.
These dialkylmagnesiums can also be obtained by reacting metallic magnesium with halogenated hydrocarbons or alcohols.

Specific examples of the alkyl magnesium halide include ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, etc. These alkyl magnesium halides are obtained by reacting metallic magnesium with halogenated hydrocarbon or alcohol. You can also get it.

Specific examples of dialkoxy magnesium include dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, diphenoxy magnesium, ethoxymethoxy magnesium, ethoxypropoxy magnesium and butoxyethoxy magnesium.

Specific examples of the halogenated alkoxy magnesium include methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride, butoxy magnesium chloride and the like.

Among these magnesium compounds in the present invention, dialkoxymagnesium is preferable, and diethoxymagnesium and dipropoxymagnesium are particularly preferable. The above magnesium compounds may be used alone or in combination of two or more.

Further, the dialkoxymagnesium used in the preparation of the solid catalyst component (A) in the present invention is any one or two or more dialkoxymagnesium having 1 to 3 carbon atoms, and is in the form of granules or powder. It is a state. The shape may be an irregular shape or a spherical shape. For example, when spherical diethoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution is obtained, the handling operability of the produced polymer powder during the polymerization operation is improved, and the produced polymer powder becomes Trouble such as blockage due to the fine powder contained is eliminated.

The above spherical diethoxymagnesium is
It does not necessarily have to be a true sphere, and an ellipse-shaped or potato-shaped one is used. Specifically, the degree of spherical shape of the particles is 3 or less, preferably 1 to 2, and more preferably 1 to 1 in terms of the ratio of the major axis diameter 1 to the minor axis diameter w (l / w). It is 5.

The dialkoxymagnesium having an average particle size of 1 to 200 μm can be used. Preferably, it is 5 to 150 microns.

In the case of spherical diethoxymagnesium, its average particle size is 1-100 microns, preferably 5-50.
Micron, and more preferably 10 to 40 micron. Regarding the particle size, it is desirable to use one having a small particle size or coarse particles and a sharp particle size distribution. Specifically, the proportion of particles having a size of 5 microns or less is 20% or less, preferably 10% or less. On the other hand, 100
10% or less of particles having a size of micron or more, preferably 5
% Or less. Furthermore, the particle size distribution is calculated as ln (D90 / D
10) (where D90 represents the particle size at 90% of the integrated particle size and D10 represents the particle size at 10% of the integrated particle size), it is 3 or less, preferably 2 or less.

The dialkoxymagnesium does not necessarily have to be used as a starting material in the preparation of the solid catalyst component (A). For example, when the solid catalyst component (A) is prepared, metal magnesium and alcohol are present in the presence of a catalyst such as iodine. You may use what was obtained by making it react below.

The titanium compound used in the preparation of the solid catalyst component (A) in the present invention has a general formula, Ti (OR
5) nX ₄ -n (wherein R 5 is an alkyl group having 1 to 4 carbon atoms, X is a chlorine, bromine or iodine atom, and n is 0 or 1).
1 to 2 or more of the titanium halides or the alkoxytitanium halides represented by 1 to 3).

Specifically, TiC is used as a titanium halide.
titanium tetrahalide such as l ₄ , TiBr ₄ and TiI ₄ , and Ti (OCH ₃ ) as an alkoxy titanium halide
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) 2Cl 2, Ti} (OC 2 H 5) 2Cl 2,
_{Ti (OC 3 H 7) 2Cl} 2, Ti (On -C 4 H 9)
2Cl ₂ , Ti (OCH ₃ ) 3Cl, Ti (OC
₂ H ₅ ) 3Cl, Ti (OC ₃ H ₇ ) 3Cl, Ti (O
n -C ₄ H ₉₎ 3Cl, and the like. Among them, titanium tetrahalide is preferable, and TiCl ₄ is particularly preferable.
Is. You may use these titanium compounds 1 type (s) or 2 or more types.

The electron-donating compound used for preparing the solid catalyst component (A) in the present invention is an organic compound containing oxygen or nitrogen, and specific examples thereof include alcohols, phenols, ethers, Esters, ketones, acid halides, aldehydes, amine acids, amides, nitriles, isocyanates, Si-
Examples thereof include an organosilicon compound containing an O—C bond.

More specifically, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol and dodecanol, phenols such as phenol and cresol, dimethyl ether, diethyl ether and dipropyl. Ethers such as ether, dibutyl ether, diamyl ether and diphenyl ether, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate, benzoic acid Monocaps such as propyl, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate Bon acid esters, diethyl maleate, dibutyl maleate, dimethyl adipate,
Diethyl adipate, dipropyl adipate, dibutyl adipate, dimethyl adipate, diisodecyl adipate, dioctyl ampicate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, phthalic acid Dicarboxylic acid esters such as diheptyl, dioctyl phthalate, dinonyl phthalate and didecyl phthalate; acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, ketones such as benzophenone, acid halides such as phthalic acid dichloride, terephthalic acid dichloride, acetaldehyde , Propionaldehyde, octyl aldehyde, benzaldehyde and other aldehydes,
Examples thereof include amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine, and nitriles such as acetonitrile, benzonitrile and tolunitrile.

Further, as the organosilicon compound having a Si--O--C bond, trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane. , Tri-iso-butylmethoxysilane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxy. Silane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-
iso-propyldiethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2 -Ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane Silane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclope Chill isopropyl dimethoxysilane, cyclohexyl (n- pentyl) dimethoxysilane, cyclopentyl Louis Seo-butyl dimethoxysilane, diphenyl dimethoxysilane, diphenyl diethoxy silane, phenylmethyl dimethoxysilane, phenylmethyl diethoxy silane, phenylethyl dimethoxysilane,
Phenylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldimethylethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, Cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (n-butyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, Cyclohexyl (n-butyl) diethoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, n- Butyltrimethoxysilane, iso-butyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane,
Cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, etc. Used.

As the electron-donating compound used for preparing the solid catalyst component (A) of the present invention, esters are preferably used, and a diester of phthalic acid is particularly preferable.
Specific examples of the diester of phthalic acid include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate and di-n-.
Butyl phthalate, di-iso-butyl phthalate, ethyl methyl phthalate, methyl (iso-propyl) phthalate, ethyl-n-propyl phthalate, ethyl-
n-butyl phthalate, di-n-pentyl phthalate,
Di-iso-pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2-methylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, di- iso-decyl phthalate, bis (2,2-dimethylheptyl) phthalate, n-butyl (iso-hexyl) phthalate, n-butyl (iso
-Octyl) phthalate, n-pentylhexylphthalate, n-pentyl (iso-hexyl) phthalate,
iso-pentyl (heptyl) phthalate, n-pentyl (isooctyl) phthalate, n-pentyl (isononyl) phthalate, iso-pentyl (n-decyl) phthalate, n-pentyl (undecyl) phthalate, i
so-pentyl (iso-hexyl) phthalate, n-
Hexyl (iso-octyl) phthalate, n-hexyl (iso-nonyl) phthalate, n-hexyl (n-
Decyl) phthalate, n-heptyl (iso-octyl) phthalate, n-heptyl (iso-nonyl) phthalate, n-heptyl (neo-decyl) phthalate,
Iso-octyl (iso-nonyl) phthalate is illustrated, and 1 type (s) or 2 or more types of these are used.

The solid catalyst component (A) can be prepared by contacting the above-mentioned magnesium compound, titanium compound, and electron-donating compound,
A conventionally known method can be appropriately selected and used as the contact method.

Known methods for preparing the solid catalyst component are described in, for example, JP-A Nos. 63-308004, 63-314211 and 64-6006.
No. 64-14210, No. 64-43506, No. 63-3010, and No. 62-158704.

A typical method for preparing the solid catalyst component (A) is as follows. (1) After dissolving magnesium chloride in tetraalkoxytitanium, polysiloxane is contacted to obtain a solid component. A method for preparing a solid catalyst component by reacting the solid component with silicon tetrachloride, then catalytically reacting with phthalic acid chloride, and then reacting with titanium tetrachloride. Alternatively, the solid catalyst component is prepolymerized with an organoaluminum compound, an organosilicon compound and an olefin to obtain a solid catalyst component.

(2) After anhydrous magnesium chloride and 2-ethylhexyl alcohol were reacted to form a uniform solution,
The solution is contacted with phthalic anhydride. Next, this solution is subjected to catalytic reaction with titanium tetrachloride and phthalic acid diester to obtain a solid component, and titanium tetrachloride is further contacted with the solid component to prepare a solid catalyst component.

(3) Metal magnesium, butyl chloride and butyl ether are reacted to synthesize an organomagnesium compound. Tetrabutoxytitanium and tetraethoxysilane are contact-reacted with the organomagnesium compound to obtain a solid product. A phthalic acid diester, dibutyl ether and titanium tetrachloride are catalytically reacted with the solid product to prepare a solid catalyst component. Alternatively, the solid catalyst component is prepolymerized with an organoaluminum compound, an organosilicon compound and an olefin to obtain a solid catalyst component.

(4) An organomagnesium compound such as dibutylmagnesium and an organoaluminum compound are brought into contact with an alcohol (eg butanol, 2-ethylhexyl alcohol, etc.) in the presence of a hydrocarbon solvent to form a uniform solution. To this solution, a silicon compound (eg SiCl ₄ , H 2
(SiCl ₃ , polysiloxane, etc.) is contacted to obtain a solid component. Next, titanium tetrachloride and phthalic acid diester are catalytically reacted with this solid component in the presence of an aromatic hydrocarbon solvent, and then titanium tetrachloride is further contacted to obtain a solid catalyst component.

(5) Magnesium chloride, tetraalkoxytitanium, and an aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon to form a homogeneous solution, titanium tetrachloride is added to the solution, and then the temperature is raised to a solid. Precipitate the ingredients. Then, the solid component is brought into contact with a phthalic acid diester and then further reacted with titanium tetrachloride to prepare a solid catalyst component.

(6) Metal magnesium powder, an alkyl monohalide and iodine are subjected to catalytic reaction, and the resulting reaction product is contacted with tetraalkoxytitanium, an acid halide and an aliphatic alcohol in the presence of an aliphatic hydrocarbon. The reaction is made into a homogeneous solution, titanium tetrachloride is added to the solution, and then the temperature is raised to precipitate a solid component. A phthalic acid diester is brought into contact with the solid component and further reacted with titanium tetrachloride to prepare a solid catalyst component.

(7) Diethoxymagnesium is suspended in an alkylbenzene or halogenated hydrocarbon solvent to form a suspension, and titanium tetrachloride is brought into contact with the suspension,
Thereafter, the temperature is raised to bring the phthalic acid diester into contact with it, and then the reaction is carried out to obtain a solid component. After washing the solid component with alkylbenzene, titanium tetrachloride is contacted again in the presence of alkylbenzene to prepare a solid catalyst component. Alternatively, the solid catalyst component is heat-treated in the presence or absence of a hydrocarbon solvent to obtain a solid catalyst component.

(8) Diethoxymagnesium is suspended in alkylbenzene to form a suspension, and the suspension is catalytically reacted with titanium tetrachloride and phthalic acid chloride to obtain a solid component. Then, the solid component is washed with alkylbenzene, and then titanium tetrachloride is contacted again in the presence of alkylbenzene to prepare a solid catalyst component. Alternatively, the solid catalyst component is contacted with titanium tetrachloride two or more times to obtain the solid catalyst component.

(9) Diethoxymagnesium, calcium chloride and a silicon compound represented by Si (OR6) ₄ (R6 is an alkyl group or an aryl group) are co-ground and the ground solid product obtained is suspended in an aromatic hydrocarbon. The solid catalyst component is prepared by making it turbid and then catalytically reacting with titanium tetrachloride and a diester of an aromatic dicarboxylic acid, and then further contacting with titanium tetrachloride.

(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 the solid component is washed with alkylbenzene, titanium tetrachloride is contacted again in the presence of alkylbenzene to prepare a solid catalyst component.

(11) A solid catalyst component is prepared by catalytically reacting 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. To do.

(12) Titanium tetrachloride is brought into contact with a suspension formed by suspending diethoxymagnesium in an alkylbenzene or halogenated hydrocarbon solvent, and then heated to bring phthalic acid diester into contact. ,
Further reaction is performed to obtain a solid component. After washing the solid component with alkylbenzene, in the presence of alkylbenzene,
A method of preparing a solid catalyst component by contacting titanium tetrachloride again, wherein aluminum chloride is contacted to prepare a solid catalyst component at any of the preparation stages.

(13) Titanium tetrachloride is brought into contact with a suspension formed by suspending diethoxymagnesium in an alkylbenzene or halogenated hydrocarbon solvent, and then heated to raise the temperature of two or more alkyl groups. After contacting phthalic acid diesters having different carbon numbers, they are reacted to obtain a solid component. Then, the solid component is washed with alkylbenzene, and then titanium tetrachloride is contacted again in the presence of alkylbenzene to prepare a solid catalyst component. Alternatively, in the preparation of the solid catalyst component, a method in which two or more kinds of phthalic acid diesters having different carbon numbers of alkyl groups are brought into contact again with the second contact with titanium tetrachloride. Alternatively, a method of using the above-mentioned electron donating compound other than phthalic acid diester in combination with phthalic acid diester.

(14) Diethoxymagnesium, titanium tetrachloride and phthalic acid diester are catalytically reacted in the presence of chlorobenzene, then titanium tetrachloride and phthalic acid dichloride are catalytically reacted, and then further reacted with titanium tetrachloride. Then, a solid catalyst component is prepared. Alternatively, the solid catalyst component is again contacted with titanium tetrachloride. Furthermore also in any of the preparation of said solid catalyst component,
A method of contacting a silicon compound.

(15) Diethoxymagnesium, 2-ethylhexyl alcohol and carbon dioxide are catalytically reacted in the presence of toluene to give a homogeneous solution. Next, titanium tetrachloride and phthalic acid diester are contact-reacted with this solution to obtain a solid component, which is dissolved in tetrahydrofuran to precipitate the solid component. Then, this solid component is catalytically reacted with titanium tetrachloride or, if necessary, the catalytic reaction with titanium tetrachloride is repeated to prepare a solid catalyst component. Alternatively, a silicon compound (for example, tetrabutoxysilane) is brought into contact with the solid catalyst component at any time during the preparation thereof.

In preparing the solid catalyst component (A) of the present invention, the amounts of each component, that is, the magnesium compound, the titanium compound and the electron-donating compound, cannot be unconditionally specified because they differ depending on the preparation method. The titanium compound is 0.5 to 100 moles, preferably 1 to 10 moles, and the electron-donating compound is 0.1 to 1 mole of the compound.
It is 0 to 1 to 3 mol, preferably 0.02 to 1 mol.

Organoaluminum Compound (B); Next, as the organoaluminum compound (B) used in the present invention, a compound represented by the general formula R7yAlY3-y (in the formula,
R7 may be a C1-4 alkyl group, Y may be hydrogen, chlorine, bromine, or iodine, and y may be a compound represented by 0 <y ≦ 3).

Such an organoaluminum compound (B)
As, triethyl aluminum, diethyl aluminum chloride, tri-iso-butyl aluminum,
Diethyl aluminum bromide, ethyl aluminum hydride and the like can be mentioned, and one kind or two or more kinds can be used. Preferably triethylaluminum, tri-is
o-Butyl aluminum.

Organosilicon compound (C): As the organosilicon compound (C) used in the present invention, an organosilicon compound represented by the following general formula 3 is used.

[0054]

[Chemical 3]

However, in the chemical formula 3, R1 and R2 are alkyl groups having 1 to 3 carbon atoms, and R1 and R2 are the same or different. R3 and R4 are each hydrogen, an alkyl group having 1 to 3 carbon atoms or a halogen atom, and R3 and R4
4 are the same or different. m and n are 0 or 1 to 2
N is an integer of 1 to 2 when m is 0
When is 0, m is an integer of 1-2.

That is, an asymmetric or symmetric organosilicon compound containing two cyclohexyl groups or derivatives thereof, preferably an asymmetric type containing a dialkoxysilicon compound in which two cyclohexyl groups or derivatives thereof are directly bonded to silicon atoms. Alternatively, it is a symmetrical organosilicon compound. By combining the organosilicon compound (C) with the solid catalyst component (A) and the organoaluminum compound (B), an olefin polymer having an extremely broad molecular weight distribution and a high stereoregularity as compared with conventionally known catalysts. The coalescence can be produced in high yield.

As specific examples of these organosilicon compounds (C), various compounds can be used, but alkyl groups such as methyl group or ethyl group at the 3-position, 4-position and 5-position of one cyclohexyl group. It is preferable that one or two groups are substituted, or that a derivative of a cyclohexyl group in which a halogen atom such as chlorine or bromine is substituted at the similar position is contained. The number of the alkyl group or the halogen atom substituting at each of the above positions of these cyclohexyl groups, that is, one position is one or two, and the substitution of the alkyl group at each position is one or plural in combination. Organosilicon compounds containing derivatives of cyclohexyl groups can be used.

Specific examples of these organosilicon compounds include 3-methylcyclohexylcyclohexyldimethoxysilane, 3-methylcyclohexylcyclohexyldiethoxysilane, 3-methylcyclohexylcyclohexyldipropoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane and 4-methylcyclohexylcyclohexyldimethoxysilane. Methylcyclohexylcyclohexyldiethoxysilane, 4-methylcyclohexylcyclohexyldipropoxysilane, 3,5
-Dimethylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldiethoxysilane, 3,5-dimethylcyclohexylcyclohexyldipropoxysilane, 3,3-dimethylcyclohexylcyclohexyldimethoxysilane, 4,4
-Dimethylcyclohexylcyclohexyldimethoxysilane,

Bis (3-methylcyclohexyl) dimethoxysilane, bis (3-methylcyclohexyl) diethoxysilane, bis (3-methylcyclohexyl) dipropoxysilane, 3-methylcyclohexyl (4-methylcyclohexyl) dimethoxysilane, 3- Methylcyclohexyl (4-methylcyclohexyl) diethoxysilane, 3-methylcyclohexyl (4-methylcyclohexyl) dipropoxysilane, 3-methylcyclohexyl (3,3-dimethylcyclohexyl) dimethoxysilane, 3-methylcyclohexyl (3,3- Dimethylcyclohexyl) diethoxysilane, 3-methylcyclohexyl (3,3-dimethylcyclohexyl) dipropoxysilane, 3-methylcyclohexyl (4,4-dimethylcyclohexyl) di Toxysilane, 3-methylcyclohexyl (4,4-dimethylcyclohexyl) diethoxysilane, 3-methylcyclohexyl (4,4-dimethylcyclohexyl) dipropoxysilane, 3-methylcyclohexyl (3,5-dimethylcyclohexyl) dimethoxysilane, 3 -Methylcyclohexyl (3,5-dimethylcyclohexyl) diethoxysilane, 3-methylcyclohexyl (3,5-dimethylcyclohexyl) dipropoxysilane,

Bis (4-methylcyclohexyl) dimethoxysilane, bis (4-methylcyclohexyl) diethoxysilane, bis (4-methylcyclohexyl) dipropoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, bis (3 , 5-dimethylcyclohexyl) diethoxysilane, bis (3,5-dimethylcyclohexyl) dipropoxysilane,

3-chlorocyclohexylcyclohexyldimethoxysilane, 4-chlorocyclohexylcyclohexyldimethoxysilane, 3,5-dichlorocyclohexylcyclohexyldimethoxysilane, bis (3-chlorocyclohexyl) dimethoxysilane, bis (4-chlorocyclohexyl) dimethoxysilane, bis (3,5-
Examples thereof include dichlorocyclohexyl) dimethoxysilane, 3-chlorocyclohexyl (4-chlorocyclohexyl) dimethoxysilane, and 3-chlorocyclohexyl (3,5-dichlorocyclohexyl) dimethoxysilane.

Of these, particularly preferred organosilicon compounds are 3-methylcyclohexylcyclohexyldimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 3,5-dimethoxycyclohexylcyclohexyldimethoxysilane, bis (3,5-
Dimethylcyclohexyl) dimethoxysilane. The organosilicon compound (C) can be used alone or in combination of two or more.

Formation of catalyst: In the polymerization method of the present invention, olefins are polymerized or co-polymerized in the presence of a catalyst comprising the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C). Polymerize.
The ratio of the amount of each component used is arbitrary and is not particularly limited as long as it does not affect the effects of the present invention, but the organoaluminum compound (B) is usually the same as that of the solid catalyst component (A). 1 mol per mol of titanium atom in
.About.500, the organosilicon compound (C) is used in a range of 0.002 to 0.5 in terms of molar ratio per mole of the component (B).

Table 1 shows a preferable combination of the components of the olefin polymerization catalyst of the present invention, that is, the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C). .

[0065]

[Table 1]

Polymerization method: The polymerization in the method of the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer can be used in either gas or liquid state. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Further, both continuous polymerization method and batch polymerization method are possible. Furthermore, the polymerization reaction may be carried out in one stage or in multiple stages of two or more stages.

Further, the olefins polymerized or copolymerized by the method of the present invention include ethylene, propylene, 1
-Butene, 1-pentene, 4-methyl-1-pentene,
Examples thereof include vinylcyclohexane, and these olefins may be used alone or in combination of two or more kinds. Among them, when the homopolymerization of propylene or the copolymerization of propylene and ethylene is carried out using the catalyst according to the present invention, an olefin polymer having high stereoregularity and a wide molecular weight distribution is obtained in a high yield. To be

Furthermore, in the present invention, the catalytic activity upon olefin polymerization (also referred to as main polymerization) carried out using a catalyst comprising the solid catalyst component (A), the organosilicon compound (B) and the organosilicon compound (C), In order to further improve the stereoregularity and the particle properties of the resulting polymer, it is preferable to carry out preliminary polymerization prior to polymerization. As the monomer for the prepolymerization, not only ethylene and propylene but also styrene, vinylcyclohexane and the like can be used.

[0069]

When the olefin polymerization is carried out in the presence of the olefin polymerization catalyst formed by the present invention, the weight average molecular weight (Mw) of the olefin polymer produced is
The value obtained by dividing by the number average molecular weight (Mn), that is, the molecular weight distribution is at least 1 or more higher than that of the polymer obtained by the conventionally known method, and the value of the stereoregular polymer is extremely high. Shows. That is, it was confirmed that a polyolefin having a wide molecular weight distribution of the produced polymer and a high stereoregularity can be obtained in an extremely high yield.

[0070]

EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples.

Example 1 Preparation of solid catalyst component (A); 10 g of diethoxymagnesium and 80 ml of toluene were charged and suspended in a 200 ml round-bottomed flask fully replaced with nitrogen gas and equipped with a stirrer. It was in a state. Then, 20 ml of titanium tetrachloride was added to the suspension and the temperature was raised. When the temperature reached 80 ° C., 2.7 ml of di-n-butyl phthalate was added and the temperature was further raised to 1
It was set to 10 ° C. After that, the reaction was carried out while stirring at a temperature of 110 ° C. for 2 hours. 90 after completion of reaction
It was washed twice with 100 ml of toluene at 0 ° C., 20 ml of titanium tetrachloride and 80 ml of toluene were newly added, the temperature was raised to 100 ° C., and the reaction was carried out while stirring for 2 hours. 40 after completion of the reaction
The solid catalyst component was obtained by washing 10 times with 100 ml of n-heptane at 0 ° C. The solid content in the solid catalyst component was separated, and the titanium content in the solid content was measured to be 2.91.
% By weight.

Formation and Polymerization of Polymerization Catalyst: Triethylaluminum was added to an autoclave equipped with a stirrer and having an internal volume of 2.0 liter, which was completely replaced with nitrogen gas. 32 mmol, 3
0.13 mmol of -methylcyclohexylcyclohexyldimethoxysilane and 0.0066 mmol of the above solid catalyst component as titanium atom were charged to form a polymerization catalyst.
After that, hydrogen gas 1.8 liters, liquefied propylene 1.4
A liter was charged and a polymerization reaction was carried out at 70 ° C. for 30 minutes.
The properties of the obtained polymer are shown in Table 2.

The properties of the polymers shown in Table 2 are as follows: after the completion of the polymerization reaction, the weight of the produced polymer is defined as (a), and the weight of the undissolved polymer when extracted with boiling n-heptane for 6 hours. The weight of the combined product was (b), and the polymerization activity, the yield of the total crystalline polymer, and the molecular weight distribution were determined by the following formulas.

[0074]

[0075]

[0076]

Example 2 An experiment was conducted in the same manner as in Example 1 except that bis (3-methylcyclohexyl) dimethoxysilane was used instead of 3-methylcyclohexylcyclohexyldimethoxysilane used in forming the polymerization catalyst. It was The obtained results are also shown in Table 2.

Example 3 An experiment was conducted in the same manner as in Example 1 except that 4-methylcyclohexylcyclohexyldimethoxysilane was used instead of 3-methylcyclohexylcyclohexyldimethoxysilane used in forming the polymerization catalyst. The obtained results are also shown in Table 2.

Example 4 Instead of 3-methylcyclohexylcyclohexyldimethoxysilane used in forming the polymerization catalyst, 3,5-
An experiment was conducted in the same manner as in Example 1 except that dimethylcyclohexylcyclohexyldimethoxysilane was used. The obtained results are also shown in Table 2.

Example 5 Preparation of solid catalyst component (A); 20 ml of titanium tetrachloride and 30 ml of toluene were charged into a round bottom flask having a capacity of 200 ml, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, to prepare a mixed solution. Was formed. Then, a suspension formed by using 10 g of spherical diethoxymagnesium, 50 ml of toluene and 3.6 ml of di-n-butyl phthalate was added to the mixed solution, and the temperature was raised to 90 ° C. The reaction was carried out with stirring for a time. After completion of the reaction, the obtained reaction product is heated to 90 ° C
Was washed twice with 100 ml of toluene, and 20 ml of titanium tetrachloride and 80 ml of toluene were newly added, and the temperature was raised to 110 ° C. and the reaction was carried out while stirring for 2 hours. 40 after completion of the reaction
The solid catalyst component was obtained by washing 10 times with 100 ml of n-heptane at 0 ° C. The solid content in the solid catalyst component was separated and the titanium content in the solid content was measured to be 2.56.
% By weight.

Polymerization catalyst formation and polymerization: Polymerization was carried out in the same manner as in Example 2 except that the solid catalyst component prepared as described above was used. The obtained results are also shown in Table 2.

Example 6 Preparation of solid catalyst component (A); 10 g of diethoxymagnesium and 80 ml of toluene were charged and suspended in a 200 ml round-bottomed flask which was sufficiently replaced with nitrogen gas and equipped with a stirrer. It was in a state. Then, 20 ml of titanium tetrachloride was added to the suspension solution, the temperature was raised, and when the temperature reached 60 ° C,
Add 1.0 ml of diethyl phthalate and heat up to 11
When the temperature reached 0 ° C, 2.5 ml of dioctyl phthalate was added, and the temperature was raised to 112 ° C. After that, the reaction was performed while stirring at a temperature of 112 ° C. for 1.5 hours. After completion of the reaction, it was washed twice with 100 ml of toluene at 90 ° C., and newly 20 ml of titanium tetrachloride and 80 ml of toluene.
Was added, the temperature was raised to 100 ° C., and the reaction was carried out while stirring for 2 hours. After completion of the reaction, 1 with 100 ml of n-heptane at 40 ° C.
The solid catalyst component was obtained by washing 0 times. The solid content in the solid catalyst component was separated, and the titanium content in the solid content was measured to be 2.40% by weight.

Polymerization catalyst formation and polymerization: Polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component prepared as described above was used, and the obtained results are also shown in Table 2.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that phenyltriethoxysilane was used instead of 3-methylcyclohexylcyclohexyldimethoxysilane used during polymerization. The obtained results are also shown in Table 2.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that cyclohexylmethyldimethoxysilane was used instead of 3-methylcyclohexylcyclohexyldimethoxysilane used during polymerization. The obtained results are also shown in Table 2.

[0086]

[Table 2]

[0087]

The olefin polymerization catalyst of the present invention comprises a specific solid catalyst component (A), an organoaluminum compound (B) and an organosilicon compound (C) containing a cyclohexyl group or a derivative thereof. By polymerizing olefins in the presence of the olefin polymerization catalyst, an olefin polymer having high stereoregularity, a wide molecular weight distribution and excellent moldability can be obtained in high yield.

[Brief description of drawings]

FIG. 1 is a schematic flowchart illustrating the configuration of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-5-301918 (JP, A) JP-A-6-1565759 (JP, A) JP-A-6-166717 (JP, A) JP-A-2- 84404 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08F 4/60-4/70 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A catalyst for olefin polymerization, which is formed from the following components (A), (B) and (C). (A) Dissolve dialkoxymagnesium in alkylbenzene
The suspension is suspended in a medium to form a suspension , and titanium tetrachloride is brought into contact with the suspension, followed by heating to bring it into contact with a phthalic acid diester, followed by reaction to obtain a solid component. Is washed with alkylbenzene and then contacted with titanium tetrachloride again in the presence of alkylbenzene (B) Organoaluminum compound (C) 3-methylcyclohexylcyclohexyldimethoate
Kishishiran, bis (3-Mechirushi Kurohekishiru) dimethoxysilane, and one or more organic silicon compound selected from 4-methylcyclohexyl cyclohexyldimethoxysilane 2. The following components (A), (B) and (C):
An olefin polymerization catalyst, characterized in that it is formed from (A) Dissolve dialkoxymagnesium in alkylbenzene
After contacting the titanium tetrachloride to form made suspension by suspending in medium causes then contacting the different phthalic acid diester having a carbon number of heating of two or more alkyl groups, is reacted To obtain a solid component, which is washed with alkylbenzene, and then contacted with titanium tetrachloride again in the presence of alkylbenzene to prepare a solid catalyst component (B) organoaluminum compound (C) 3-methylcyclohexylcyclohexyldiene Met
Xysilane