JPH10218928A - Olefin polymerization catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymn. catalyst which improves the stereoregularity or crystallinity of a base polymer itself by combining a solid catalyst component essentially contg. magnesium, titanium, an electron-donating compd., and a halogen with an organoaluminum compd. and a carbonyl compd. SOLUTION: The solid catalyst component is prepd. by bringing a magnesium compd., a titanium compd., and an electron-donating compd. into contact with each other. A compd. represented by formula I (wherein R<1> is 1-4C alkyl; Y is H, Cl, Br, or I; and 0<q<=3) is used as the organoaluminum compd. The carbonyl compd. is represented by formula II [wherein A<2> is R<2> -(O)x2 , or a group represented by formula III; A<3> is R<3> -(O)x3 -; A<4> is R<4> -(O)x4 -; A<5> is H or R<5> -(O)x5 -(C=O)y5 -; R<2> to R<5> are each a 1-20C hydrocarbon group optionally having O, F, or Si; L<2> is 1-8C alkylene; x2 to x5, y5, and z2 are each 0 or 1; and n is 5-100,000]. Copolymn. is conducted in the presence of a catalyst comprising these ingredients.

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, and particularly to a high-performance polymer capable of obtaining a polymer having high stereoregularity when used for polymerization of propylene in a high yield. It relates to a catalyst system.

[0002]

2. Description of the Related Art Conventionally, in the polymerization of olefins,
Magnesium, titanium, an olefin polymerization catalyst comprising an organic aluminum compound and a solid catalyst component containing an electron-donating compound and a halogen as essential components, and an olefin for polymerizing or copolymerizing olefins in the presence of the catalyst. Many polymerization methods have been proposed.

[0003] Each of the above-mentioned prior arts has a high activity enough to omit a so-called deashing step for removing catalyst residues such as chlorine and titanium remaining in a produced polymer, and also has 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.

[0004] Incidentally, a propylene polymer obtained by using the above-mentioned catalyst, a so-called crystalline polypropylene, has high rigidity and generally has a high heat deformation temperature, melting point and crystallization temperature, so that it exhibits excellent heat resistance. It is used for various uses such as molded articles such as automobiles and home electric appliances, containers and films.

However, in recent years, there has been an urgent need to reduce the weight of plastics used in automobiles, home electric appliances and the like in order to save energy resources due to global environmental problems.
In order to solve this problem, it is necessary to reduce the thickness of the plastic while maintaining strength such as impact resistance. In order to solve this problem, it is important to improve the crystallinity of the base polymer and the rigidity of the resin by the polymerization technique in addition to the improvement by the polymer compounding technique to solve this problem.

[0006]

However, the above-mentioned prior art is not enough to solve the above-mentioned problems, and a catalyst component for olefin polymerization which can further improve the stereoregularity or crystallinity of the base polymer itself. The development of a catalyst was desired.

[0007] That is, an object of the present invention is to provide an olefin polymerization catalyst capable of improving the stereoregularity or crystallinity of the base polymer itself.

[0008]

The present inventors have conducted various studies to solve the problems left in the prior art, and as a result,
By using an olefin polymerization catalyst formed from a solid catalyst component prepared by contacting a specific component, it was confirmed that a polymer having high stereoregularity could be obtained in high yield, and the present invention was completed.

That is, the olefin polymerization catalyst provided by the present invention is characterized by being formed using the following components (A) to (C).

(A) A solid catalyst component containing magnesium, titanium, an electron donating compound and a halogen as essential components formed by contacting a magnesium compound, a titanium compound and an electron donating compound. (B) a general formula R ¹ _q AlY _3-q (wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms, Y is a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom;
q is a positive number satisfying 0 <q ≦ 3. (C) a carbonyl compound represented by the following general formula (I)

Embedded image Here, A ² : R ² — (O) _x2 — or the following substituent

Embedded image ^{A 3: R 3 - (O} ) x3 - A 4: R 4 - (O) x4 - A 5: hydrogen atom or _{^{R 5 - (O) x5 -}} (C = O) y5 - wherein, R ² to R ⁵ represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms having or not having at least one of an oxygen atom, a fluorine atom and a silicon atom, and two of R ^{2 to} R ⁵ May form a ring with a hydrocarbon group corresponding to L ² represents an alkylene group having 1 to 8 carbon atoms. x2, x3, x4, x5, y5 and z2 are each independently 0 or 1. n is 5 to 100,000
Is an integer.

When the carbonyl compound represented by the general formula (I) shows an enol type tautomer, the enol type compound is also included. When n in the general formula of the above substituent is 10 or more, the carbonyl compound may be a homopolymer or a block copolymer comprising a plurality of segments comprising the substituent, A ³ , A ⁴ and / or A ^5. Including polymers.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The component (A) of the catalyst of the present invention, that is, a solid catalyst component (hereinafter sometimes referred to as a solid catalyst component (A)) is brought into contact with a magnesium compound, a titanium compound and an electron donating compound. Thus, magnesium, titanium, an electron donating compound, and a halogen formed as essential components are contained.

The solid catalyst component (A) is prepared by contacting a magnesium compound, a titanium compound and an electron donating compound as described below.

In the present invention, the magnesium compound used for preparing the solid catalyst component (A) includes magnesium halide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium or diaryloxymagnesium, alkoxymagnesium halide, 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, butyl ethyl magnesium and the like. ,
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 dialkoxymagnesium or diaryloxymagnesium include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, diphenoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium and the like. Can be.

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

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

As the magnesium compound in the present invention, the above-mentioned magnesium compounds can be used alone or in combination of two or more.

In the present invention, among these, magnesium halide and dialkoxymagnesium are preferred, and particularly preferred are magnesium chloride, diethoxymagnesium and dipropoxymagnesium.

Further, in the present invention, among the magnesium compounds used for preparing the solid catalyst component (A),
The above dialkoxymagnesium has 1 to 3 carbon atoms.
And any one or more of the dialkoxymagnesiums in the form of granules or powder. The shape may be irregular or spherical. When a spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrower particle size distribution is obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved, and is included in the produced polymer powder. Troubles such as clogging caused by the fine powder are eliminated.

The above-mentioned spherical dialkoxymagnesium does not necessarily have to be a true sphere, but an oval or potato-shaped one is used. Specifically, the degree of the spherical shape of the particles is 3 or less, preferably 1 to 2, more preferably 1 to 1. 1 / w, expressed as the ratio of the major axis diameter l to the minor axis diameter w, 1 / w. 5

The average particle size of the dialkoxymagnesium may be from 1 to 200 microns. Preferably, it is between 5 microns and 150 microns. Further, its specific surface area is 5 to 50 m ² / g, preferably 10 to 40 m ² / g, more preferably 15 to 30 m ² / g.

When a spherical dialkoxymagnesium is used among the above dialkoxymagnesium, its average particle size is 1 to 100 microns, preferably 5 to 100 microns.
Microns to 50 microns, more preferably 1 micron.
0 microns to 40 microns. Further, as for the particle size, it is desirable to use a fine particle or coarse powder having a small particle size distribution. Specifically, particles of 5 microns or less are 20% or less, preferably 10% or less, and particles of 100 microns or more are 10% or less, preferably 5% or less. Further, the particle size distribution is expressed by ln (D
90 / D10) (where D90 is the particle size at 90% of the integrated particle size and D10 is the particle size at 10% of the integrated particle size), and is 3 or less, preferably 2 or less. .

Further, when a spherical dialkoxymagnesium is used, one having a bulk density of 0.20 to 0.35 g / ml measured according to JIS K6721 is usually used. Generally, when olefin polymerization is carried out using a solid catalyst component using the spherical bulk alkoxymagnesium having a high bulk density, a polymer having a higher bulk density can be obtained, but in the present invention, the bulk density of the spherical dialkoxymagnesium is relatively high. Even if a polymer having a low density, for example, less than 0.20 g / ml, is used, the bulk density of a polymer polymerized using the solid catalyst component using the same does not decrease, and a polymer having a high bulk density can be obtained.

The dialkoxymagnesium does not necessarily need 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,
Those obtained by reacting metal magnesium and alcohol in the presence of a catalyst such as iodine may be used.

The component (b) used for preparing the solid catalyst component (A) of the present invention is a tetravalent halogen-containing titanium compound (hereinafter sometimes referred to as "component (b)"). ,
Titanium halide or alkoxy titanium halide. Specifically, as titanium tetrahalide, TiC
l ₄ , TiBr ₄ , TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC
_{2 H 5) Cl 3, Ti} (OC 3 H 7) Cl 3, Ti (O
_{n-C 4 H 9) Cl} 3, Ti (OCH 3) 2 Cl 2, T
i (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 (OC
H 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 these, titanium tetrahalide is preferable, and TiCl ₄ is particularly preferable. Two or more of these components (b) may be used, and they may be used by dissolving and diluting in an organic solvent such as an aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as hexane or heptane. Is also good.

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

Further, in the present invention, the electron donating compound used for preparing the solid catalyst component (A) includes:
Organic compounds containing oxygen or nitrogen atoms,
Specific examples thereof include alcohols, phenols, ethers, esters, ketones, acid halides, acid anhydrides, aldehydes, amines, amides,
Examples thereof include nitriles, isocyanates, organosilicon compounds having a Si—O—C bond, and silicon halide compounds.

More specifically, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol and dodecanol, phenols such as phenol and cresol, methyl ether, ethyl ether and propyl Ethers such as ether, butyl ether, amyl ether and diphenyl ether, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, Octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, P-methoxyethyl benzoate P- ethoxyethyl benzoate, monocarboxylic acid esters such as anisic acid methyl, ethyl anisate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, di -
iso-butyl, di-iso-decyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, phthalic acid Dinonyl, didecyl phthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate,
Dihexyl terephthalate, dioctyl terephthalate, dicarboxylic acid esters such as didecyl terephthalate, acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, ketones such as benzophenone, phthalic acid dichloride, acid halides such as terephthalic acid dichloride,
Acid anhydrides such as phthalic anhydride and maleic anhydride, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, acetonitrile, benzonitrile And nitriles such as tolunitrile.

Examples of the organosilicon compound containing a Si—O—C bond include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, and 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, cyclohexylethyldimethoxy Silane, cyclohexyl (iso-propyl) dimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, Black pentyl ethyldiethoxysilane, cyclopentyl (an iso-propyl) dimethoxysilane, cyclohexyl (n- pentyl) dimethoxysilane, cyclopentyl (an iso-butyl) dimethoxysilane, cyclohexyl cyclopentyl dimethoxy silane, cyclohexyl cyclopentyl distearate ethoxysilane,
Diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldimethylethoxysilane, cyclohexyldiethylmethoxysilane,
Cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, cyclopentylethyldimethoxysilane,
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, is
o-propyltrimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, i
so-butyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane and the like are used.

Examples of the silicon halide compound include SiC
l ₄ , SiBr ₄ , SiI ₄ , SiF ₄ , HSiCl ₃
And the like.

Further, the carbonyl compound used as the component (C) of the present invention can be used as an electron donating compound of the solid catalyst component (A).

Among the above compounds, the electron donating compounds used for preparing the solid catalyst component (A) of the present invention include:
Esters are preferably used, and phthalic acid diester is particularly preferred. 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, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate, ethyl methyl phthalate, butyl ethyl phthalate, Methyl (i
(so-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-isodecyl phthalate, bis (2,2-dimethylheptyl) phthalate, n- Butyl (iso-hexyl) phthalate, ethyl (iso-octyl) phthalate, n-butyl (is
o-octyl) phthalate, n-pentylhexyl phthalate, n-pentyl (iso-hexyl) phthalate, iso-pentyl (heptyl) phthalate, n-pentyl (iso-octyl) phthalate, n-pentyl (iso-nonyl) phthalate, iso-pentyl (n
-Decyl) phthalate, n-pentyl (undecyl) phthalate, iso-pentyl (iso-hexyl) phthalate, n-hexyl (iso-octyl) phthalate, n-hexyl (iso-nonyl) phthalate, n-
Hexyl (n-decyl) phthalate, n-heptyl (i
(so-octyl) phthalate, n-heptyl (iso-
Nonyl) phthalate, n-heptyl (neo-decyl)
Examples thereof include phthalate, iso-octyl (iso-nonyl) phthalate, dibenzyl phthalate, n-butylbenzyl phthalate, ethyl benzyl phthalate, and dicyclohexyl phthalate, and one or more of these are used. Of these, diethyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate and bis (2-ethylhexyl) phthalate are particularly preferably used.

In order to further improve the stereoregularity or crystallinity of the produced polymer, it is preferable to use two or more of the above electron donating compounds. Although the combination is not particularly limited, when phthalic diester is used, the total number of carbon atoms of one phthalic diester alkyl group (two) and the other one or two or more phthalic diester alkyl groups (2 And four or more) are particularly preferably selected and combined so that the difference in the total number of carbon atoms becomes 4 or more.

A specific example of the combination is as follows. (1) Diethyl phthalate and di-n-butyl phthalate (2) Diethyl phthalate and di-iso-butyl phthalate (3) Diethyl phthalate and di-n-octyl phthalate (4) Diethyl phthalate and bis (2-ethylhexyl)
Phthalate (5) di-n-butyl phthalate and di-n-octyl phthalate (6) di-n-butyl phthalate and bis (2-ethylhexyl) phthalate (7) diethyl phthalate, di-n-butyl phthalate and bis (2 -Ethylhexyl) phthalate (8) Diethyl phthalate, di-iso-butyl phthalate and bis (2-ethylhexyl) phthalate The above electron-donating compounds can be used alone or in combination of two or more. You can also.

The solid catalyst component (A) can be prepared by bringing the above-mentioned magnesium compound, titanium compound and electron donating compound into contact, and a known method can be employed.

Known methods for the solid catalyst component are described in, for example, JP-A-63-308004 and 63-31.
Nos. 4211, 64-6006, 64-1
Nos. 4210, 64-43506, 63-3010, and 62-158704.

The solid catalyst component (A) of the present invention is prepared by bringing a magnesium compound, a titanium compound and an electron donating compound as described above into contact with each other.
Although it is possible to carry out the treatment in the absence of an inert organic solvent, it is preferable to carry out the treatment in the presence of the solvent in view of the ease of operation. Examples of the inert organic solvent used include saturated hydrocarbons such as hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and halogens such as ortho-dichlorobenzene, methylene chloride, carbon tetrachloride, and dichloroethane. Hydrocarbon, etc., among which the boiling point is 90 to 150 ° C.
Aromatic hydrocarbons in a liquid state at about normal temperature, specifically, toluene, xylene, and ethylbenzene are preferably used.

As a method for preparing the solid catalyst component (A) of the present invention, a method of 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 in which a compound is suspended in a titanium compound or an inert hydrocarbon solvent to obtain a solid catalyst component, or the like can be employed. Among these, the particles of the solid catalyst component obtained by the former method are almost spherical, and the particle size distribution is sharp. Also, in the latter method, a spherical and sharp particle size distribution of the solid catalyst component can be obtained by using the spherical magnesium compound as described above. By forming particles by a dry method, 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 a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or when dispersed or suspended for denaturation treatment,
40 to 130 when reacting after contact to obtain a product
C. is preferred. If the temperature during the reaction is lower than 40 ° C., the reaction does not proceed sufficiently, and the performance of the solid catalyst component prepared as a result becomes insufficient. If the temperature exceeds 130 ° C., the 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) will be briefly described below with several examples.

(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,
The solution is contacted with phthalic anhydride. 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 in which a phthalic acid diester, dibutyl ether and titanium tetrachloride are contacted with the solid product 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.

(4) An organomagnesium compound such as dibutylmagnesium and an organoaluminum compound are brought into contact with an alcohol (for example, butanol, 2-ethylhexyl alcohol or the like) in the presence of a hydrocarbon solvent to form a uniform solution. A silicon compound (for example, SiC) is added to this solution.
l ₄ , HSiCl ₃ , polysiloxane, etc.)
Obtain a solid component. Then, in the presence of an aromatic hydrocarbon solvent, the solid component is contacted with titanium tetrachloride and a 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 to form a homogeneous solution, and titanium tetrachloride is added to the solution. Is precipitated.
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.

(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 to form a homogeneous solution. Then, 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) Suspending diethoxymagnesium in an alkylbenzene or halogenated hydrocarbon solvent,
Titanium tetrachloride is brought into contact, the temperature is raised, and phthalic acid diester is brought into contact with and reacted 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 heat-treating the solid catalyst component 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. A method of obtaining a solid catalyst component by contacting the solid catalyst component with titanium tetrachloride two or more times.

(9) Diethoxymagnesium, calcium chloride and a silicon compound represented by Si (OR) ₄ (R is an alkyl group or an aryl group) are co-pulverized, and the pulverized solid is suspended in an aromatic hydrocarbon. A method of preparing a solid catalyst component by contacting with titanium tetrachloride and a diester of an aromatic dicarboxylic acid, followed by contact 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. 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.

(11) A solid catalyst component is prepared by contacting a fatty acid such as calcium halide and magnesium stearate with titanium tetrachloride and a diester of an aromatic dicarboxylic acid, and then contacting the titanium tetrachloride. Method. (12) Diethoxymagnesium is suspended in an alkylbenzene or halogenated hydrocarbon solvent, contacted with titanium tetrachloride, heated, and contacted with phthalic diester,
React 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 preparation steps, preparing a solid catalyst component to be brought into contact with aluminum chloride how to.

(13) Diethoxymagnesium is suspended in an alkylbenzene or halogenated hydrocarbon solvent,
Titanium tetrachloride is brought into contact, the temperature is raised, and phthalic acid diesters having two or more alkyl groups having different carbon numbers are brought into contact with each other to react 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 acid dichloride are contact-reacted, and titanium tetrachloride is further contact-reacted. And 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 contacting a silicon compound in any of the preparations of the solid catalyst component.

(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 to obtain a solid component, and this solid component is dissolved in tetrahydrofuran to further precipitate a solid component. Next, titanium tetrachloride is brought into contact with the solid component in a contact reaction, and optionally,
A method of preparing a solid catalyst component by repeatedly performing a contact reaction with titanium tetrachloride. In any of the preparations of the solid catalyst component, a silicon compound (eg, tetrabutoxysilane)
Can also be brought into contact.

(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. This solution is contacted with phthalic anhydride and titanium tetrachloride to obtain a solid component, and further reacted with phthalic acid diester. Then, the solid component is washed with an alkylbenzene, and then contacted again with titanium tetrachloride in the presence of the alkylbenzene to prepare a solid catalyst component.

In preparing the solid catalyst component (A) of the present invention, the amounts of each component, ie, the magnesium compound, the titanium compound and the electron donating compound, vary depending on the preparation method, and therefore cannot be specified unconditionally. For example, 0.5 to 1 titanium compound per mole of magnesium compound
The amount is 00 mol, preferably 1 to 10 mol, and the amount of the electron donating compound is 0.01 to 3 mol, preferably 0.02 to 1 mol.

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. As it is without drying, the component (B) described below,
The catalyst for polymerization of olefins of the present invention is formed in combination with the components (C) and (D).

The organoaluminum compound of the component (B) used in the present invention includes a compound represented by the following general formula: R ¹ _q AlY _{3 -q} (wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, and Y is hydrogen) Atom, chlorine atom, bromine atom or iodine atom,
q is a positive number satisfying 0 <q ≦ 3. The compound represented by ()) is used.

Examples of the component (B) include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide, and ethylaluminum hydride, and one or more of them can be used. Preferred are triethylaluminum and tri-iso-butylaluminum.

Next, as the carbonyl compound of the component (C) used in the present invention, a compound represented by the following general formula (I) is used.

[0065]

Embedded image Here, A ² : R ² — (O) _x2 — or the following substituent

Embedded image ^{A 3: R 3 - (O} ) x3 - A 4: R 4 - (O) x4 - A 5: hydrogen atom or _{^{R 5 - (O) x5 -}} (C = O) y5 - wherein, R ² to R ⁵ represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms having or not having at least one of an oxygen atom, a fluorine atom and a silicon atom, and two of R ^{2 to} R ⁵ May form a ring with a hydrocarbon group corresponding to L ² represents an alkylene group having 1 to 8 carbon atoms. x2, x3, x4, x5, y5 and z2 are each independently 0 or 1. n is 5 to 100,000
Is an integer.

When the carbonyl compound represented by the above general formula (I) shows an enol type tautomer, the enol type compound is also included. When n in the general formula of the substituent is 10 or more, the carbonyl compound may be a homopolymer or a block copolymer comprising a plurality of segments having different substituents, A ³ , A ⁴ and / or A ^5. Including polymers.

Among the carbonyl compounds represented by the above general formulas, carbonyl compounds represented by the following general formulas (II) to (IV) are preferably used.

[0068]

Embedded image Here, A ⁶ is _{^{R 6 - (O) x6 -}} , A 7 is R ⁷ - (O)
_x7 -, A ⁸ is _{^{R 8 - (O) x8 -}} , A 9 is hydrogen atom or R ⁹ - indicates, R ⁶ to R ⁸ each independently contains at least one of oxygen atoms and fluorine atoms Or a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms which does not contain, and a ring may be formed by a hydrocarbon group corresponding to two of R ^{6 to} R ⁸ . R ⁹ represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms containing a fluorine atom. x6, x7, x8 are each independently 0 or 1. When each shows an enol type tautomer, the enol type compound is also included.

[0069]

Embedded image Here, A ¹⁰ is _{^{R 10 - (O) x10 -}} , A 11 is R ¹¹ -
(O) _x11 - or _{(CH 3) m11 (R '} 11 -O) 3-m11
^{Si-L 11 - (O)} z11 -, A 12 is R ¹² - (O) _x12 -
Or _{(CH 3) m12 (R '} 12 -O) 3-m12 Si-L 12 -
(O) _z12 −, and R ^{10 to} R ¹² each independently represent a group having 1 to 2 carbon atoms.
And 0 represents a saturated or unsaturated hydrocarbon group. R ′ ¹¹ and R ′ ¹² each independently represent an alkyl group having 1 to 6 carbon atoms. L ¹¹ and L ¹² each independently have 2 to 2 carbon atoms
And 10 alkylene groups. x10, x11, x12, z11, z12
Is each independently 0 or 1. m11 and m12 are each independently 0, 1 or 2. However, A ¹¹ and A
^At least one of the ^twelve contains a silicon atom. When each shows an enol type tautomer, the enol type compound is also included.

[0070]

Embedded image Here, A ¹³ : the following substituent

Embedded image A ¹⁴ is _{^{R 14 - (O) x14 -}} , A 15 is R ¹⁵ - (O) _x15 -
Is shown.

R ¹⁴ and R ¹⁵ are each independently
A saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, or a fluorine atom-substituted hydrocarbon group of the hydrocarbon group, R ¹⁴
And at least one of R ¹⁵ is the fluorine atom-substituted hydrocarbon group. L ¹³ is an alkylene group having 1 to 8 carbon atoms. x14, x15 and z13 are each independently 0 or 1. n is an integer of 5 to 100,000.

When the carbonyl compound represented by the above general formula (IV) shows an enol type tautomer, the enol type compound is also included. When n in the general formula of the substituent is 10 or more, the carbonyl compound may be a homopolymer or a block copolymer including a plurality of segments having different substituents, A ¹⁴ and / or A ^15. Including. Examples thereof include a block copolymer in which two kinds of the carbonyl compounds are bonded at a terminal methyl group of the substituent.

Further, among the carbonyl compounds represented by the above general formulas (II) to (III), the following general formulas (V) to (VI)
The carbonyl compound represented by I) is particularly preferably used.

[0074]

Embedded image Here, A ¹⁶ is R ¹⁶ − (O) _{× 16} −, and A ¹⁷ is R ¹⁷ −
(O) _x17 -, A ¹⁸ is R ¹⁸ - (O) _x18 - indicates, R ¹⁶
To R ¹⁸ each independently represent a saturated or unsaturated hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms;
A ring may be formed by a hydrocarbon group corresponding to two of R ^{16 to} R ¹⁸ . x16, x17, and x18 are each independently 0 or 1. When each shows an enol type tautomer, the enol type compound is also included.

[0075]

Embedded image Here, A ¹⁹ is _{^{R 19 - (O) x19 -}} , A 20 is (R ^'20 -
^{_{O) 3 Si-L 20 -}} (O) z20 -, A 21 is (R ^'21 -
^{_{O) 3 Si-L 21 -}} (O) z21 - indicates, R ¹⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 saturated or unsaturated. ^R'20 and ^R'21 each independently represent a linear or branched alkyl group having 1 to 6, preferably 1 to 4 carbon atoms. L ²⁰ and L ²¹ are each independently 2 to 10 carbon atoms, preferably 2-5 alkylene group. x19, z20 and z21 are each independently 0 or 1. When each shows an enol type tautomer, the enol type compound is also included.

[0076]

Embedded image Here, A ²² is _{^{R 22 - (O) x22 -}} , A 23 is R ²³ -
(O) _x23 -, A ²⁴ is ^{_{(CH 3) m24 (R '24}} -O)
^{_{3-m24 Si-L 24 -}} (O) z24 - indicates, R ²² and ²³ are each independently 1 to 20 carbon atoms, preferably 1 to 1
And 0 represents a saturated or unsaturated hydrocarbon group. ^R'24 represents an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms.
L ²⁴ is an alkylene group having 2 to 10 carbon atoms. x22, x2
3 and z24 are each independently 0 or 1. m24 is 0,
1 or 2. When each shows an enol type tautomer, the enol type compound is also included.

In the compounds of the above general formulas (I) to (VII), the hydrocarbon group constituting R ^{2 to} R ²³ has 1 to 1 carbon atoms.
Preferred are 20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, aralkyl groups and alkenyl groups, and specific examples include the following groups.

As the alkyl group and the cycloalkyl group,
Methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, iso-butyl, t-butyl, pentyl, iso-pentyl, cyclopentyl, hexyl,
iso-hexyl, cyclohexyl, cyclopentylmethyl, methylcyclopentyl, heptyl, iso-heptyl, cyclohexylmethyl, methylcyclohexyl,
Octyl, iso-octyl, dimethylcyclohexyl, 4-methylcyclohexylmethyl, 1-cyclohexylethyl, 2-cyclohexylethyl, ethylcyclohexyl, nonyl, iso-nonyl, 3-cyclohexylpropyl, decyl, iso-decyl, 4-cyclohexylbutyl, Butylcyclohexyl, 3,3,5,5-
Tetramethylcyclohexyl, undecyl, iso-undecyl, dodecyl, iso-dodecyl, tridecyl,
iso-tridecyl, tetradecyl, iso-tetradecyl, pentadecyl, iso-pentadecyl, hexadecyl, iso-hexadecyl, heptadecyl, iso-
Heptadecyl, octadecyl, iso-octadecyl,
Nonadecyl, icosyl and the like can be mentioned.

The aryl group and the alkylaryl group include phenyl, 2-, 3- or 4-methylphenyl,
-, 3- or 4-ethylphenyl, 2,3-, 2,4-
Or 2,5-dimethylphenyl, 2-, 3- or 4-i
so-propylphenyl, 2,3,5-, 2,3,6-
Or 3,4,5-trimethylphenyl, 2-, 3- or 4-t-butylphenyl, 2-, 3- or 4-iso-
Butylphenyl, 4- or 5-iso-propyl-3-
Methylphenyl, 4-t-amylphenyl, 3-, 4-
Or 5-methyl-2-t-butylphenyl, pentamethylphenyl, naphthyl, 2-methylnaphthyl, 2,6-
Di-iso-propylphenyl, 4-iso-octylphenyl, 2,4-, 2,6- or 3,5-di-t-butylphenyl, di-iso-butylphenyl, 2,6-
Di-t-butyl-4-methylphenyl, 2,4,6-tri-t-butylphenyl and the like.

As the aralkyl group, benzyl, 2-,
3- or 4-methylbenzyl, phenethyl, sec-phenethyl, 2,4-, 2,5-, 3,4- or 3,5-dimethylbenzyl, 4-ethylbenzyl, 2-, 3- or 4-methyl Phenethyl, α- or β-methylphenethyl, α, α-dimethylbenzyl, 1- or 3-phenylpropyl, α- or β-ethylphenethyl, 4-iso
-Propylbenzyl, α-iso-propylbenzyl,
α, α-dimethylphenethyl, 1-, 3- or 4-phenylbutyl, α-ethyl-α-methylbenzyl, 4-butylbenzyl, 4-t-butylbenzyl, 1,1-dimethyl-3-phenylpropyl, 1- or 3-phenyl-
2,2-dimethylpropyl, α-propylphenethyl,
5-phenylpentyl, naphthylmethyl, naphthylethyl, 6-phenylhexyl and the like.

Examples of the alkenyl group include vinyl, allyl,
And propenyl and butenyl.

Further, at least one of the above hydrocarbon groups
Preferred examples of the fluorine atom-containing hydrocarbon group in which two hydrogen atoms have been replaced by fluorine atoms include the following.

Perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, 2,2,3,3,3-pentane Fluoropropyl, 2
-(Perfluorobutyl) ethyl, 2- (perfluorohexyl) ethyl, 2- (perfluorooctyl) ethyl, 2- (perfluorodecyl) ethyl, 6- (perfluoroethyl) hexyl, 6- (perfluorobutyl) )
Hexyl, 6- (perfluorohexyl) hexyl, 6
-(Perfluorooctyl) hexyl, 2- (perfluoro-3-methylbutyl) ethyl, 2- (perfluoro-5-methylhexyl) ethyl, 2- (perfluoro-
7-methyloctyl) ethyl, 2- (perfluoro-1)
-Methylethyl) hexyl, 6- (perfluoro-3-
Methylbutyl) hexyl, 6- (perfluoro-5-methylhexyl) hexyl, 6- (perfluoro-7-methyloctyl) hexyl, 1H, 1H, 5H-octafluoropentyl, 1H, 1H, 7H-dodecafluoroheptyl, 1H, 1H, 9H-hexafluorononyl,
2,2-bis (trifluoromethyl) propyl, 2,
2,3,3,4,4-hexafluorobutyl, 3-perfluorohexyl-2-propyl, 3-perfluorooctyl-2-propyl, 6H-dodecafluorohexyl, 8H-hexadecafluorooctyl, 10H-eico Safluorodecyl, perfluorophenyl and the like.

The hydrocarbon group containing a fluorine atom and an oxygen atom includes perfluoro-1,4,7-trimethyl-
2,5,8-trioxaundecyl, perfluoro-
1,4-dimethyl-2,5-dioxaoctyl, perfluoro-2,5,8-trimethyl-3,6,9-trioxadodecyl, perfluoro-2,5-dimethyl-3,
6-dioxanonyl and the like are preferred.

Specific examples of the carbonyl compound represented by the general formula (V) include the following.

[0086]

Embedded image

Embedded image Specific examples of the carbonyl compound represented by the general formula (VI) include the following.

[0087]

Embedded image Specific examples of the carbonyl compound represented by the general formula (VII) include the following.

[0088]

Embedded image Other than the compounds represented by the general formulas (V) to (VII),
The following are preferred as the carbonyl compound contained in the compound represented by the general formula (I).

[0089]

Embedded image

Embedded image Specific examples of the carbonyl compound represented by the general formula (IV) include the following.

[0090]

Embedded image

Embedded image The above carbonyl compounds can be used alone or in combination of two or more.

The method for polymerizing olefins using the catalyst of the present invention is a method for the polymerization of a catalyst comprising the solid catalyst component (component (A)), an organoaluminum compound (component (B)) and a carbonyl compound (component (C)). In the presence, olefins are polymerized or copolymerized, but the usage ratio of each component is
It is optional as long as it does not affect the effects of the present invention, and is not particularly limited. Usually, the molar ratio of component (C) to component (C) is 0.1 mol per mol of titanium atom in component (A).
001 to 1,000, preferably 0.01 to 500, particularly preferably 0.03 to 100, and the component (B) is 1 to 1,
000, preferably 50 to 500.

The order of contact of the components is arbitrary.
It is preferable to first charge the component (B), then contact the component (C), and further contact the component (A) into the polymerization system.

The olefins homopolymerized or copolymerized using the catalyst of the present invention include ethylene and α-olefins such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. And is preferably suitable for the polymerization of α-olefin, especially propylene. The catalyst of the present invention is also effective in random copolymerization and block copolymerization of propylene with one or more other olefins such as ethylene and 1-butene, and particularly, in block copolymerization of propylene and ethylene. Even when the ratio of the propylene-ethylene rubber component is increased, a polymer having good particle properties, for example, a polymer having no tackiness and having good fluidity can be obtained.

Further, in the present invention, in the polymerization of olefin (also referred to as main polymerization) using the above-mentioned catalyst,
In order to further improve the catalytic activity, stereoregularity, and particle properties of the produced 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, but 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 contacting the solid catalyst component (A), followed by contacting one or more olefins. When the prepolymerization is carried out by combining the carbonyl compound (C), the organoaluminum compound (B) is first charged into the prepolymerization system in an inert gas atmosphere or an olefin gas atmosphere for polymerization, and then the carbonyl compound is added. After contacting the compound (C) and further contacting the solid catalyst component (A), it is preferable 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, preferably 5 MPa or lower, more preferably 2.5 MPa or lower.

[0097]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples,% is% by weight.

The carbonyl compounds A and B used as the component (C) in each of the examples are the following compounds. Carbonyl compound A:

Embedded image Carbonyl compound B:

Embedded image (Example 1) <Preparation of solid catalyst component> 20 g of diethoxymagnesium and 160 ml of toluene were put into a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas to form a suspended state. After stirring at room temperature for 15 minutes, 40 ml of titanium tetrachloride at room temperature was added thereto, the temperature was raised to 80 ° C. while stirring, 5.7 ml of di-n-butyl phthalate was added, and the temperature in the system was further reduced. The temperature was raised to 110 ° C., and the reaction was performed 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 7 times with 200 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. The Ti content in the solid catalyst component was measured and found to be 2.72%.

<Formation and polymerization of polymerization catalyst> 700 ml of n-heptane was put into a 1700 ml stainless steel autoclave equipped with a stirrer, which was thoroughly dried with nitrogen gas and replaced with propylene gas. While maintaining, 2.1 mmol of triethylaluminum
Then, 0.21 mmol of carbonyl compound B and 5.25 × 10 ⁻³ mmol of the solid catalyst component as Ti were added to form a catalyst for polymerization. Next, a propylene pressure of 0.2 MPa was applied, and preliminary polymerization was performed at 20 ° C. for 30 minutes while maintaining stirring. Thereafter, 80 ml of hydrogen was added thereto, and the polymerization was continued at 70 ° C. for 2 hours at a propylene pressure of 0.7 MPa in the system. The pressure that decreases as the polymerization proceeds was supplemented by continuously supplying only propylene, and was maintained at a constant pressure during the polymerization. According to the above polymerization method, propylene was polymerized, and the produced polymer was separated by filtration and dried under reduced pressure to obtain a solid polymer.

On the other hand, the filtrate is condensed to obtain a polymer dissolved in the polymerization solvent, the weight of which is (A), and the weight of the solid polymer is (B). Further, the obtained solid polymer is boiled n-
Extraction was performed with heptane for 6 hours to obtain a polymer insoluble in n-heptane, and its weight was designated as (C). The polymerization activity (Y) per solid catalyst is represented by the following formula. Y = {(A) + (B)} / weight of solid catalyst component Further, an atactic polymer generation rate (APP) is represented by the following formula: APP = (A) / {(A) + (B)} All crystals The yield (t-II) of the reactive polymer is determined by the following formula. t-II = (C) / {(A) + (B)} Furthermore, the melt flow rate (MF
R: JIS K7210; load 2.16 kg, 230
C), the results shown in Table 1 were obtained.

(Example 2) An experiment was conducted in the same manner as in Example 1 except that carbonyl compound A was used instead of carbonyl compound B. Table 1 shows the obtained results.

(Example 3) <Preparation of solid catalyst component> The flask used in Example 1 was charged with 7.14 g of anhydrous magnesium chloride, 37.5 ml of decane and 35.1 ml of 2-ethylhexyl alcohol, and the mixture was heated at 130 ° C. For 2 hours to obtain a homogeneous solution.
Thereafter, 1.67 g of phthalic anhydride was added, and the mixture was stirred and treated at 130 ° C. for 1 hour. The obtained homogeneous solution was cooled to room temperature, and added to 200 ml of titanium tetrachloride cooled to -20 ° C.
It was dropped over time. The resulting solution was added over 4 hours to 11
The temperature was raised to 0 ° C., and when the temperature reached 110 ° C., 5.03 ml of diisobutyl phthalate was added, followed by stirring at the same temperature for 2 hours. A solid product was separated by filtration, and the solid product was suspended in 275 ml of titanium tetrachloride.
The mixture was stirred at 0 ° C. for 2 hours. Thereafter, the solid product was separated again by filtration, and decane and heptane 20 at 110 ° C.
After washing 7 times with 0 ml, a solid catalyst component was obtained. When the Ti content in this solid catalyst component was measured, it was 2.06%. <Formation and polymerization of polymerization catalyst> A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component obtained as described above was used. Results were obtained.

(Example 4) <Preparation of solid catalyst component> 10 g of diethoxymagnesium and 80 ml of toluene were put into the flask used in Example 1 and suspended. After stirring at room temperature for 15 minutes, 20 ml of room temperature titanium tetrachloride was added thereto, and the mixture was stirred for 50 minutes.
C., and di-iso-octyl phthalate 5.2
After adding ml, the temperature was further raised to 70 ° C., and 1.0 ml of diethyl phthalate was added. Then, the temperature in the system was raised to 85 ° C., a mixed solution of 4.0 ml of dimethylpolysiloxane having a viscosity of 100 cst at room temperature and 0.36 ml of carbonyl compound A was added, and the mixture was further reacted at 112 ° C. for 1 hour and 30 minutes. . After the reaction, the supernatant was removed, treated with 80 ml of toluene and 20 ml of titanium tetrachloride at 100 ° C. for 15 minutes, and further washed with 100 ml of toluene at 100 ° C. three times. Thereafter, 80 ml of toluene and 20 parts of titanium tetrachloride were used.
The mixture was treated with stirring at 100 ° C. for 1 hour and 30 minutes, and then treated with 100 ml of n-heptane at 40 ° C. for 7 hours.
Washing was performed twice to obtain a solid catalyst component. When the Ti content in this solid catalyst component was measured, it was 1.88%. <Formation and polymerization of polymerization catalyst> A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component obtained as described above was used. The result was obtained. (Comparative Example 1) An experiment was performed in the same manner as in Example 1 except that carbonyl compound B was not used, and the results shown in Table 1 were obtained.

[0104]

[Table 1]

[0105]

By polymerizing propylene using the polymerization catalyst of the present invention, it is possible to produce a polymer having an extremely small amount of atactic polymer and a high stereoregularity in a high yield.

[Brief description of the drawings]

FIG. 1 is a flowchart showing the steps for preparing a polymerization catalyst of the present invention.

Claims (1)

[Claims] (A) a solid catalyst component containing magnesium, titanium, an electron donating compound and a halogen as essential components formed by bringing a magnesium compound, a titanium compound and an electron donating compound into contact with each other; Formula R ¹ _q AlY _3-q (wherein, R ¹ is an alkyl group having 1 to 4 carbon atoms, Y is a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom;
q is a positive number satisfying 0 <q ≦ 3. And (C) a carbonyl compound represented by the following general formula (I): Here, A ² : R ² — (O) _x2 — or the following substituent: ^{A 3: R 3 - (O} ) x3 - A 4: R 4 - (O) x4 - A 5: hydrogen atom or _{^{R 5 - (O) x5 -}} (C = O) y5 - wherein, R ² to R ⁵ represents a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms having or not having at least one of an oxygen atom, a fluorine atom and a silicon atom, and two of R ^{2 to} R ⁵ May form a ring with a hydrocarbon group corresponding to L ² represents an alkylene group having 1 to 8 carbon atoms. x2, x3, x4, x5, y5 and z2 are each independently 0 or 1. n is 5 to 100,000
Is an integer. An olefin polymerization catalyst characterized by being formed from