JP2010229277A - Process for producing solid catalyst component for olefin polymerization, catalyst, and process for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid catalyst for olefin polymerization producing granular or spherical polymers having high stereoregularity, narrow particle size distribution and less fine powder; a process for producing the same; a catalyst; and a process for olefin polymerization. <P>SOLUTION: A magnesium compound (a), a titanium halogen compound (b), and an electron donating compound (c) are contacted to obtain a solid component, which is brought into contact with 0.1-15 times amount of a halogen compound (d) in terms of a molar ratio based on the titanium atom of the titanium compound contained in the solid component so that the components (d) and (e) remain on the surface of or in the solid component by means of an inert organic solvent containing a vinylsilane compound (e), followed by drying and pulverization to give a solid catalyst component for olefin polymerization. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a solid catalyst component for olefin polymerization, a catalyst and a method for producing an olefin polymer, which can maintain a high degree of stereoregularity of the polymer and obtain a polymer in a high yield. .

  Conventionally, in the polymerization of olefins, solid catalysts comprising a transition metal catalyst component such as titanium and a typical metal catalyst component such as aluminum are widely known.

  The catalyst for olefin polymerization is greatly increased in polymerization activity due to the appearance of a supported catalyst using a magnesium compound as a carrier, and further added with an electron donor such as an ester compound, thereby having 3 carbon atoms. From the above α-olefin, a highly stereoregular polymer can be produced.

  The above-mentioned supported catalyst has a high activity capable of omitting the so-called deashing step for removing catalyst residues such as chlorine and titanium remaining in the produced polymer, and also has a high degree of stereoregularity. These efforts are focused on improving the yield of coalescence and increasing the sustainability of the catalytic activity during polymerization, and each has achieved excellent results. This type of highly active catalyst component, organoaluminum compound and silicon Polymerization of olefins using a polymerization catalyst composed of an electron donating compound typified by a compound causes a fine polymer of the solid catalyst component itself and particle breakage due to heat of reaction when polymerized, resulting in a polymer produced There was a tendency to broaden the particle size distribution with a lot of fine powder contained therein. Increasing the amount of finely divided polymer prevents process continuation, causing blockage of piping during polymer transfer, etc., and widening the particle size distribution results in favorable polymer processing. As a result, the amount of fine powder polymer is as small as possible, and a polymer having a uniform particle size and a narrow particle size distribution has been sought.

  Patent Document 1 (Japanese Patent Laid-Open No. 6-157659) discloses an aromatic hydrocarbon as a means for solving the problems of fluidity and particle size distribution of the produced polymer and the preparation process while simplifying the preparation process. Solid catalyst component obtained by adding a suspension of spherical dialkoxymagnesium, aromatic hydrocarbon and phthalic acid diester to a mixed solution of titanium tetrachloride and titanium tetrachloride, allowing them to react, reacting with titanium tetrachloride, and then washing An olefin polymerization catalyst comprising:

  Moreover, in patent document 2 (Unexamined-Japanese-Patent No. 6-287225), the suspension of spherical dialkoxymagnesium, aromatic hydrocarbons, and phthalic acid diesters is a mixed solution of aromatic hydrocarbons and titanium tetrachloride. In addition to the reaction, the reaction product obtained is washed with an aromatic hydrocarbon, again reacted with titanium tetrachloride, and then the solid component obtained by washing is dried and obtained through a fine powder removal treatment step. A solid catalyst component for polymerizing olefins characterized by the above has been proposed.

JP-A-6-157659 JP-A-6-287225

  Although the above-mentioned technique has yielded the produced polymer in a high yield to some extent, further enhancement of the activity has been desired.

  Accordingly, the object of the present invention is to provide a method for producing a solid catalyst component for olefin polymerization, which can maintain a high degree of stereoregularity of the polymer when subjected to olefin polymerization, and obtain a polymer in a high yield, catalyst And providing a process for producing an olefin polymer.

  Under such circumstances, as a result of intensive studies, the present inventors contacted the solid component and the solution containing the component (d) and the component (e) under specific conditions as a subsequent step when preparing the solid catalyst component. The catalyst prepared by allowing the free component (d) and the component (e) to remain on the surface and inside of the solid catalyst component, and leaving the free component (d) and the component (e) to remain The present inventors have found that polymerizing olefins in the presence of can maintain a high degree of stereoregularity of the polymer and obtain a polymer in a high yield, thereby completing the present invention.

  That is, in the present invention, a solid component obtained by contacting a magnesium compound (a), a titanium halogen compound (b) and an electron donating compound (c) is converted into a titanium atom equivalent of the titanium compound contained in the solid component. An inert organic solvent containing a halogen compound (d) and a vinylsilane compound (e) in a molar ratio of 0.1 to 15 times leaves (d) component and (e) component on the surface of the solid component or in the solid component. And a method for producing a solid catalyst component for olefin polymerization, characterized in that it is dried to form a powder.

  Further, the present invention provides a liquid (X) in which a solid component (A1) obtained by contacting a magnesium compound (a), a titanium halogen compound (b) and an electron donating compound (c) is suspended in an inert organic solvent. ) And an inert organic solvent (Y) containing a halogen compound (d) and a vinylsilane compound (e) in a molar ratio in terms of titanium atom of the titanium compound contained in the solid component (A1) 0.1 to 15 times. A method for producing a solid catalyst component for olefin polymerization, comprising the step I of mixing and stirring at 40 to 110 ° C. for 2 to 10 minutes, and removing the supernatant liquid after standing to obtain a solid component (A2). It is to provide.

The present invention also provides (A) the solid catalyst component for olefin polymerization,
(B) The following general formula (1); R ² _p AlQ _3-p (1)
(Wherein R ² represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3) and ( C) An olefin polymerization catalyst characterized by being formed from an external electron donating compound.

  The present invention also provides a method for producing an olefin polymer, characterized in that olefins are polymerized in the presence of the olefin polymerization catalyst.

  If the catalyst formed using the solid catalyst component for olefin polymerization of the present invention is used, the stereoregularity of the polymer can be maintained at a high level, and a polymer can be obtained in a high yield. Therefore, general-purpose polyolefin can be provided at low cost.

It is a flowchart figure which shows the process of preparing the catalyst component and polymerization catalyst of this invention.

  Among the olefin polymerization catalysts of the present invention, the magnesium compound (a) (hereinafter simply referred to as “component (a)”) used for the preparation of the solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”). Examples thereof include magnesium dihalogenide, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, and fatty acid magnesium. Among these magnesium compounds, magnesium dihalide, a mixture of magnesium dihalide and dialkoxymagnesium, dialkoxymagnesium is preferable, dialkoxymagnesium is particularly preferable, specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, Examples include butoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium. Diethoxymagnesium is particularly preferable.

These dialkoxymagnesium may be obtained by reacting metal magnesium with alcohol in the presence of a halogen-containing organic metal or the like. The above dialkoxymagnesium can be used alone or in combination of two or more.
Furthermore, dialkoxymagnesium that is preferably used is in the form of granules or powder, and the shape thereof may be indefinite or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution is obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as filter clogging in the polymer separation apparatus due to the fine powder contained are solved.

  The spherical dialkoxymagnesium does not necessarily need to be a true sphere, and an elliptical or potato-shaped one can also be used. Specifically, the particle shape is such that the ratio (L / W) of the major axis diameter L to the minor axis diameter W is 3 or less, preferably 1 to 2, more preferably 1 to 1.5. .

  The dialkoxymagnesium having an average particle size of 1 to 200 μm can be used. Preferably it is 5-150 micrometers. In the case of spherical dialkoxymagnesium, the average particle size is 1 to 100 μm, preferably 5 to 80 μm, and more preferably 10 to 60 μm. Moreover, about the particle size, it is preferable to use a thing with few fine powder and coarse powder and a narrow particle size distribution. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, when the particle size distribution is represented by D90 / D10 (where D90 is the integrated particle size at 90%, D10 is the integrated particle size at 10%), it is 3 or less, preferably 2 or less. .

  For example, JP-A-58-4132, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-4-36891 can be used for producing spherical dialkoxymagnesium as described above. It is illustrated in the 8-73388 gazette etc.

The titanium halogen compound (b) used for the preparation of the component (A) (hereinafter sometimes simply referred to as “component (b)”) has the general formula Ti (OR ² ) _n X _4-n (wherein R ² Represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and n is an integer of 0 ≦ n ≦ 4.) Selected from the group of tetravalent titanium halides or alkoxy titanium halides One type or two or more types of compounds.

  Specifically, titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide is exemplified as the titanium halide, and methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n- Butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride, etc. Is exemplified. Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.

  The electron donating compound (c) used for the preparation of the component (A) (hereinafter sometimes simply referred to as “component (c)”) is an organic compound containing an oxygen atom or a nitrogen atom, such as alcohols, Phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds containing Si—O—C bonds or Si—N—C bonds, etc. Is mentioned.

  Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyle ether, diphenyl ether, 9, Ethers such as 9-bis (methoxymethyl) fluorene, 2-iso-propyl-2-iso-pentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, Ethyl propionate, ethyl butyrate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate phenyl, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, etc. Monocarboxylic acid esters, diethyl malonate, dipropyl malonate, dibutyl malonate, di-iso-butyl malonate, dipentyl malonate, dineopentyl malonate, diethyl iso-propylbromomalonate, diethyl butylbromomalonate, iso- Diethyl butyl bromomalonate, dimethyl di-iso-propylmalonate, diethyl di-iso-propylmalonate, dimethyl dibutylmalonate, diethyl dibutylmalonate, dimethyl di-iso-butylmalonate, di-iso-butylmalonic acid Diethyl, di-iso-pentylmalonate dimethyl, di-iso-pentylmalonate diethyl, iso-propylbutylmalonate diethyl, iso-propyl-iso-pentylmalonate dimethyl, bis (3-chloro-n-propyl) malon Diethyl acid Diethyl bis (3-bromo-n-propyl) malonate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dipropyl adipate, dibutyl adipate, di-iso-decyl adipate , Dicarboxylic acid diesters such as dioctyl adipate, phthalic acid diester, phthalic acid diester derivatives, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, acid chlorides such as phthalic dichloride, terephthalic acid dichloride, acetaldehyde , Aldehydes such as propionaldehyde, octylaldehyde, benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, Amides such as refinic acid amide and stearic acid amide, nitriles such as acetonitrile, benzonitrile and tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkyl Organosilicon compounds containing Si—O—C bonds such as alkoxysilanes, cycloalkylalkylalkoxysilanes, bis (alkylamino) dialkoxysilanes, bis (cycloalkylamino) dialkoxysilanes, alkyl (alkylamino) dialkoxysilanes, An organosilicon compound containing a Si—N—C bond such as dialkylaminotrialkoxysilane and cycloalkylaminotrialkoxysilane can be given.

  Among the above electron donating compounds, esters, particularly aromatic dicarboxylic acid diesters are preferably used, and phthalic acid diesters and phthalic acid diester derivatives are particularly preferable. Specific examples of these phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate , Ethyl methyl phthalate, methyl phthalate-iso-propyl, ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate-iso-butyl, di-n-pentyl phthalate, phthalic acid Di-iso-pentyl, dineopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, bis (2-ethylhexyl) phthalate , Di-n-nonyl phthalate, di-isodecyl phthalate, bis (2,2-dimethylheptyl) phthalate, n-butyl phthalate Ru-isohexyl, n-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, n-pentylisohexyl phthalate, isopentyl phthalate (heptyl), n-pentyl phthalate (2-ethylhexyl), phthalic acid n-pentyl-iso-nonyl, iso-iso-pentyl phthalate (n-decyl), n-pentylundecyl phthalate, -iso-pentyl-iso-hexyl phthalate, n-hexyl phthalate (2,2- Dimethylhexyl), n-hexyl-iso-nonyl phthalate, n-hexyl phthalate (n-decyl), n-heptyl phthalate (2-ethylhexyl), n-heptyl-iso-nonyl phthalate, n-phthalate Heptyl (neo-decyl), 2-ethylhexyl phthalate-iso-nonyl phthalate, Diesters one or two or more kinds are used.

  Further, as the phthalic acid diester derivative, one or two hydrogen atoms of the benzene ring to which the two ester groups of the above phthalic acid diester are bonded are an alkyl group having 1 to 5 carbon atoms, or a chlorine atom, bromine atom and fluorine. Examples thereof include those substituted with a halogen atom such as an atom. The solid catalyst component prepared by using the phthalic acid diester derivative as an electron donating compound can improve the hydrogen response more, and can improve the melt flow rate of the polymer even when the amount of hydrogen added during polymerization is the same or small. Can do. Specifically, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, 4,5, dineopentyl dimethylphthalate, dineopentyl 4,5-diethylphthalate, diethyl 4-chlorophthalate, di-n-chlorochlorophthalate Butyl, dineopentyl 4-chlorophthalate, diisobutyl 4-chlorophthalate, diisohexyl 4-chlorophthalate, diisooctyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n-butyl 4-bromophthalate, dineopentyl 4-bromophthalate, 4- Di-iso-butyl bromophthalate, di-iso-hexyl 4-bromophthalate, di-iso-octyl 4-bromophthalate, diethyl 4,5-dichlorophthalate, di-n-butyl 4,5-dichlorophthalate, 4,5-dichlorophthalic acid di- so-hexyl, di-iso-octyl 4,5-dichlorophthalate, among which dineopentyl 4-bromophthalate, di-n-butyl 4-bromophthalate, and di-iso-butyl 4-bromophthalate preferable.

  In addition, it is also preferable to use the above-mentioned esters in combination of two or more. When the total carbon number of the alkyl group of the ester used is 4 or more compared to that of other esters, the esters are combined. Is desirable.

  In the present invention, a method of preparing the solid component (A1) by contacting the components (a), (b) and (c) in the presence of an inert organic solvent is a preferred embodiment. As the active organic solvent, the above-mentioned titanium halogen compound is dissolved and dialkoxymagnesium is not dissolved. Specifically, pentane, hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1 , 2-diethylcyclohexane, methylcyclohexene, decalin and other saturated hydrocarbon compounds, benzene, toluene, xylene, ethylbenzene and other aromatic hydrocarbon compounds, orthodichlorobenzene, methylene chloride, 1,2-dichlorobenzene, carbon tetrachloride , Halogenated hydrocarbon compounds such as dichloroethane Among them, aromatic hydrocarbon compounds which have a boiling point of about 50 to 150 ° C. and are liquid at room temperature, specifically, hexane, heptane, octane, ethylcyclohexane, toluene, xylene, and ethylbenzene are preferably used. . Moreover, these may be used independently or may be used in mixture of 2 or more types.

  As a particularly preferred method for preparing the solid component (A1) in the preparation of the component (A) in the present invention, a suspension is prepared from the component (a), the component (c), and an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C. Examples of the preparation method include forming a mixed solution formed from the component (b) and the aromatic hydrocarbon compound, and then reacting with the suspension.

In the preparation of the solid component, in addition to the above components, it is preferable to use polysiloxane. By using polysiloxane, the stereoregularity or crystallinity of the produced polymer can be improved. Fine powder can be reduced. Polysiloxane is a polymer having a siloxane bond (—Si—O bond) in the main chain, but is also collectively referred to as silicone oil, and has a viscosity at 25 ° C. of 0.02 to 100 cm ² / s ( ^{2 to} 1000 centistokes). It is a liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature.

  As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used. As the partially hydrogenated polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylcyclotrimethyl is used. Siloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid groups. Examples thereof include substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable, and decamethylcyclopentasiloxane is particularly preferable.

  In the present invention, the above components (a), (b) and (c) and, if necessary, an aromatic hydrocarbon compound or polysiloxane are brought into contact with each other to form a solid component. The method is described. Specifically, the magnesium compound (a) is suspended in a titanium halogen compound (b) or an aromatic hydrocarbon compound, and an electron donating compound (c) such as phthalic acid diester, and further a tetravalent if necessary. The method of obtaining a solid component by contacting a titanium halogen compound (b) is mentioned. In this method, by using a spherical magnesium compound, a solid component having a spherical shape and a sharp particle size distribution can be obtained. As a result, the same component (A) can be obtained, and without using a spherical magnesium compound, For example, a solid component having a spherical shape and a sharp particle size distribution can be obtained by forming particles by spraying and drying a solution or suspension using a spraying device, that is, a so-called spray drying method.

  The contact of each component is performed with stirring in a container equipped with a stirrer in a state where moisture and the like are removed under an inert gas atmosphere. The contact temperature is the temperature at the time of contact of each component at the time of contact of each component, and may be the same temperature as the reaction temperature or a different temperature. 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 is dispersed or suspended for modification, but the product is allowed to react after contact. When obtaining, the temperature range of 40-130 degreeC is preferable. If the temperature during the reaction is less than 40 ° C, the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid catalyst component, and if it exceeds 130 ° C, evaporation of the solvent used becomes remarkable. Therefore, it becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

  The amount of each component used in preparing the solid component varies depending on the preparation method, and thus cannot be determined unconditionally. For example, the tetravalent titanium halogen compound (b) is 0.5 per mol of the magnesium compound (a). To 100 mol, preferably 0.5 to 10 mol, more preferably 1 to 5 mol, and the electron-donating compound (c) is 0.01 to 10 mol, preferably 0.01 to 1 mol, more preferably 0.02 to 0.6 mol, the aromatic hydrocarbon compound is 0.001 to 500 mol, preferably 0.001 to 70 mol, more preferably 0.005 to 50 mol, and the polysiloxane is 0.00. It is 01-100g, Preferably it is 0.05-80g, More preferably, it is 1-50g.

  In the solid catalyst component (A) of the present invention, the solid component is 0.1 to 15 times, more preferably 0.1 to 15 times in terms of a molar ratio in terms of titanium atom of the titanium compound contained in the solid component (A1). 5 times, particularly preferably 0.1 to 3 times, most preferably 0.1 to 1.5 times the halogen compound (d) (hereinafter sometimes simply referred to as “component (d)”) and its solid components 0.01 to 1 time, preferably 0.05 to 0.5 times, and particularly preferably 0.08 to 0.3 times the vinylsilane compound (e) (hereinafter referred to as a molar ratio in terms of titanium atom) of the titanium compound contained in An inert organic solvent containing "component (e)") in contact with the surface of the solid component or the solid component so that the component (d) and the component (e) remain, and then dried. Can be obtained. When the components (d) and (e) are brought into contact with the solid component in the above-mentioned usage amount, the effect of higher activity, lower fine powder and good particle size distribution is produced.

  Component (d) is a halogen compound, and component (b), halogenated hydrocarbon, halogen-containing alcohol, halogenated silicon compound having a hydrogen-silicon bond, halogen of Group IIIB, Group IV, Group V elements of the periodic table And the like (hereinafter referred to as metal halide).

  The halogenated hydrocarbons are mono- and poly-halogen substitutes of saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. Specific examples of such compounds are aliphatic chlorides such as methyl chloride, methyl bromide, methyl iodide, methylene chloride, methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, tetra Carbon iodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1,2-diiodoethane, methyl chloroform, methyl bromoform, methyl iodoform, 1,1,2-trichloroethylene, 1,1,2-tribromoethylene, 1,1,2,2-tetrachloroethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene Examples include octachloropropane, decabromobutane, and chlorinated paraffin. Examples of alicyclic compounds include chlorocyclopropane, tetrachlorocyclopentane, hexachlorocyclopentadiene, and hexachlorocyclohexane. Examples of aromatic compounds include chlorobenzene, bromobenzene, and o. -Dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, benzotrichloride, p-chlorobenzotrichloride and the like. These compounds may be used alone or in combination of two or more.

  As the halogen-containing alcohol, a compound in which any one or two or more hydrogen atoms other than a hydroxyl group in a mono- or polyhydric alcohol having one or two or more hydroxyl groups in one molecule is substituted with a halogen atom is used. it can. Examples of the halogen atom include chlorine, bromine, iodine and fluorine atoms, and a chlorine atom is desirable.

  Examples of these compounds are 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol, 4-chloro-1-butanol, 5-chloro -1-pentanol, 6-chloro-1-hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol, 6-chloro- (m, o) -cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-4-chloro Phenol, 4-chloro-1-naphthol, (m, o, p) -chlorophenol, p-chloro-o-methylbenzylalco 2-chloro-4-phenylphenol, 6-chlorothymol, 4-chlororesorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol, 1-bromo-2-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m, o, p) -bromophenol, 4-bromoresorcin, (m, o, p) -fluorophenol P-iodophenol, 2,2-dichloroethanol, 2,3-dichloro-1-propanol, 1,3-dichloro-2-propanol, 3-chloro-1- (α-chloromethyl) -1-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo-2-propanol, 2,4-dibromophenol, 2,4-dibromo-1- Naphthol, 2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, β, β, β, -trichloro-tert-butanol, 2,3,4-trichlorophenol, 2,4,5 -Trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,3,5-tribromo-4-hydroxytoluene, 2 , 2,2-trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,6-triiodophenol, 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachloro Bisphenol A, tetrabromobisphenol A, 2,2,3,8 tetrafluoro-1-propanol, 2,3,5,6 Tetrafluoro phenol, tetrafluoro resorcinol, and the like.

Examples of the halogenated silicon compound having a hydrogen-silicon bond include HSiCl ₃ , H ₂ SiCl ₂ , H ₃ SiCl, HSiMeCl ₂ , HSiEtCl ₂ , HSi (t-Bu) Cl ₂ , HSiPhCl ₂ , HSiMe ₂ Cl, HSi (i _{-Pr) 2 Cl, H 2 SiEtCl} , H 2 Si (n-Bu) Cl, H 2 (C 6 H 4 CH 3) SiCl, HSiPh 2 Cl and the like.

Metal halides include Ti, Zr, Hf, V, Nb, Ta, B, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi chloride, fluoride, bromide, iodine. In particular, TiCl ₄ , BCl ₃ , BBr ₃ , BI ₃ , AlCl ₃ , AlBr ₃ , GaCl ₃ , GaBr ₃ , InCl ₃ , TlCl ₃ , SiCl ₄ , SnCl ₄ , SbCl ₅ , SbF _5, etc. are preferred. It is. Of these, metal halides are preferred, and titanium tetrachloride is particularly preferred. In the case of titanium tetrachloride, fine powder is reduced and the particle size distribution becomes sharper.

As the vinylsilane compound used in the present invention, the following general formula:
^{_{(CH 2 = CH) m SiR}} 1 n X 4-m-n (1)
(Where R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, X represents a halogen, m represents a number satisfying 1 ≦ m ≦ 4, and n represents a number satisfying m + n ≦ 4) The thing represented by these is preferable.

_{Examples, CH 2 = CH-SiH 3} , CH 2 = CH-SiH 2 (CH 3), CH 2 = CH-SiH (CH 3) 2, CH 2 = CH-Si (CH 3) 3, CH ₂ = CH-SiCl ₃ , CH ₂ = CH-SiCl ₂ (CH ₃ ), CH ₂ = CHSiCl (CH ₃ ) H, CH ₂ = CH-SiCl (C ₂ H ₅ ) ₂ , CH ₂ = CH-Si ( _{C 2 H 5) 3, CH} 2 = CH-Si (CH 3) (C 2 H5) 2, CH 2 = CH-Si (C 6 H 5) (CH 3) 2, CH 2 = CH-Si (CH _{3) 2 (C 6 H 4} CH 3), (CH 2 = CH) 2 SiCl 2, (CH 2 = CH) 2 Si (CH 3) 2, (CH 2 = CH) 3 SiCH 3, (CH 2 = _{CH) 3 SiCl, (CH 2} = CH) 4 Si _{(CH 2 = CH) 2 Si} (CH 3) Cl, can be exemplified _{(CH 2 = CH) 2 SiCl} 2, (CH 2 = CH) 2 Si (C 2 H 5) 2 and the like. Among them, (CH ₂ ═CH) ₂ Si (CH ₃ ) ₂ , (CH ₂ ═CH) ₂ Si (CH ₃ ) Cl, (CH ₂ ═CH) ₂ SiCl ₂ , (CH ₂ ═CH ) ₂ Si (C ₂ H ₅ ) ₂ , (CH ₂ ═CH) ₃ SiCH ₃ .

  As the inert organic solvent, the aforementioned inert organic solvent is used in the same manner.

  As a suitable contact method between the solid component (A1) and the inert organic solvent containing the component (d) and the component (e), a liquid in which the solid component (A1) is suspended in an inert organic solvent ( X) and an inert organic solvent (Y) containing a specific amount of the halogen compound (d) and the vinylsilane compound (e) with respect to the molar ratio in terms of titanium atom of the titanium compound contained in the solid component (A1). 40 to 110 ° C., preferably 85 to 105 ° C., particularly preferably 85 to 100 ° C., mixed and stirred for 2 to 10 minutes, and after standing, the supernatant liquid is removed to obtain a solid component (A2) (hereinafter referred to as “step I”). , Simply referred to as “post-contact step such as component (d)”).

  Further, the solid component (A2) and the inert organic solvent (Y) containing the halogen compound (d) and the vinylsilane compound (e) are mixed and stirred at 40 to 110 ° C. for 2 to 10 minutes, and then left standing. The method which further has the II process of removing a supernatant liquid and obtaining a solid component (A3) is preferable. In addition, the mixing and stirring contact between the solid component and the inert organic solvent (Y) containing the component (d) is preferably performed 2 to 8 times, preferably 3 to 6 times, on the surface of the solid component or the solid component. It is preferable in that the component (d) and the component (e) can be left in a specific amount.

  In Step I or Step II, after removing the supernatant liquid, the solid catalyst component (A) may be obtained by drying to form a powder. After the contact treatment of the solid component with the inert organic solvent containing the component (d) and the component (e), the component (d) and the component (e) released from the solvent and on the surface of the solid component or in the solid component. In the present invention, the component (d) and the component (e) are dehydrated and dried. As a drying method, the used inert organic solvent may be removed and dried to form a powder, and examples thereof include vacuum drying, heat drying, and heat vacuum drying.

  In the present invention, after the contact treatment of the solid component and the inert organic solvent containing the component (d) and the component (e), the solid catalyst component thus obtained is dried without washing. The components (d) and (e) that are somewhat free components apart from the catalytically active components are incorporated in specific amounts, and the solid catalyst components are used for the polymerization of olefins to obtain a high yield of polymer. Can be obtained.

  When the component (d) is a titanium halogen compound titanium tetrachloride, the solid catalyst component (A) of the present invention is washed with 10 ml of heptane per gram of the component at 40 ° C. for 5 minutes. When washed repeatedly, the amount of titanium washed away is 0.3 wt% or more and 2.5 wt% or less. That is, the amount of titanium washed away is the desorption component (d). The amount of titanium washed away is a value obtained by subtracting the titanium content of the solid catalyst component (A) after washing from the titanium content of the solid catalyst component (A) before washing. By repeating the washing 8 times, the desorption component (d) can be almost completely washed away. If the washing is performed several times, some of the desorbed component (d) remains in the solid catalyst component (A).

  Specifically, the above-described washing method for measuring the desorption component (d) includes a solid catalyst component (A) in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas. Charge 10 g, and then add 100 ml of 40 ° C. heptane and stir at 40 ° C. for 5 minutes. The stirrer has a stirring shaft attached to the stirring shaft provided at the center of the round bottom flask, and the stirring condition is 200 revolutions per minute.

  Moreover, it is preferable that the solid catalyst component (A) of this invention contains 0.05 weight% or more and 1.2 weight% or less of a component (e). Component (e) reduces the solid catalyst component with 10 ml heptane per gram of the component with a 5 minute wash at 40 ° C. In particular, after repeated washing five times, the component (e) in the solid catalyst component (A) is almost completely washed away. Therefore, the component (e) in the solid catalyst component (A) can be quantified by such washing.

  In the present invention, when preparing the solid catalyst component from the solid component, the component (d) and the component (e) are brought into contact with each other as in triethylaluminum described in the patent document (Japanese Patent Laid-Open No. 3-234707). Organic organoaluminum compounds are not contacted. That is, in the conventional solid catalyst component, the organosilicon compound is brought into contact with the solid component containing magnesium and titanium, the organoaluminum compound is brought into contact therewith, and then washed to form a solid catalyst component. On the other hand, the solid catalyst component of the present invention is obtained by bringing only the component (d) and the component (e) into contact with each other.

  Based on the above, as a particularly preferable preparation method of the component (A) in the present invention, the magnesium compound (a) is suspended in an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C., and then the titanium halogen compound is suspended in this suspension. After contacting (b), a reaction treatment is performed. At this time, before or after the titanium halogen compound (b) is brought into contact with the suspension, one or more electron donating compounds (c) such as phthalic acid diester are added at −20 to 130 ° C. Contact, and if necessary, contact with polysiloxane to perform a reaction treatment to obtain a solid component. At this time, it is desirable to conduct the aging reaction at a low temperature before or after contacting one or more of the electron donating compounds. This solid component is washed with a hydrocarbon compound (intermediate washing) to obtain a solid component. Next, the above-described “post-contact step such as component (d)” is performed to obtain component (A).

  Further, the content of titanium, magnesium, halogen atom and electron donating compound in the component (A) in the present invention is not particularly defined, but preferably titanium is 1.0 to 10% by weight, preferably 2.0 to 10%. % By weight, more preferably 3.0 to 10% by weight, magnesium is 10 to 70% by weight, more preferably 10 to 50% by weight, particularly preferably 15 to 40% by weight, still more preferably 15 to 25% by weight, halogen 20 to 90% by weight of atoms, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, still more preferably 45 to 80% by weight, and the total amount of electron donating compounds is 0.5 to 30% by weight, More preferably, the total is 1 to 25% by weight, and particularly preferably the total is 2 to 20% by weight.

The organoaluminum compound (B) (hereinafter sometimes referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention is a compound represented by the above general formula (1). As long as there is no particular limitation, R ² is preferably an ethyl group or an isobutyl group, Y is preferably a hydrogen atom, a chlorine atom or a bromine atom, and n is preferably 2 or 3, particularly preferably 3. Specific examples of such organoaluminum compounds include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and triisobutylaluminum are preferable.

  In the catalyst of the present invention, an external electron donating compound (C) (hereinafter sometimes referred to as “component (C)”) is used in addition to the solid catalyst component (A) and the component (B).

  The external electron donating compound (C) (hereinafter sometimes referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention is used for the preparation of the solid catalyst component described above. The same electron donating compound (c) that can be used is used, and among them, ethers, esters, and organosilicon compounds are preferable. Among the ethers, 1,3 diether is preferable, and 9,9-bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are particularly preferable. Of the esters, methyl benzoate and ethyl benzoate are preferred.

As said organosilicon compound, following General formula (3)
R ³ _q Si (NR ⁴ R ⁵ ) _r (OR ⁶ ) _{4- (q + r)} (3)
(In the formula, q is an integer of 0, 1 to ⁴ , r is an integer of 0, 1 to ⁴ , provided that q + r is an integer of 0 to 4, R ³ , R ⁴ or R ⁵ is a hydrogen atom, 1 to Any of 12 linear or branched alkyl groups, substituted or unsubstituted cycloalkyl groups, phenyl groups, vinyl groups, allyl groups, aralkyl groups, which may contain heteroatoms, and may be the same or different R ⁶ represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, may contain a hetero atom, may be the same or different, and R ⁴ And R ⁵ may combine to form a ring.).

In general formula (3), R ³ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and particularly a linear or branched group having 1 to 8 carbon atoms. An alkyl group and a cycloalkyl group having 5 to 8 carbon atoms are preferred. R ⁴ or R ⁵ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, particularly a linear or branched alkyl group having 1 to 8 carbon atoms. And a cycloalkyl group having 5 to 8 carbon atoms is preferred. In addition, R ⁴ and R ⁵ are combined to form a ring (NR ⁴ R ⁵ ) is preferably a perhydroquinolino group or a perhydroisoquinolino group. R ⁶ is preferably a linear or branched alkyl group having 1 to ⁶ carbon atoms, and particularly preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  Examples of such organosilicon compounds include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, alkyl ( Alkylamino) silane, alkylaminosilane and the like.

  In the formula, specific examples of the organosilicon compound in which r is 0 include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri -Iso-butylmethoxysilane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxy Silane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-iso-propyldi Toxisilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butyl (n-propyl) dimethoxysilane, t-butyl (isopropyl) dimethoxysilane, t-butyl (n-butyl) dimethoxysilane, t-butyl (isobutyl) dimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) Dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclone) Hexyl) dimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxy Silane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane , Cyclopen Tylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxy Silane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (iso-propyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (N-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphe Rudimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane N-propyltrimethoxysilane, iso-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimeth Sisilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra Butoxysilane is mentioned.

  Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane , T-butylethyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane Cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane , Cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane Is preferred.

  In the formula, as the organosilicon compound in which r is 1 to 4, (alkylamino) trialkylsilane, (alkylamino) dialkylcycloalkylsilane, (alkylamino) alkyldicycloalkylsilane, (alkylamino) tricycloalkylsilane , (Alkylamino) (dialkylamino) dialkylsilane, (alkylamino) (dialkylamino) dicycloalkylsilane, bis (alkylamino) dialkylsilane, bis (alkylamino) alkylcycloalkylsilane, bis (alkylamino) dicyclo Alkylsilane, bis (alkylamino) (dialkylamino) alkylsilane, bis (alkylamino) (dialkylamino) cycloalkylsilane, di (alkylamino) dialkylsilane, di (alkylamino) al Dicycloalkylsilane, di (alkylamino) dicycloalkylsilane, di (cycloalkylamino) dialkylsilane, di (cycloalkylamino) alkylcycloalkylsilane, di (cycloalkylamino) dicycloalkylsilane, tris (alkylamino) ) Alkylsilane, Tris (alkylamino) cycloalkylsilane, Tri (alkylamino) alkylsilane, Tri (alkylamino) cycloalkylsilane, Tri (cycloalkylamino) alkylsilane, Tri (cycloalkylamino) cycloalkylsilane, Tetrakis (Alkylamino) silane, tris (alkylamino) dialkylaminosilane, tris (cycloalkylamino) dialkylaminosilane, bis (dialkylamino) bis (alkylamino) Lan, dialkylaminotris (alkylamino) silane, bis (per-hydroisoquinolino) bis (alkylamino) silane, bis (perhydroquinolino) bis (alkylamino) silane, bis (cycloalkylamino) bis (alkylamino) ) Silane, tetra (alkylamino) silane, tri (alkylamino) dialkylaminosilane, tri (cycloalkylamino) dialkylaminosilane, di (dialkylamino) di (alkylamino) silane, dialkylaminotri (alkylamino) silane, di ( Alkyl-substituted per-hydroisoquinolino) di (alkylamino) silane, di (alkyl-substituted perhydroquinolino) di (alkylamino) silane, di (cycloalkylamino) di (alkylamino) silane, alkyl (dialkylamino) ) (Alkylamino) alkoxysilane, cycloalkyl (dialkylamino) (alkylamino) alkoxysilane, vinyl (dialkylamino) (alkylamino) alkoxysilane, allyl (dialkylamino) (alkylamino) alkoxysilane, aralkyl (dialkylamino) (Alkylamino) alkoxysilane, dialkyl (alkylamino) alkoxysilane and the like can be mentioned.

  The organosilicon compound (C) can be used alone or in combination of two or more. These external electron donating compounds can be used alone or in combination of two or more.

  In the method for producing an olefin polymer of the present invention, homopolymerization, random copolymerization or block copolymerization of olefins is carried out in the presence of the olefin polymerization catalyst of the present invention. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. In particular, ethylene, propylene, and 1-butene are preferably used, and propylene is particularly preferable. In the case of propylene, copolymerization with other olefins can be performed. Examples of the olefin to be copolymerized include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. . In particular, ethylene and 1-butene are preferably used. Copolymerization of propylene and other olefins includes random copolymerization in one stage using propylene and a small amount of ethylene as a comonomer, and homopolymerization of propylene in the first stage (first polymerization tank). The so-called propylene-ethylene block copolymerization in which propylene and ethylene are copolymerized in a stage (second polymerization tank) or more stages (multistage polymerization tank) is typical. Even in such random copolymerization and block copolymerization, the catalyst of the present invention comprising the component (A), the component (B) and the component (C) is effective and has catalytic activity, stereoregularity and / or hydrogen. Not only is the response good, but the copolymerization properties and the properties of the resulting copolymer are also good. Also, alcohols can be added to the polymerization system in order to prevent gel formation in the final product, especially when shifting from homopolymerization of propylene to block copolymerization. Specific examples of alcohols include ethyl alcohol, isopropyl alcohol and the like, and the amount used is 0.01 to 10 mol, preferably 0.1 to 2 mol, per 1 mol of component (II).

  The amount of each component used is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, component (B) is used per 1 mole of titanium atom in component (A). , 1 to 2000 mol, preferably 50 to 1000 mol. Component (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.1 to 0.5 mol, per mol of component (B).

  The order of contacting the components is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the component (C) is charged, and then the solid catalyst component (A) is contacted. desirable.

  The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used for polymerization in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 6 MPa or lower. In addition, either a continuous polymerization method or a batch polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

  Furthermore, in polymerizing olefins using the catalyst formed from component (A) and component (B) or component (C) in the present invention (also referred to as “main polymerization”), catalytic activity, stereoregularity and In order to further improve the particle properties and the like to be generated, it is desirable to perform preliminary polymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used. Specifically, component (A) and component (B), or component (C) are contacted in the presence of olefins, and 0.1 to 100 g of polyolefin per 1 g of component (A) is preliminarily polymerized, Further, component (B) and / or component (C) are contacted to form a catalyst.

  In carrying out the prepolymerization, the order of contacting the components and the monomers is arbitrary, but preferably, the component (B) is first placed in a prepolymerization system set to an inert gas atmosphere or a gas atmosphere for carrying out polymerization such as propylene. Then, after contacting component (A), an olefin such as propylene and / or one or more other olefins are contacted. The prepolymerization temperature is arbitrary and is not particularly limited, but is preferably in the range of -10 ° C to 70 ° C, more preferably in the range of 0 ° C to 50 ° C.

  When olefins are polymerized in the presence of the olefin polymerization catalyst of the present invention, a polymer having a high stereoregularity, a small amount of fine powder and a narrow particle size distribution is higher than when a conventional catalyst is used. The yield can be obtained.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples. However, this is merely an example and does not limit the present invention.

<Preparation of solid components>
A 3000 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 75 g of diethoxymagnesium and 375 ml of toluene to form a suspension. The suspension was then added to a suspension of 150 ml of toluene and 225 ml of titanium tetrachloride pre-charged in a 3000 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. did. The suspension was then reacted at 6 ° C. for 1 hour. Thereafter, 22.5 ml of di-n-butyl phthalate was added, the temperature was further raised to 105 ° C., and the reaction treatment was performed for 2 hours with stirring. After completion of the reaction, the product was washed 4 times with 750 ml of toluene at 100 ° C. to obtain a solid component. The titanium content in the solid catalyst component was measured and found to be 3.3% by weight.

<Preparation of solid catalyst component (A)>
A 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 20 g of the solid component and 120 ml of toluene, and suspended. After adding 120 ml of a heptane solution containing 2 ml of titanium tetrachloride at room temperature and 0.3 ml of divinyldimethylsilane to the suspension, the temperature was raised and the mixture was stirred at 100 ° C. for 5 minutes. After stirring, the mixture was allowed to stand, and then the supernatant was removed. The contact of the above solid components with titanium tetrachloride and divinyldimethylsilane was made one time. Next, 120 ml of a heptane solution containing 2 ml of titanium tetrachloride at room temperature and 0.3 ml of divinyldimethylsilane is added to the solid components in the round bottom flask, and the mixture is stirred at 100 ° C. for 5 minutes. Then, the supernatant was removed (convenient contact twice). Thereafter, the same operation as the second contact was repeated, and the solid component was contacted with titanium tetrachloride and divinyldimethylsilane five times for convenience. Then, it filtered and dried and obtained the powdery solid catalyst component (A). The titanium content in the solid catalyst component was measured and found to be 3.9% by weight. That is, in the “post-contact step such as component (d)”, 0.6 wt% (3.9 wt% to 3.3 wt%) was incorporated as the amount of titanium in the solid catalyst component (A). become. And the confirmation test that the following washing | cleaning method is appropriate was performed as a fixed_quantity | quantitative_assay method of desorption titanium tetrachloride. The molar amount of titanium tetrachloride used in heptane was 1.3 times in terms of a molar ratio in terms of titanium atom of the titanium compound contained in the solid component. The molar amount of divinyldimethylsilane used was 0.1 times as a molar ratio in terms of titanium atom of the titanium compound contained in the solid component.

<Quantification of desorbed titanium tetrachloride>
The solid catalyst component (A) 10 g was charged into a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and then 100 ml of 40 ° C. heptane was added, and 40 ° C. for 5 minutes. Stir at 200 rpm. After the stirring was stopped, filtration was performed to obtain a washed solid catalyst component (A). This was taken as one time, and batch washing was repeated 8 times. The stirrer had a stirring blade attached to a stirring shaft provided at the center of the round bottom flask. As a result, the amount of titanium in the solid catalyst component (A) after washing eight times was 3.3% by weight, and the desorbed titanium tetrachloride was 0.6% by weight, and the washing method is appropriate. Was confirmed.

<Formation and polymerization of polymerization catalyst>
In an autoclave with a stirrer having an internal volume of 2.0 liters completely substituted with nitrogen gas, 0.0026 mmol of triethylaluminum 1.32 mmol, cyclohexylmethyldimethoxysilane 0.13 mmol and the solid catalyst component (A) as titanium atoms was charged. To form a polymerization catalyst. Thereafter, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 1 hour. Polymerization activity per 1 g of the solid catalyst component at this time, ratio of boiling n-heptane insoluble matter in the produced polymer (HI), value of melt flow rate of the produced polymer (MFR), 44 μm or less of the produced solid polymer or The amount of fine powder of 75 μm or less, the average particle size and particle size distribution of the produced solid polymer are shown in Table 1.

The polymerization activity per solid catalyst component used here was calculated by the following equation.
Polymerization activity = produced polymer (g) / solid catalyst component (g)
Further, the ratio (HI) of boiling n-heptane insoluble matter in the produced polymer is the ratio (% by weight) of the polymer insoluble in n-heptane when this produced polymer is extracted with boiling n-heptane for 6 hours. ). Further, the melt flow rate value (MFR) of the produced polymer was measured according to ASTM D 1238. In addition, the amount of fine powder of 44 μm or less or 75 μm or less of the produced solid polymer is obtained by flowing ethanol through the produced polymer placed on a 330 mesh or 200 mesh sieve, and centrifuging the ethanol suspension containing the fine particles that have passed through the sieve. The solid content (fine particles) was recovered by separation and further measured by a method of drying under reduced pressure and measuring the weight. Next, the amount of coarse powder of 1700 μm or more of the produced solid polymer was measured by collecting the produced polymer on a 10 mesh sieve. The average particle size of the produced solid polymer was measured by measuring the particle size distribution according to JISK0069 and determining the particle size corresponding to an integrated weight of 50%.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the solid catalyst component (A) was prepared using the same mole of divinyldichlorosilane instead of divinyldimethylsilane. The obtained results are shown in Table 1.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the solid catalyst component (A) was prepared using the same mole of trivinylmethylsilane instead of divinyldimethylsilane. The obtained results are shown in Table 1.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the solid component was prepared using the same mole of diisobutyl phthalate instead of di-n-butyl phthalate. The obtained results are shown in Table 1.

<Preparation of solid components>
Anhydrous magnesium chloride (75 g), decane (375 ml) and 2-ethylhexyl alcohol (300 g) were heated at 135 ° C. for 4 hours to obtain a homogeneous solution, and 16.9 g of phthalic anhydride was added to the solution, and further at 135 ° C. for 1 hour. The mixture was stirred and dissolved to dissolve phthalic anhydride. After cooling the homogeneous solution thus obtained to room temperature, 113 ml of this homogeneous solution was charged dropwise into 300 ml of titanium tetrachloride maintained at -20 ° C. over 45 minutes. After dripping, the temperature of the liquid was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 1.6 ml of diisobutyl phthalate was added. The mixture was further stirred at the above temperature for 2 hours. After the reaction for 2 hours, it was filtered. The solid part was washed with decane to obtain a solid component. The titanium content in the solid component was measured and found to be 4.5% by weight.

  The solid catalyst component (A) was prepared, the polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the solid component obtained above was used. The titanium content in the solid catalyst component (A) was measured and found to be 4.9% by weight. That is, in the “post-contact step such as component (d)”, 0.4% by weight (4.9% by weight to 4.5% by weight) of titanium was incorporated into the solid catalyst component (A). become. The molar amount of titanium tetrachloride used in heptane was 1.0 times in terms of a molar ratio in terms of titanium atom of the titanium compound contained in the solid component. The molar amount of divinyldimethylsilane used was 0.1 times as a molar ratio in terms of titanium atom of the titanium compound contained in the solid component. The obtained results are shown in Table 1.

Comparative Example 1
<Preparation of solid catalyst component>
A 3000 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 75 g of diethoxymagnesium and 375 ml of toluene to form a suspension. The suspension was then added into a solution of 150 ml of toluene and 225 ml of titanium tetrachloride, pre-charged in a 3000 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. The suspension was then reacted at 6 ° C. for 1 hour. Thereafter, 22.5 ml of di-n-butyl phthalate was added and the temperature was raised to 105 ° C., followed by a reaction treatment for 2 hours with stirring. After completion of the reaction, the product was washed 4 times with 750 ml of toluene at 100 ° C., 75 ml of titanium tetrachloride and 1.1 ml of divinyldimethylsilane were newly added, and the reaction treatment was carried out at 100 ° C. for 0.5 hour with stirring. It was. The product was then washed 4 times with 600 ml of 40 ° C. heptane, filtered and dried to obtain a powdery solid catalyst component. The titanium content in the solid catalyst component was measured and found to be 3.8% by weight.

<Formation and polymerization of polymerization catalyst>
The experiment was performed in the same manner as in Example 1 except that the solid catalyst component obtained above was used. The obtained results are shown in Table 1.

Comparative Example 2
A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that divinyldimethylsilane was not used during the preparation of the solid catalyst component (A). The obtained results are shown in Table 2.

Comparative Example 3
At the time of preparing the solid catalyst component (A), a polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that titanium tetrachloride was not used. The obtained results are shown in Table 2.

Comparative Example 4
A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the solid catalyst component (A) was prepared using the same mole of diallyldimethylsilane instead of divinyldimethylsilane. The obtained results are shown in Table 2.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the solid catalyst component (A) was prepared using the same mole of silicon tetrachloride instead of 2 ml of titanium tetrachloride. The obtained results are shown in Table 3.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the solid catalyst component (A) was prepared using the same mole of 1,2-dichloroethane instead of 2 ml of titanium tetrachloride. . The obtained results are shown in Table 3.

  A polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the solid catalyst component (A) was prepared using the same mole of HSiCl 3 instead of 2 ml of titanium tetrachloride. The obtained results are shown in Table 3.

  From the results of Tables 1, 2 and 3, a polymer having high stereoregularity is obtained in a high yield by polymerizing propylene using the solid catalyst component and catalyst obtained by the method of the present invention. You can see that

Claims (9)

  The solid component obtained by bringing the magnesium compound (a), the titanium halogen compound (b) and the electron donating compound (c) into contact with each other is 0.1 in terms of a molar ratio in terms of titanium atom of the titanium compound contained in the solid component. Contact with an inert organic solvent containing ˜15 times the halogen compound (d) and the vinylsilane compound (e) so that the component (d) and the component (e) remain on the surface of the solid component or in the solid component; A method for producing a solid catalyst component for olefin polymerization, which is then dried to a powder.   A liquid (X) and a solid component (A1) obtained by suspending a solid component (A1) obtained by contacting a magnesium compound (a), a titanium halogen compound (b) and an electron donating compound (c) in an inert organic solvent. ) An inert organic solvent (Y) containing a halogen compound (d) and a vinylsilane compound (e) 0.1 to 15 times the molar ratio of the titanium compound contained in the titanium compound at 40 to 110 ° C. A method for producing a solid catalyst component for olefin polymerization, comprising the step I of mixing and stirring for 2 to 10 minutes and removing the supernatant after standing to obtain a solid component (A2).   The solid component (A2), an inert organic solvent (Y) containing a halogen compound (d) and a vinylsilane compound (e) are mixed and stirred at 40 to 110 ° C. for 2 to 10 minutes, and after standing, the supernatant is removed. The method for producing a solid catalyst component for olefin polymerization according to claim 2, further comprising a step II of obtaining a solid component (A3).   The olefin according to claim 3, wherein the mixing and stirring contact between the solid component and the inert organic solvent (Y) containing the halogen compound (d) and the vinylsilane compound (e) is carried out 2 to 8 times. For producing a solid catalyst component for polymerization. The vinylsilane compound is represented by the following general formula (1):
^{_{(CH 2 = CH) m SiR}} 1 n X 4-m-n (1)
(Where R ¹ represents a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms, X represents a halogen, m represents a number satisfying 1 ≦ m ≦ 4, and n represents a number satisfying m + n ≦ 4)
The method for producing a solid catalyst component for olefin polymerization according to any one of claims 1 to 4, wherein:   The method for producing a solid catalyst component for olefin polymerization according to any one of claims 1 to 4, wherein the halogen compound is titanium tetrachloride.   The method for producing a solid catalyst component for olefin polymerization according to any one of claims 1 to 6, wherein the inert organic solvent is an aliphatic hydrocarbon solvent. (A) a solid catalyst component for olefin polymerization obtained by the production method according to claim 1,
(B) The following general formula (1); R ² _p AlQ _3-p (1)
(Wherein R ² represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is an integer of 0 <p ≦ 3) and ( C) Olefin polymerization catalyst characterized by being formed from an external electron donating compound.   A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 8.