JP5785807B2 - Method for producing solid catalyst component for olefin polymerization - Google Patents

Description

  The present invention relates to a method for producing a solid catalyst component for olefin polymerization, which can obtain a polymer having high stereoregularity in a high yield.

  Conventionally, the polymerization of olefins is carried out in the presence of an olefin polymerization catalyst comprising a solid catalyst component containing magnesium, titanium, an electron donating compound and halogen as essential components, an organoaluminum compound and an organosilicon compound. Many polymerization methods of olefins to be polymerized or copolymerized have been proposed.

  For example, in Patent Document 1 (Japanese Patent Laid-Open No. 1-315406), titanium tetrachloride is brought into contact with a suspension formed of diethoxymagnesium and alkylbenzene, and then phthalic acid dichloride is added and reacted. Presence of a solid catalyst component prepared by obtaining a solid product and further reacting the solid product with titanium tetrachloride in the presence of alkylbenzene, and an olefin polymerization catalyst comprising an organoaluminum compound and an organosilicon compound A method for polymerizing olefins is disclosed below.

  Patent Document 2 (Japanese Patent Publication No. 2002-522578) discloses a step of reacting a magnesium compound (a) with an alcohol (b) in a solution to obtain a first intermediate, and the first intermediate is dicarboxylic. Reactive halogenated hydrocarbon for at least one of the step of reacting with acid dihalide (c) in solution to obtain a second intermediate and the step of reacting the second intermediate with titanium tetrahalide (d) A method for producing an olefin polymerization catalyst component containing magnesium dihalide, titanium tetrahalide, and dicarboxylic acid diester, characterized in that (e) is brought into contact with each other, is disclosed.

  Further, in Patent Document 3 (Japanese Patent Laid-Open No. 10-30004), a titanium compound mixed solution comprising a magnesium compound, a titanium compound 88 to 99% by weight, and a halogen-containing hydrocarbon-containing hydrocarbon 1 to 12% by weight. A method for preparing a solid titanium catalyst component containing titanium, magnesium and halogen as essential components by contacting them is disclosed.

  However, these conventional methods are not always satisfactory in order to develop a further high polymerization activity while maintaining high stereoregularity, and further improvement has been desired.

JP-A-1-315406 JP-T-2002-522578 JP-A-10-30004

  Accordingly, an object of the present invention is to provide a method for producing a solid catalyst component for olefin polymerization, which can be prepared in a non-complex process and can provide a polymer having high stereoregularity in high yield when subjected to olefin polymerization. Is to provide.

  In such a situation, the present inventors have made extensive studies, and as a result, a magnesium compound, a tetravalent titanium halogen compound, and an electron donating compound are brought into contact with each other in the presence of a hydrocarbon compound solvent, and reacted to obtain a solid obtained. In the method for producing a solid catalyst component in which the product is washed with a hydrocarbon compound solvent, when washing with a hydrocarbon compound solvent containing a halogen-containing hydrocarbon compound is performed at least once in the washing, as compared with a conventional catalyst, It has been found that the stereoregularity and yield of the polymer can be maintained at a high level, and the present invention has been completed.

That is, the present invention was obtained by contacting and reacting a magnesium compound (a), a tetravalent titanium halogen compound (b) and an electron donating compound (c) in the presence of a hydrocarbon compound solvent (d). In the method for producing a solid catalyst component in which a solid product is washed with a hydrocarbon compound solvent, at least one of the washings is performed with a mixed solvent of an aliphatic hydrocarbon compound containing a halogen-containing hydrocarbon compound and an aromatic hydrocarbon compound. The present invention provides a method for producing a solid catalyst component for olefin polymerization, characterized by performing washing.

  Conventionally, it has been known to use an organic solvent containing a halogen-containing hydrocarbon as a reaction solvent, but it has not been known to use a halogen-containing hydrocarbon compound as a cleaning solvent. According to the present invention, since the specific mixed solvent containing the halogen-containing hydrocarbon is used as a cleaning solvent, the obtained solid catalyst component is used as a component for the polymerization catalyst for olefins due to the effect of increasing the cleaning effect. In this case, a high activity and a stereoregular polymer can be obtained in a high yield. Therefore, usefulness is expected in polyolefin production.

[Magnesium compound]
Magnesium compound (a) used in the method for producing a solid catalyst component for olefin polymerization of the present invention (hereinafter, simply referred to as “component (a)” includes dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, Dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, fatty acid magnesium, etc. Among these magnesium compounds, dihalogenated magnesium, a mixture of dihalogenated magnesium and dialkoxymagnesium, and dialkoxymagnesium are preferred, particularly preferably Alkoxy magnesium.

  Examples of dialkoxymagnesium include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutoxymagnesium, methoxyethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium. Those having a group are preferred, and diethoxymagnesium is particularly preferred.

  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 50 μm, and more preferably 10 to 40 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, the particle size distribution is (D90-D10) / D50 (where D90 is the integrated particle size at 90% of the particle size, D50 is the integrated particle size at 50% of the particle size (that is, the average particle size), and D10 is the integrated particle size of 10). % Is 3 or less, preferably 2 or less, more preferably 1.5 or less.

  The spherical dialkoxymagnesium as described above can be produced by spraying and drying a solution or suspension using a spraying device, by forming particles by a so-called spray drying method, or by reacting magnesium metal with alcohol. For example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-8-73388. It is exemplified in the publication.

[Tetravalent titanium halogen compound]
The tetravalent titanium halogen compound (b) (hereinafter sometimes simply referred to as “component (b)”) used in the method for producing the component (A) of the present invention is represented by the general formula (1);
Ti (OR ¹ ) _n X _4-n (1)
(Wherein, R ¹ represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and n is an integer of 0 ≦ n <4). One or more selected compounds. 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.

[Electron donating compound]
The electron donating compound (c) (hereinafter sometimes simply referred to as “component (c)”) used in the method for producing a solid catalyst component in the present invention is an organic compound containing an oxygen atom or a nitrogen atom, For example, including alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, Si—O—C bonds or Si—N—C bonds Examples include organosilicon compounds.

  Specifically, alcohols, phenols, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3- Ethers such as dimethoxypropane, formic acid ester, acetic acid ester, propionic acid ester, butyric acid ester, methyl benzoate, benzoic acid ester, p-toluic acid ester, monocarboxylic acid esters such as anisic acid ester, malonic acid diester, succinic acid Dicarboxylic acid diesters such as acid diesters, adipic acid diesters, maleic acid diesters, phthalic acid diesters, cycloalkane dicarboxylic acid diesters, cycloalkene dicarboxylic acid diesters, ketones, alkoxyesters Diol diesters, acid halides such as phthalic dichloride, terephthalic dichloride, aldehydes, amines, amides, sulfonylamines, nitriles, isocyanates, Si-O-C bonds or Si-N-C bonds The organosilicon compound containing can be mentioned. Of these electron donating compounds, ethers and carboxylic acid esters are preferred, monocarboxylic acid monoesters and dicarboxylic acid diesters are particularly preferred, and dicarboxylic acid diesters are more preferred.

  Dicarboxylic acid diesters include maleic acid diester, substituted maleic acid diester, malonic acid diester, substituted malonic acid diester, phthalic acid diester, substituted phthalic acid diester, succinic acid diester, substituted succinic acid diester, cycloalkane dicarboxylic acid diester, Alkane dicarboxylic acid diesters, cycloalkene dicarboxylic acid diesters and substituted cycloalkene dicarboxylic acid diesters are preferred.

  Examples of maleic acid diesters include diethyl maleate, dipropyl maleate, dibutyl maleate, diisobutyl maleate, dipentyl maleate, dineopentyl maleate, dihexyl maleate, dioctyl maleate, and the like. Particularly preferred are diethyl acid, dibutyl maleate, and diisobutyl maleate.

  Examples of substituted maleic diesters include alkyl substituted maleic diesters, halogen substituted maleic diesters and halogenated alkyl substituted maleic diesters, such as diethyl isopropyl bromomaleate, diethyl butyl bromomaleate, diethyl isobutyl bromomaleate, diisopropyl maleate Diethyl acetate, diethyl dibutyl maleate, diethyl diisobutyl maleate, diethyl diisopentyl maleate, diethyl isopropyl isobutyl maleate, dimethyl isopropyl isopentyl maleate, diethyl (3-chloro-n-propyl) maleate, bis (3- Bromo-n-propyl) diethyl maleate, dibutyl dimethyl maleate, dibutyl diethyl maleate, etc. Among them, dimethyl maleate, dibutyl, dibutyl diethyl maleate and diisobutyl maleate Diethyl is particularly preferred.

  Examples of the malonic acid diester include diethyl malonate, dipropyl malonate, dibutyl malonate, diisobutyl malonate, dipentyl malonate, dineopentyl malonate, and the like. Among these, diethyl malonate, dibutyl malonate, and Diisobutyl malonate is particularly preferred.

  Examples of the substituted malonic acid diester include alkyl-substituted malonic acid diester, halogen-substituted malonic acid diester, halogenated alkyl-substituted malonic acid diester, and the like, such as diethyl isopropyl bromomalonate, diethyl butyl bromomalonate, diethyl isobutyl bromomalonate, diisopropyl malon Diethyl diethyl, dibutyl malonate, dimethyl diisobutyl malonate, diethyl dibutyl malonate, diethyl diisobutyl malonate, diethyl diisopentyl malonate, diethyl isopropyl isobutyl malonate, dimethyl isopropyl isopentyl malonate, (3-chloro-n- Propyl) diethyl malonate, diethyl bis (3-bromo-n-propyl) malonate, etc., among them, dimethyl dibutylmalonate Diisobutyl dimethyl malonate, Jibuchirumaron diethyl, and diisobutyl diethyl malonate, it is particularly preferred.

  Examples of the phthalic acid diester include diethyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), and phthalate Ethyl isobutyl acid is particularly preferred from the standpoint of easy availability and high industrial versatility. One or more of these phthalic acid diesters are used.

Examples of substituted phthalic acid diesters include alkyl-substituted phthalic acid diesters, halogen-substituted phthalic acid diesters, halogenated alkyl-substituted phthalic acid diesters, and the following general formula (2);
^{_{R 3 k (C 6 H 4}} -k) (COOR 4) (2)
(In the formula, R ³ is a halogen atom or an alkyl group having 1 to 20 carbon atoms, k is the number of R ³ substituents, is an integer of 1 to 4, and R ⁴ is a straight chain having 1 to 6 carbon atoms. An alkyl group, a branched alkyl group, or an alkenyl group, and two R ^{5 s} may be the same or different. Among these, dineopentyl 4-bromophthalate, di-n-butyl 4-bromophthalate, and diisobutyl 4-bromophthalate are preferable.

  Examples of the succinic acid diester include diethyl succinate, dipropyl succinate, dibutyl succinate, diisobutyl succinate, dipentyl succinate, dineopentyl succinate, dihexyl succinate, dioctyl succinate, and the like. Particularly preferred are diethyl acid, dibutyl succinate, and diisobutyl succinate.

  Examples of substituted succinic acid diesters include diethyl isopropyl bromosuccinate, diethyl butyl bromosuccinate alkyl substituted succinic acid diester, halogen substituted succinic acid diester, halogenated alkyl substituted succinic acid diester, and the like. Diethyl acetate, diethyl dibutyl succinate, diethyl diisobutyl succinate, diethyl diisopentyl succinate, diethyl isopropyl isobutyl succinate, dimethyl isopropyl isopentyl succinate, diethyl (3-chloro-n-propyl) succinate, bis (3- Bromo-n-propyl) diethyl succinate, dibutyl dimethyl succinate, dibutyl diethyl succinate etc. can be exemplified, among these, dibutyl dimethyl succinate, di Chirukohaku dibutyl and diisobutyl diethyl succinate is particularly preferred. As the cycloalkanedicarboxylic acid diester, diethyl cyclobutane-1,1-dicarboxylate, diethyl cyclohexane-1,2-dicarboxylate, and dibutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate are particularly preferable. Examples of the cycloalkene dicarboxylic acid diester include diethyl 1-cyclohexene-1,2-dicarboxylate, dipropyl 1-cyclohexene-1,2-dicarboxylate, dibutyl 1-cyclohexene-1,2-dicarboxylate, 4-cyclohexene-1, Particularly preferred are diethyl 2-dicarboxylate, dipropyl 4-cyclohexene-1,2-dicarboxylate, and dibutyl 4-cyclohexene-1,2-dicarboxylate. In addition, it is also preferable to use the above esters in combination of two or more. When the total number of carbon atoms of the alkyl residue of the ester used at this time is compared with that of other esters, the ester having a difference of 4 or more. It is desirable to combine them.

The monocarboxylic acid monoester is an aliphatic monocarboxylic acid ester or an aromatic monocarboxylic acid ester, specifically, 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, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl anisate, ethyl anisate, and the following general formula (3);
(R ⁵ ) ₃ CCOOR ⁶ (3)
(Wherein R ⁵ represents an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and R ⁶ represents an alkyl group having 1 to 12 carbon atoms). And the like.

In the above general formula (3), R ⁵ is a methyl group, an ethyl group, a propyl group or an isopropyl group, preferably a methyl group. A compound in which R ⁵ is a methyl group is an ester of pivalic acid. R ⁶ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a t-butyl group, and particularly preferably a methyl group or an ethyl group. Among the above monocarboxylic acid esters, ethyl benzoate, ethyl p-ethoxybenzoate, ethyl anisate, methyl pivalate and ethyl trimethylacetate are preferred. These monocarboxylic acid esters can be used alone or in combination of two or more.

[Hydrocarbon compound solvent (d)]
In the present invention, the hydrocarbon compound solvent (d) used when the component (a), the component (b) and the component (c) are brought into contact with each other and reacted (hereinafter also simply referred to as “component (d)”). Examples thereof include aromatic hydrocarbon compounds such as benzene and alkylbenzene, and saturated hydrocarbon compounds such as hexane and heptane. Specifically, benzene, toluene, xylene, ethylbenzene, ethyltoluene, propylbenzene, butylbenzene, pentyl. Benzene, hexylbenzene, heptylbenzene, octylbenzene, decylbenzene, dodecylbenzene, allylbenzene, trimethylbenzene, diethylbenzene, cyclohexane, pentane, hexane, heptane, octane, nonane, decane, and the like are used. Among these hydrocarbon compounds, benzene, toluene, xylene, ethylbenzene, ethyltoluene, cyclohexane, hexane, heptane, decane and the like are preferably used. Moreover, these may be used independently or may be used in mixture of 2 or more types. In the case of using a mixture of two or more kinds, a mixture of an aromatic hydrocarbon and an aliphatic hydrocarbon is preferably used. In addition, the component (d) may contain a halogenated hydrocarbon compound.

  In the present invention, the hydrocarbon compound solvent for washing the obtained solid product may be the same as the component (d) described above, and the component (a), the component (b) and the component (c) are brought into contact with each other. The hydrocarbon compound solvent (d) used in the reaction may be the same compound or a different compound.

[Hydrocarbon compound solvent containing halogenated hydrocarbon compound]
In the washing of the obtained solid product of the present invention, a halogenated hydrocarbon compound (d1) (hereinafter simply referred to as “component ( d1) "also includes halogenated hydrocarbon compounds having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, preferably saturated or unsaturated aliphatic and aromatic hydrocarbon mono and polyhalogens. Monohalogen hydrocarbon compounds and polyhalogen hydrocarbon compounds which are substituted products, particularly preferably monohalogen hydrocarbon compounds having 1 to 10 carbon atoms. The monohalogen hydrocarbon compound preferably has 2 to 10 carbon atoms, particularly preferably 3 to 8 carbon atoms, and more preferably 3 to 4 carbon atoms.

  Specific examples of the component (d1) include chloromethane, chloroethane, chloropropane, chlorobutane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, 1,2-dichloroethane and the like. Among these halogenated hydrocarbon compounds, chloroethane, chloropropane, chlorobutane, chlorooctane, chlorononane, and chlorodecane are preferable, and in particular, 1-chloropropane, 1-chlorobutane, 1-chloro-2-methylpropane, and 3- (chloromethyl) heptane. 1-chloropropane, 1-chlorobutane and 1-chloro-2-methylpropane are more preferable. Moreover, these components (d1) may be used independently or may be used in mixture of 2 or more types.

  Examples of the hydrocarbon compound solvent containing the halogenated hydrocarbon compound, that is, the hydrocarbon compound solvent mixed with the component (d1) include the same as the component (d), and the components (a) and (b ) And component (c) may be the same compound as or different from the hydrocarbon compound solvent (d) used in the reaction. Further, it may be the same compound as the component (d) used in washing or a different compound.

  The content of the component (d1) in the component (d) is such that the content of the component (d1) is 3 to 20,000 ppm by weight, preferably 5 to 2,000 ppm by weight, particularly preferably 30% of the whole component (d). -200 ppm by weight. When the content ratio of the component (d1) in the component (d) is within the above range, the cleaning efficiency can be increased, and the component (d1) in the component (d) can be used as a halogen source, which is a highly active solid. A catalyst component can be obtained, and the stereoregularity of the resulting polymer can be maintained high.

[Polysiloxane]
In the method for producing the solid catalyst component (A) of the present invention, polysiloxane (hereinafter sometimes simply referred to as “component (e)”) is further used when the components (a) to (d) are brought into contact with each other. It is preferable that the stereoregularity or crystallinity of the produced polymer can be improved, and further the fine powder of the produced polymer 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} 10,000 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 method for producing component (A) of the present invention, first, component (a), component (b), component (c) and optionally component (e) are contacted in the presence of component (d), React. 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. Contact means simply contacting and stirring and mixing, or dispersing or suspending and modifying treatment, and the contact temperature is the temperature at the time of contact of each component, even in a relatively low temperature range near room temperature, It may be the same temperature as the reaction temperature. The reaction temperature at the time of reaction after contact to obtain a product is preferably in the temperature range of 40 to 130 ° C. 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 solid product obtained by the catalytic reaction of component (a), component (b), component (c) and, if necessary, component (e) is washed with component (d) to obtain component (A). The washing is performed at least once, preferably twice, particularly preferably 3, 4, 5, 6 or 7 times with a hydrocarbon compound solvent (d) containing a halogen-containing hydrocarbon compound (d1). Do. Thereby, the washing | cleaning efficiency of a solid product increases and the titanium seed | species which does not become an active point can be removed efficiently. Moreover, residual magnesium can be halogenated, a highly active solid catalyst component can be obtained, and the stereoregularity of the resulting polymer can be maintained high.

  In the present invention, the solid product obtained by the contact reaction of the component (a), the component (b), the component (c) and, if necessary, the component (e) is further converted into a hydrocarbon compound solvent (d). In the presence of, the tetravalent titanium halogen compound (b) is contacted and reacted, and then the operation of washing the resulting solid product with a hydrocarbon compound solvent is repeated. Washing with a hydrocarbon compound solvent (d) containing a halogen-containing hydrocarbon compound (d1) at least once, preferably twice, particularly preferably 3, 4, 5, 6 or 7 times Is preferred. Thereby, a highly active solid catalyst component can be obtained, and the stereoregularity of the produced polymer can be maintained high.

The following are illustrated as a preferable manufacturing method of the component (A) of this invention.
(1) The component (a) is suspended in the component (d), and then the component (b) is contacted, and then the component (c) is contacted and reacted, and then the obtained solid product is converted into the component A method of preparing component (A) by washing with (d) comprising (d1);
(2) The component (a) is suspended in the component (d), and then the component (c) is contacted and then the component (b) is contacted and reacted. A method of preparing component (A) by washing with (d) comprising (d1);
(3) After preparing a suspension composed of component (a), component (c) and component (d), and then contacting and reacting the mixture formed from component (b) and component (d), A method of preparing component (A) by washing the resulting solid product with (d) comprising component (d1);
(5) In the above (1) to (3), after washing with (d) containing the component (d1), the resulting solid product is added to the component (b) or component in the presence of (d). A method of preparing component (A) by contacting (b) and component (c) and then repeating washing with (d) containing component (d1) a plurality of times;

  In addition, in the contact of the component (a), the component (b), the component (c), and the component (d), the usage ratio of the component (b) to the component (a) is 1 to 10 ml per 1 g of the component (a), The use ratio of (c) to component (a) is 0.1 to 1 ml per 1 g of component (a), and the use ratio of component (d) to component (a) is 3 to 20 ml per 1 g of component (a). It is preferable that the usage-amount with respect to the component (a) of (d) containing (d1) is 3-20 ml per 1g of component (a).

  In the washing using the component (d) containing the component (d1), the replacement ratio of the liquid phase part after the reaction with the component (d) containing the component (d1) is 80% by volume or more, preferably 95% by volume. As described above, it is preferable to carry out until 99% by volume or more.

  That is, as a preferred method for preparing the component (A) of the present invention, first, a suspension is formed from the component (a), the component (c) and the component (d). Then, a mixed solution is formed from the component (b) and the component (d), and the suspension is added to the mixed solution. Then, the obtained mixed solution is heated and subjected to a reaction treatment (first reaction treatment). After completion of the reaction, the obtained solid product is washed with the component (d) which is liquid at room temperature, and further the component (b) and the component (d) are further added to -20 to 100 ° C. in the washed solid product. Then, the temperature is raised, the reaction treatment (secondary reaction treatment) is performed, and after completion of the reaction, the operation of washing the obtained solid product with the component (d) is repeated 1 to 10 times to obtain the component (A ) And in the said washing | cleaning process, it wash | cleans by (d) containing a component (d1) at least 1 time, Preferably it is 2 times, Especially preferably, 3 times, 4 times, 5 times, 6 times, or 7 times. Thus, in the washing step, by using the component (d) containing the component (d1) as the washing liquid at least once, the polymerization activity of the solid catalyst component and the stereoregularity of the resulting polymer can be improved. it can.

  Based on the above, as a particularly preferable preparation method of the solid catalyst component (A) in the present invention, the component (a) is suspended in the mixed solvent (d), and then the component (b) is contacted with the suspension. Thereafter, a reaction process is performed. At this time, before or after contacting the component (b) with the suspension, one or more of the components (c) such as carboxylic acid esters are contacted at −20 to 130 ° C. Correspondingly, the component (e) is brought into contact and subjected to a reaction treatment to obtain a solid product. At this time, it is desirable to perform the aging reaction at a low temperature before or after contacting one or more of the electron donating compounds. After washing this solid product with a liquid hydrocarbon compound (d) at room temperature (intermediate washing), the tetravalent titanium halogen compound (b) was again added at −20 to 100 ° C. in the presence of the solvent (d). Contact is performed and a reaction treatment is performed to obtain a solid product. If necessary, intermediate cleaning and reaction treatment may be repeated a plurality of times. Subsequently, the solid product is washed with liquid component (d) at room temperature by decantation to obtain a solid catalyst component (A). And in the said washing | cleaning process, it wash | cleans by (d) containing a component (d1) at least 1 time, Preferably it is 2 times, Especially preferably, 3 times, 4 times, 5 times, 6 times, or 7 times. Thus, in the washing step, by using the component (d) containing the component (d1) as the washing liquid at least once, the polymerization activity of the solid catalyst component and the stereoregularity of the resulting polymer can be improved. it can.

  The amount ratio of each component used in preparing the solid catalyst component (A) varies depending on the preparation method and cannot be determined unconditionally. For example, the component (b) is 0.5 to 100 per mole of the component (a). Mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and component (c) is 0.01 to 10 mol, preferably 0.01 to 1 mol, more preferably 0.02 to 0 mol. 0.6 mol, and the polysiloxane (e) is 0.01 to 100 g, preferably 0.05 to 80 g, more preferably 1 to 50 g.

  Further, the content of titanium, magnesium, a halogen atom, and an electron donating compound in the solid catalyst component (A) in the present invention is not particularly limited, but preferably titanium is 0.5 to 10.0% by weight, preferably 1.0-8.0 wt%, more preferably 1.5-5.0 wt% magnesium is 10-70 wt%, more preferably 10-50 wt%, particularly preferably 15-40 wt%, still more preferably Is 15 to 25% by weight, halogen atoms are 20 to 90% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, still more preferably 45 to 75% by weight, and the total amount of electron-donating compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight in total, and particularly preferably 2 to 20% by weight in total.

[Organic aluminum compound (B)]
The solid catalyst component (A) obtained by the production method of the present invention is used as an olefin polymerization catalyst. In the olefin polymerization catalyst, as the organoaluminum compound (B) (hereinafter sometimes simply referred to as “component (B)”) used together with the solid catalyst component (A), the following general formula (4);
R ⁷ _p AlQ _3-p (4)
(Wherein R ⁷ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3). Although not particularly limited, R ⁷ is preferably an ethyl group or an isobutyl group, and Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, p is preferably 2 or 3, and 3 is particularly preferable. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and triisobutylaluminum are preferable.

[Electron-donating compound (C)]
The electron donating compound (C) used in forming the olefin polymerization catalyst (hereinafter sometimes simply referred to as “component (C)”) is an organic compound containing an oxygen atom or a nitrogen atom, Examples thereof include alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds, aminosilane compounds, and the like.

  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, amyl ether, diphenyl ether, 9,9- Ethers such as bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 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, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, p-toluyl Monocarboxylic acid esters such as methyl, ethyl p-toluate, methyl anisate, ethyl anisate, dimethyl malonate, diethyl malonate, diethyl maleate, dibutyl maleate, diethyl succinate, dimethyl adipate, diethyl adipate Dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, phthalate Dicarboxylic acid esters such as dinonyl acid and didecyl phthalate, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone and benzophenone, phthalic acid dichloride, terephthalic acid dichlora Acid halides such as acetaldehyde, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, amides such as oleic acid amide and stearic acid amide Nitriles such as acetonitrile, benzonitrile and tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, organosilicon compounds containing Si—O—C bonds, aminosilane compounds containing Si—N—C bonds, etc. Can do.

  Among the external electron donating compounds (C) above, ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, anisic acid Monocarboxylic acid esters such as ethyl, ethers such as 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and organosilicon compounds containing Si—O—C bonds And aminosilane compounds containing Si-N-C bonds are preferred.

Among the external electron donating compounds of the above (C), as the organosilicon compound having a Si—O—C bond, the following general formula (5);
R ⁸ _q Si (OR ⁹ ) _4-q (5)
(In the formula, R ⁸ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, an alkylamino group having 1 to 12 carbon atoms, or a carbon number. Any one of 1 to 12 dialkylamino groups, which may be the same or different, R ⁹ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a vinyl group, or an allyl group; And an aralkyl group, which may be the same or different, and q is an integer of 0 ≦ q ≦ 3).

Among the external electron donating compounds (C) above, the aminosilane compound having a Si—N—C bond is represented by the following general formula (6);
(R ¹⁰ R ¹¹ N) _s SiR ¹² _4-s (6)
(Wherein R ¹⁰ and R ⁹ are a hydrogen atom, a straight chain having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, and a cycloalkyl having 3 to 20 carbon atoms. R ¹⁰ and R ¹¹ may be the same or different, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring, and R ¹² is a straight chain having 1 to 20 carbon atoms. Or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a linear or branched alkoxy group having 1 to 20 carbon atoms, a vinyloxy group, an allyloxy group, and a cycloalkyl group having 3 to 20 carbon atoms. , aryl group, aryloxy group, and shows their derivatives, if R ¹² there are a plurality, the plurality of R ¹² is an integer of good .s be the same or different 1 to 3.) aminosilane compound represented by the And the like.

  Examples of such organosilicon compounds include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, alkyl (cycloalkyl) alkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, Cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane, trialkyl (alkylamino) silane, 1,3-diether compound Specifically, phenyltrimethoxysilane, t-butyltrimethoxysilane, diisopropyldimethoxysilane, diisopentyl Dimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, tetra Butoxysilane, bis (ethylamino) methylethylsilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) Methylsilane, diethylaminotriethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (perhydroisoxy) And lino) dimethoxysilane, bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, and the like. Among them, phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopropyldimethoxysilane , Isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) Dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (perhydroisoquinolino) dimethoxysilane, diethylamino Notriethoxysilane and the like are preferably used, and the above organosilicon compounds can be used alone or in combination of two or more.

[Polymerization of olefins]
In the present invention, olefins are polymerized or copolymerized in the presence of an olefin polymerization catalyst obtained by bringing the components (A), (B) and (C) into contact with each other. 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. Particularly preferred is propylene. In the case of polymerization of propylene, copolymerization with other olefins can also be performed. Examples of olefins to be copolymerized include ethylene, 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.

  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, the organoaluminum compound (B) is titanium in the solid catalyst component (A). It is used in the range of 1 to 2000 mol, preferably 50 to 1000 mol, per mol of atoms. The organosilicon compound (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per 1 mol of the component (B).

  The order of contacting the components is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the external electron-donating compound (C) is contacted, and then the solid catalyst component (A ) Is 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 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 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Further, in the present invention, when the olefin is polymerized using a catalyst containing the solid catalyst component (A), the component (B) and the component (C) for olefin polymerization (also referred to as main polymerization), the catalytic activity and the stereoregulation are determined. In order to further improve the properties and particle properties of the resulting polymer, it is desirable to perform pre-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.

  In carrying out the prepolymerization, the order of contacting the respective components and monomers is arbitrary, but preferably, the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the olefin. After contacting the solid catalyst component (A) for homopolymerization, an olefin such as propylene and / or one or more other olefins are contacted. When the prepolymerization is performed by combining the component (C), the component (B) is first charged in the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the component (C) is contacted. A method of contacting an olefin such as propylene and / or one or other two or more olefins after contacting the solid catalyst component (A) for olefin polymerization is desirable.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

<Preparation of solid catalyst component (A1)>
A 200 ml round bottom flask, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, was charged with 10 g of diethoxymagnesium, 80 ml of toluene and 2.4 ml of di-n-butyl phthalate to obtain a suspended state. Next, the suspension was added to the mixed solution in which 20 ml of titanium tetrachloride and 30 ml of toluene were previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and the liquid temperature was kept at 3 ° C. The liquid was added. Thereafter, the liquid temperature was raised from 3 ° C. to 90 ° C. over 90 minutes, and the reaction was carried out with stirring for 1.5 hours while maintaining the temperature of 90 ° C. After completion of the reaction, it was washed four times with 100 ml of a toluene solution containing 5 ppm by weight of 1-chlorobutane and maintained at a temperature of 70 ° C., 20 ml of titanium tetrachloride and 40 ml of toluene were newly added, and the temperature was raised to 100 ° C. The reaction was allowed to stir for an hour. After completion of the reaction, the solid catalyst component (A1) was obtained by washing 7 times with 100 ml of n-heptane. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.7 weight%.

<Formation and polymerization of polymerization catalyst>
In an autoclave with a stirrer with 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 (A1) as titanium atoms was charged. To form a polymerization catalyst. Thereafter, 4 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 60 minutes. The polymerization activity per gram of the solid catalyst component at this time, the ratio of boiling n-heptane insoluble matter in the produced polymer (HI), the bulk density (BD) of the produced polymer (a) and the melt index value (MI) It is 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. ). The bulk density of the produced polymer (a) was measured according to JIS K 6721. The melt index value (MI) of the produced polymer (a) was measured according to ASTM D 1238 and JIS K 7210.

  Preparation of a solid catalyst component and polymerization catalyst in the same manner as in Example 1 except that the same amount of toluene solution containing 34 ppm by weight of 1-chlorobutane was used instead of the toluene solution containing 5 ppm by weight of 1-chlorobutane. Formation and polymerization evaluation. The results are shown in Table 1. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.7 weight%.

  Preparation of a solid catalyst component and polymerization catalyst in the same manner as in Example 1 except that the same amount of toluene solution containing 1 wt.-chlorobutane was substituted for the toluene solution containing 1 wt.-chlorobutane. Formation and polymerization evaluation. The results are shown in Table 1. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.6 weight%.

  Preparation of a solid catalyst component and polymerization catalyst in the same manner as in Example 1 except that the same amount of toluene solution containing 200 ppm by weight of 1-chlorobutane was used instead of the toluene solution containing 5 ppm by weight of 1-chlorobutane. Formation and polymerization evaluation. The results are shown in Table 1. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.6 weight%.

  Preparation of a solid catalyst component, polymerization catalyst in the same manner as in Example 1 except that the same amount of toluene solution containing 2000 ppm by weight of 1-chlorobutane was used instead of the toluene solution containing 5 ppm by weight of 1-chlorobutane Formation and polymerization evaluation. The results are shown in Table 1. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.6 weight%.

  Preparation of a solid catalyst component, polymerization catalyst in the same manner as in Example 1 except that the same amount of toluene solution containing 10000 chloroppm of 1-chlorobutane was used instead of the toluene solution containing 5 ppm by weight of 1-chlorobutane Formation and polymerization evaluation. The results are shown in Table 1. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.6 weight%.

  Preparation of a solid catalyst component, formation of a polymerization catalyst and evaluation of polymerization were carried out in the same manner as in Example 3 except that 90 wt ppm of 1-chloro-2-methylpropane was used instead of 90 wt ppm of 1-chlorobutane. It was. The results are shown in Table 1. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.7 weight%.

  Preparation of a solid catalyst component, formation of a polymerization catalyst, and evaluation of polymerization were carried out in the same manner as in Example 3 except that 90 wt ppm of 3- (chloromethyl) heptane was used instead of 90 wt ppm of 1-chlorobutane. . The results are shown in Table 1. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.8 weight%.

  Instead of using a toluene solution containing 5 ppm by weight of 1-chlorobutane, the same amount of a solution containing 200 ppm by weight of 1-chlorobutane in a mixture of 2% by weight of ethyltoluene, 13% by weight of heptane and 85% by weight of toluene was used. In the same manner as in Example 1, preparation of a solid catalyst component, formation of a polymerization catalyst, and evaluation of polymerization were performed. The results are shown in Table 1. In addition, when the solid-liquid in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.9 weight%.

<Preparation of solid catalyst component (A2)>
A 200 ml round bottom flask, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, was charged with 10 g of diethoxymagnesium, 80 ml of toluene and 2.4 ml of di-n-butyl phthalate to obtain a suspended state. Next, the suspension was added to the mixed solution in which 40 ml of titanium tetrachloride and 10 ml of toluene were previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and the liquid temperature was kept at 3 ° C. The liquid was added. Thereafter, the liquid temperature was raised from 3 ° C. to 90 ° C. over 90 minutes, and the reaction was carried out with stirring for 1.5 hours while maintaining the temperature of 90 ° C. After completion of the reaction, the mixture was washed 4 times with 100 ml of a toluene solution containing 90 wt ppm of 1-chlorobutane at a temperature of 70 ° C., 40 ml of titanium tetrachloride and 40 ml of toluene were newly added, the temperature was raised to 100 ° C., and the mixture was stirred for 1 hour. It was made to react. After completion of the reaction, the solid catalyst component (A2) was obtained by washing 7 times with 100 ml of n-heptane. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.6 weight%.

<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 (A2) was used instead of the solid catalyst component (A1). The polymerization results are shown in Table 1.

<Preparation of solid catalyst component (A3)>
A 200 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer was charged with 10 g of diethoxymagnesium, 80 ml of toluene and 2.4 ml of di-n-butyl phthalate to form a suspended state. . Next, the suspension was added to the mixed solution in which 20 ml of titanium tetrachloride and 30 ml of toluene were previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and the liquid temperature was kept at 3 ° C. The liquid was added. Thereafter, the liquid temperature was raised from 3 ° C. to 90 ° C. over 90 minutes, and the reaction was carried out with stirring for 1.5 hours while maintaining the temperature of 90 ° C. After completion of the reaction, the mixture was washed 4 times with 100 ml of 80 ° C. toluene, 20 ml of titanium tetrachloride and 40 ml of toluene were newly added, and the temperature was raised to 100 ° C. and reacted for 1 hour with stirring. After completion of the reaction, the solid catalyst component (A3) was obtained by washing with 100 ml of n-heptane solution containing 90 ppm by weight of 1-chlorobutane and maintained at a temperature of 40 ° C. The solid-liquid component in the solid catalyst component was separated and the titanium content in the solid content was measured and found to be 3.5% by weight.

<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 (A3) was used instead of the solid catalyst component (A1). The polymerization results are shown in Table 1.

<Preparation of solid catalyst component (A4)>
A 200 ml round bottom flask, which was sufficiently substituted with nitrogen gas and equipped with a stirrer, was charged with 10 g of diethoxymagnesium, 80 ml of toluene and 3.2 ml of dimethyl diisobutylmalonate to obtain a suspended state. Next, the suspension was added to the mixed solution in which 20 ml of titanium tetrachloride and 30 ml of toluene were previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and the liquid temperature was kept at 3 ° C. The liquid was added. Thereafter, the liquid temperature was raised from 3 ° C. to 90 ° C. over 90 minutes, and the reaction was carried out with stirring for 1.5 hours while maintaining the temperature of 90 ° C. After completion of the reaction, the mixture was washed 4 times with 100 ml of a toluene solution containing 200 ppm by weight of 1-chlorobutane and maintained at a temperature of 70 ° C., 20 ml of titanium tetrachloride and 40 ml of toluene were newly added, and the temperature was raised to 100 ° C. The reaction was allowed to stir for an hour. After completion of the reaction, it was washed again with 100 ml of a toluene solution containing 200 ppm by weight of 1-chlorobutane and maintained at a temperature of 70 ° C., 20 ml of titanium tetrachloride and 40 ml of toluene were newly added, and the temperature was raised to 100 ° C. The reaction was allowed to stir for 1 hour. The solid catalyst component (A4) was obtained by washing 7 times with 100 ml of n-heptane. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.4 weight%.

<Formation and polymerization of polymerization catalyst>
In the same manner as in Example 1, except that the solid catalyst component (A3) was used instead of the solid catalyst component (A1), and 1.5 liters of hydrogen gas was used instead of 4 liters of hydrogen gas. Formation and polymerization evaluation was performed. The results are shown in Table 1.

<Preparation of solid catalyst component (A5)>
A 200 ml round bottom flask, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, was charged with 10 g of diethoxymagnesium, 80 ml of toluene and 2.8 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. In a suspended state. Next, the suspension was added to the mixed solution in which 20 ml of titanium tetrachloride and 30 ml of toluene were previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and the liquid temperature was kept at 3 ° C. The liquid was added. Thereafter, the liquid temperature was raised from 3 ° C. to 90 ° C. over 90 minutes, and the reaction was carried out with stirring for 1.5 hours while maintaining the temperature of 90 ° C. After completion of the reaction, the mixture was washed 4 times with 100 ml of a toluene solution containing 200 ppm by weight of 1-chlorobutane and maintained at a temperature of 70 ° C., 20 ml of titanium tetrachloride and 40 ml of toluene were newly added, and the temperature was raised to 100 ° C. The reaction was allowed to stir for an hour. After the completion of the reaction, the solid catalyst component (A5) was obtained by washing 7 times with 100 ml of n-heptane. In addition, when the solid-liquid in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.0 weight%.

<Formation and polymerization of polymerization catalyst>
In the same manner as in Example 1, except that the solid catalyst component (A1) was used instead of the solid catalyst component (A1), and the hydrogen gas was changed to 4 liters instead of 4 liters of hydrogen gas. Polymerization evaluation was performed. The results are shown in Table 1.
Using this solid catalyst component, a polymerization catalyst was formed and evaluated in the same manner as in Example 1 except that 3 liters of hydrogen gas was used instead of 4 liters of hydrogen gas. The results are shown in Table 1.

<Preparation of solid catalyst component (A6)>
A 200 ml round bottom flask, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, was charged with 10 g of diethoxymagnesium, 80 ml of toluene and 3.6 ml of diethyl diisopropyl succinate to form a suspended state. Next, the suspension was added to the mixed solution in which 20 ml of titanium tetrachloride and 30 ml of toluene were previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and the liquid temperature was kept at 3 ° C. The liquid was added. Thereafter, the liquid temperature was raised from 3 ° C. to 90 ° C. over 90 minutes, and the reaction was carried out with stirring for 1.5 hours while maintaining the temperature of 90 ° C. After completion of the reaction, the mixture was washed 4 times with 100 ml of a toluene solution containing 200 ppm by weight of 1-chlorobutane and maintained at a temperature of 70 ° C., 20 ml of titanium tetrachloride and 40 ml of toluene were newly added, and the temperature was raised to 100 ° C. The reaction was allowed to stir for an hour. After completion of the reaction, the solid catalyst component (A6) was obtained by washing 7 times with 100 ml of n-heptane. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.8 weight%.

<Formation and polymerization of polymerization catalyst>
In the same manner as in Example 1 except that the solid catalyst component (A6) was used instead of the solid catalyst component (A1), and 3 liters of hydrogen gas was used instead of 4 liters of hydrogen gas. Polymerization evaluation was performed. The results are shown in Table 1.

Comparative Example 1
A solid catalyst component was prepared, a polymerization catalyst was formed, and polymerization was evaluated in the same manner as in Example 1 except that the same amount of toluene was used instead of the toluene solution containing 1 ppm of 1-chlorobutane. The results are shown in Table 1. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.6 weight%.

Comparative Example 2
Preparation of a solid catalyst component, formation of a polymerization catalyst and evaluation of polymerization were carried out in the same manner as in Example 1 except that the same amount of 1-chlorobutane was used instead of the toluene solution containing 1 ppm of 1-chlorobutane. It was. The results are shown in Table 1. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.6 weight%.

Comparative Example 3
A solid catalyst component was prepared, a polymerization catalyst was formed, and polymerization was evaluated in the same manner as in Example 12 except that the same amount of toluene was used instead of the toluene solution containing 1-chlorobutane at 200 ppm by weight. The solid-liquid component in the solid catalyst component was separated and the titanium content in the solid content was measured and found to be 3.5% by weight. The polymerization results are shown in Table 1.

  As is apparent from Table 1, when the solid catalyst component obtained by the method of the present invention is used as one component of an olefin polymerization catalyst, it exhibits high activity and obtains a stereoregular polymer in high yield. I was able to.

  In the production of olefins, high productivity can be increased, and general-purpose polyolefins can be provided at low cost.

Claims (9)

A magnesium compound (a), a tetravalent titanium halogen compound (b), and an electron donating compound (c) are contacted and reacted in the presence of a hydrocarbon compound solvent (d), and the resulting solid product is converted to a hydrocarbon. In the method for producing a solid catalyst component washed with a compound solvent, the washing is performed with a mixed solvent of an aliphatic hydrocarbon compound containing a halogen-containing hydrocarbon compound and an aromatic hydrocarbon compound at least once. A method for producing a solid catalyst component for olefin polymerization.   The solid product is further contacted and reacted with the tetravalent titanium halogen compound (b) in the presence of the hydrocarbon compound solvent (d), and then the obtained solid product is washed with the hydrocarbon compound solvent. 2. The method for producing a solid catalyst component for olefin polymerization according to claim 1, further comprising a step of repeatedly performing the operation.   The method for producing a solid catalyst component for olefin polymerization according to claim 1 or 2, wherein the halogen-containing hydrocarbon compound has 1 to 10 carbon atoms.   The said halogen-containing hydrocarbon compound is a monohalogenated hydrocarbon compound, The manufacturing method of the solid catalyst component for olefin polymerization of any one of Claims 1-3 characterized by the above-mentioned.   2. The halogen-containing hydrocarbon compound is one or more selected from chloroethane, 1-chloropropane, 1-chlorobutane, 1-chloro-2-methylpropane and 3- (chloromethyl) heptane. The manufacturing method of the solid catalyst component for olefin polymerization of any one of -4.   The solid catalyst component for olefin polymerization according to any one of claims 1 to 5, wherein the halogen-containing hydrocarbon compound is contained in the hydrocarbon compound solvent in an amount of 3 to 20,000 ppm by weight. Production method.   The method for producing a solid catalyst component for olefin polymerization according to any one of claims 1 to 6, wherein the tetravalent titanium halogen compound (b) is titanium tetrachloride.   The method for producing a solid catalyst component for olefin polymerization according to any one of claims 1 to 7, wherein the electron donating compound (c) is a carboxylic acid ester or an ether compound.   The method for producing a solid catalyst component for olefin polymerization according to any one of claims 1 to 8, wherein the magnesium compound (a) is dialkoxymagnesium.