JP5105480B2 - SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION, PROCESS FOR PRODUCING THE SAME AND CATALYST, AND METHOD FOR PRODUCING OLEFIN POLYMER USING THE SAME - Google Patents

Description

  The present invention relates to a solid catalyst component for polymerizing olefins, a method for producing the same, and a catalyst that can maintain a high degree of stereoregularity and yield of a polymer and can obtain a polymer with less fine powder.

  Conventionally, in the polymerization of olefins, many solid catalyst components for olefin polymerization containing magnesium, titanium, an electron donating compound and halogen as essential components have been proposed. In particular, diethoxymagnesium is representative as a magnesium raw material. Solid catalyst components prepared using alkoxymagnesium compounds have high performance and are widely used industrially.

  For example, in Patent Document 1 (Japanese Patent Laid-Open No. 63-3010), a product obtained by contacting dialkoxymagnesium, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon compound and a titanium halide is in a powder state. A method for polymerizing olefins and a solid catalyst component prepared by heat treatment with olefin, an olefin polymerization catalyst comprising an organoaluminum compound and an organosilicon compound have been proposed.

  In Patent Document 2 (Japanese Patent Laid-Open No. 62-50309), water is brought into contact with a solid composition obtained by contacting dialkoxymagnesium, a diester of an aromatic dicarboxylic acid, a halogenated hydrocarbon and a titanium halide. Then, a catalyst component obtained by contacting the titanium halide again, a catalyst for polymerizing olefins composed of an organoaluminum compound and an organosilicon compound, and a method for polymerizing olefins in the presence of the catalyst have been proposed.

  Moreover, in patent document 3 (Unexamined-Japanese-Patent No. 11-12316), it contains magnesium, titanium, an electron-donating compound, and a halogen atom prepared by making a magnesium compound, a titanium compound, and an electron-donating compound contact. A solid catalyst component for olefin polymerization, which is obtained by bringing an alcohol into contact with a solid component; an olefin polymerization catalyst comprising an organoaluminum compound and an organosilicon compound; and an olefin in the presence of the catalyst. A polymerization method has been proposed.

  Moreover, in patent document 4 (Unexamined-Japanese-Patent No. 2003-261612), it contains magnesium, titanium, an electron-donating compound, and a halogen atom prepared by contacting a magnesium compound, a titanium compound, and an electron-donating compound. A solid catalyst component for olefin polymerization, which is obtained by bringing ether into contact with a solid component, an olefin polymerization catalyst comprising an organoaluminum compound and an organosilicon compound, and an olefin in the presence of the catalyst. A polymerization method has been proposed.

  Each of the above prior arts has a high activity capable of omitting a 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.

  As means for solving this problem, in Patent Document 5 (Japanese Patent Laid-Open No. 6-287225), a suspension of spherical dialkoxymagnesium, aromatic hydrocarbon compound and phthalic acid diester is used as an aromatic hydrocarbon compound. It is added to the mixed solution of titanium tetrachloride and allowed to react. The resulting reaction product is washed with an aromatic hydrocarbon compound, and the solid component obtained by reacting with titanium tetrachloride again is dried to remove fine powder. A solid catalyst component for olefin polymerization obtained through a process has been proposed.

Although the above-mentioned proposal has the effect of removing the fine powder of the solid catalyst component itself and reducing the amount of fine powder of the resulting polymer to some extent, the generation of ultrafine polymer called microfine is still in particular. The development of a catalyst with little generation of a fine polymer has been desired, but the above-described prior art is not sufficient to solve the problem.
JP 63-3010 A (Claims) JP-A-62-50309 (Claims) JP-A-11-12316 (Claims) JP 2003-261612 A (Claims) JP-A-6-287225 (Claims)

  Therefore, an object of the present invention is to provide olefins that can maintain a high degree of polymer stereoregularity and yield when subjected to olefin polymerization, and that can obtain a polymer having a small particle size and a sharp particle size distribution. An object of the present invention is to provide a solid catalyst component as a component of a polymerization catalyst, a production method thereof, and a catalyst.

  In this situation, as a result of intensive studies, the present inventor has suppressed the generation of fine particles as much as possible when forming the solid catalyst component in order to suppress the amount of fine powder polymer generated when olefins are polymerized. For that purpose, if the solid product obtained in the process of producing the solid catalyst component is brought into contact with alcohol vapor or ether vapor and water vapor, the fine powder existing on the particle surface of the solid product is removed and peeled off. As a result, the present inventors have found that the particles that can be easily removed can be removed and the fracture strength of the particle surface is improved, and the present invention has been completed.

  That is, the present invention contacts a magnesium compound (a), a tetravalent titanium halogen compound (b) and an electron donating compound (c) other than alcohol and ether to form a solid product, and then the solid product A solid catalyst component for olefin polymerization obtained by bringing alcohol vapor or ether vapor into contact with water vapor and then bringing the solid product after the vapor contact into contact with a tetravalent titanium halogen compound (b) Is to provide.

  In addition, the present invention contacts a magnesium compound (a), a tetravalent titanium halogen compound (b), and an electron donating compound (c) other than alcohol and ether to form a solid product, and then the solid product A method for producing a solid catalyst component for olefin polymerization, comprising contacting an alcohol vapor or an ether vapor with water vapor, and further contacting a tetravalent titanium halogen compound (b) with the solid product after the vapor contact Is to provide.

Further, the present invention provides (A) a solid catalyst component for olefin polymerization according to claims 1 to 4, (B) the following general formula (1); R ¹ _p AlQ _3-p (1)
(Wherein R ¹ 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) and ( C) An olefin polymerization catalyst characterized by being formed by an external electron donating compound.

  The present invention also provides a method for producing an olefin polymer or copolymer, which comprises polymerizing olefins in the presence of the olefin polymerization catalyst.

  When the catalyst formed using the solid catalyst component for olefin polymerization of the present invention is used, a polymer with very little fine powder can be obtained while maintaining the high degree of stereoregularity and yield of the polymer. Therefore, general-purpose polyolefin can be provided at low cost.

  Among the olefin polymerization catalysts of the present invention, a magnesium compound (hereinafter sometimes simply referred to as “component (a)”) used for the preparation of the solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”). ”Includes dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, fatty acid magnesium, etc. Among these magnesium compounds, dialkoxymagnesium is preferable. In particular, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium Diethoxymagnesium is particularly preferred, and these dialkoxymagnesium may be obtained by reacting metal magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound. Dialkoxymagnesium can be used alone or in combination of two or more.

  Furthermore, the dialkoxymagnesium used for the preparation of the component (A) in the present invention 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 can be obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as blockage caused by the contained fine powder 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 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle diameter is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. As for the particle size, it is desirable to use one having a small particle size distribution and a small amount of fine powder and coarse powder. 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 expressed by ln (D90 / D10) (where D90 is the cumulative particle size and the particle size at 90%, D10 is the cumulative particle size and the particle size at 10%), it is preferably 3 or less, preferably 2 or less.

  For example, JP-A-58-41832, 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 tetravalent titanium halogen compound (b) (hereinafter sometimes referred to as “component (b)”) used for the preparation of the component (A) in the present invention is represented by the general formula Ti (OR ² ) _m Cl _4-m ( In the formula, R ² represents an alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 or 1 to 3). 2 or more types.

  Specifically, titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide as titanium halide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride as alkoxytitanium halide. Examples include chloride, 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. The Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These tetravalent titanium halogen compounds can be used alone or in combination of two or more.

  The electron-donating compound other than the alcohol and ether used for the preparation of the solid catalyst component (A) in the present invention (hereinafter sometimes simply referred to as component (c)) is an alcohol or ether containing an oxygen atom or a nitrogen atom. Other organic compounds such as phenols, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, Si—O—C bonds and Si—N—C bonds. Examples thereof include organic silicon compounds and the like, which can be used alone or in combination of two or more.

  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, Monocarboxylic acid esters such as cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate Dicarboxylates such as dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, diester phthalate, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, Acid halides such as taric acid dichloride, terephthalic acid dichloride, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, oleic acid amide, stearin Amides such as acid amides, Nitriles such as acetonitrile, benzonitrile and tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkyl Organosilicon compounds containing Si—O—C bonds such as alkylalkoxysilanes, (alkylamino) alkoxysilanes, alkyl (a Kiruamino) alkoxysilane, alkyl (alkyl) silane, and organic silicon compound containing Si-N-C bond, such as alkylamino silane.

  Of the above-mentioned electron donating compounds, esters, particularly aromatic dicarboxylic acid diesters are preferably used, and phthalic acid diesters and substituted phthalic acid diesters are particularly preferred in terms of improving hydrogen activity during polymerization. Among these, specific examples of phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso-phthalate. Butyl, ethyl methyl phthalate, methyl phthalate (iso-propyl), ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate (iso-butyl), di-n-pentyl phthalate Di-iso-pentyl phthalate, di-neo-pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, phthalate Bis (2-ethylhexyl) acid, di-n-nonyl phthalate, di-iso-decyl phthalate, bis (2,2-dimethylheptyl phthalate) ), N-butyl phthalate (iso-hexyl), n-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, n-pentyl phthalate (iso-hexyl), iso-pentyl phthalate (heptyl) ), N-pentyl (2-ethylhexyl) phthalate, n-pentyl phthalate (iso-nonyl), iso-pentyl phthalate (n-decyl), n-pentylundecyl phthalate, iso-pentyl phthalate (iso) -Hexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate (2-ethylhexyl), n-hexyl phthalate (iso-nonyl), n-hexyl phthalate (n-decyl) N-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (iso-nonyl), n-phthalate Heptyl (neo-decyl) are exemplified phthalate 2-ethylhexyl (an iso-nonyl) is, these one or more kinds are used.

Moreover, as substituted phthalic acid diester, following General formula (3);
(R ³ ) ₁ C ₆ H ₄ (COOR ⁴ ) (COOR ⁵ ) (3)
(In the formula, R ⁵ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, R ⁴ and R ⁵ represent an alkyl group having 1 to 12 carbon atoms, and R ⁴ and R ⁵ are the same or different. The number 1 of the substituent R ³ may be 1 or 2, and when 1 is 2, the R ³ may be the same or different.

In the general formula (3), the alkyl group having 1 to 8 carbon atoms of R ³ is specifically a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl. Group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, isooctyl group, 2,2-dimethylhexyl group, The halogen atom of R ³ is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. R ³ is preferably a methyl group, a bromine atom or a fluorine atom, more preferably a methyl group or a bromine atom.

In the general formula (3), R ⁴ and R ⁵ are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group. Group, n-hexyl group, isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, or isooctyl group, 2,2-dimethylhexyl group, n-nonyl group, isononyl group, n-decyl group , Isodecyl group and n-dodecyl group. Among these, an ethyl group, an n-butyl group, an isobutyl group, a t-butyl group, a neopentyl group, an isohexyl group, and an isooctyl group are preferable, and an ethyl group, an n-butyl group, and a neopentyl group are particularly preferable. The number l of the substituent R ³ is 1 or 2, and when 1 is 2, the R ³ may be the same or different. When l is 1, R ³ is substituted with a hydrogen atom at the 3-position, 4-position or 5-position of the substituted phthalic diester of the above general formula (3), and when l is 2, R ³ is at the 4-position and Substitution with a hydrogen atom at the 5-position is preferred.

  Examples of the substituted phthalic diester represented by the general formula (3) include diethyl 4-methylphthalate, di-n-butyl 4-methylphthalate, diisobutyl 4-methylphthalate, dineopentyl 4-bromophthalate, and diethyl 4-bromophthalate. Di-n-butyl 4-bromophthalate, diisobutyl 4-bromophthalate, dineopentyl 4-methylphthalate, dineopentyl 4,5-dimethylphthalate, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, 4-methylphthalate-t -Butyl neopentyl, 4-ethyl phthalate-t-butyl neopentyl, 4,5-dimethylphthalate dineopentyl, 4,5-diethyl phthalate dineopentyl, 4,5-dimethyl phthalate-t-butyl neopentyl, 4, 5-Diethylphthalic acid- - butyl neopentyl, 3-fluoro-phthalic acid dineopentyl, 3-chlorophthalic acid dineopentyl, 4-chlorophthalic acid dineopentyl, include 4-bromophthalic acid dineopentyl.

  The above esters are preferably used in combination of two or more, and the esters are used so that the total carbon number of the alkyl group of the ester used is 4 or more compared to that of other esters. It is desirable to combine.

  In the present invention, the components (a), (b), and (c) are contacted in the presence of the aromatic hydrocarbon compound (d) (hereinafter sometimes referred to simply as “component (d)”). The method of preparing the solid product by this is a preferred embodiment of the preparation method. Specifically, as this component (d), an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C. such as toluene, xylene, ethylbenzene and the like is specifically mentioned. Preferably used. Moreover, these may be used independently or may be used in mixture of 2 or more types.

In the preparation of the solid catalyst component (A) in the present invention, it is preferable to use a polysiloxane (hereinafter sometimes simply referred to as “component (e)”) in addition to the above components. As a result, 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, and 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). ), More preferably 0.03 to ⁵ cm ² / s, 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, decamethylcyclopentasiloxane, 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, the component (d) or the component (e) are contacted to form a solid product. A method for preparing the product will be described. Specifically, a magnesium compound (a) is suspended in a tetravalent titanium halogen compound (b) or an aromatic hydrocarbon compound (d), and an electron donating compound (c) such as phthalic acid diester and / or Examples include a method of obtaining a solid component by contacting a tetravalent titanium halogen compound (b). In this method, a spherical solid compound having a sharp particle size distribution and a solid catalyst component can be obtained by using a spherical magnesium compound, and without using a spherical magnesium compound, for example, using a spray device. By forming particles by a so-called spray drying method in which a solution or suspension is sprayed and dried, a solid product having a spherical shape and a sharp particle size distribution can be obtained.

  The contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture and the like are removed. The contact temperature is a temperature 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 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 component, and if it exceeds 130 ° C., the evaporation of the solvent used becomes remarkable. , 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.

  A preferred method for preparing a solid product of the present invention is to suspend component (a) in component (d), then contact component (b), and then contact component (c) and component (d), A method of preparing a solid product by reacting, or by suspending component (a) in component (d) and then contacting component (c), then contacting component (b) and reacting Mention may be made of the method of preparing the solid product. Moreover, the performance of the final solid catalyst component can be improved by bringing the component (b) or the component (b) and the component (c) into contact with the solid product thus prepared again or multiple times. At this time, it is desirable to carry out in the presence of the aromatic hydrocarbon compound (d).

  The solid product obtained as described above is brought into contact with alcohol vapor or ether vapor and water vapor (hereinafter sometimes referred to as component (e)). The alcohol vapor or ether vapor includes a combination of alcohol vapor and ether vapor. Therefore, component (e) refers to three forms of steam: water vapor and alcohol vapor, water vapor and ether vapor, water vapor, alcohol vapor and ether vapor. Thereby, the fine powder which exists in the particle | grain surface of a solid product is removed, and the particle | grains which are easy to peel are removed. Furthermore, the breaking strength of the particle surface of the solid product is further improved. Therefore, the amount of fine powder polymer produced when olefins are polymerized can be remarkably suppressed.

  As the alcohol, those having a relatively high vapor pressure at normal temperature are preferable, and methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-butanol, t-butyl alcohol, allyl alcohol, t-pentyl alcohol, Isoamyl alcohol, neoamyl alcohol, 2-pentanol, 3,3-dimethyl-2-butanol, 2-buten-1-ol, 2-chloroethanol, 2-methyl-1-butanol, 2-methyl-1-butanol 3-methyl-1-butanol, 4-methyl-2-pentanol, 1-pentanol, 2-ethylbutanol, 1-hexanol, 2-hexanol, 4-heptanol, cyclohexanol, 3-chloro-1-propanol 2-ethyl-1-hexa Lumpur, 1-octanol, ethylene glycol, isoamyl alcohol and the like, preferably methanol and ethanol. These alcohols can be used alone or in combination of two or more.

  The ether preferably has a relatively high vapor pressure at room temperature, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctyl ether, Diallyl ether, methyl butyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl 1-propenyl ether, ethyl isopropyl ether, ethyl isobutyl ether, ethyl isopentyl ether, allyl methyl ether, allyl ethyl ether, isopropenyl methyl ether, isopentyl methyl ether , Ethylene glycol dimethyl ether, chloromethyl ethyl ether, chloromethyl methyl ether, diglycy Ether, 1,2-dichloroethyl ethyl ether, divinyl ether, vinyl ethyl ether, vinyl methyl ether, bis (1-chloroethyl) ether, bis (2-chloroethyl) ether, bis (chloromethyl) ether, monochlorodiethyl ether, etc. Preferably, it is diethyl ether. These ethers can be used alone or in combination of two or more.

  In the present invention, the component (e) may be directly brought into contact with the solid product, but alcohol vapor or ether vapor and water vapor are contained in an inert gas such as nitrogen gas or argon gas, and this inert gas is used. Is in contact with the solid product in order to improve the activity of the obtained solid catalyst component and to suppress the amount of fine powder obtained. In addition, the contact between the component (e) and the solid product may be performed by bringing the alcohol vapor or ether vapor and water vapor separately into contact with the solid product, or mixing the alcohol vapor or ether vapor and the water vapor at a time. The mixture may be contacted with a solid product.

  As a suitable contact method, an inert gas atmosphere vessel is filled with a solid product, and an inert gas such as nitrogen containing a mixture vapor obtained by mixing alcohol vapor or ether vapor with water vapor is contained in the vessel. A method in which a predetermined amount is filled and contacted, or a container in an inert gas atmosphere is filled with a solid product, and further, an inert organic solvent is filled to form a suspension, in which alcohol vapor or ether vapor is previously added. And a method of contacting by injecting a predetermined amount of an inert gas such as nitrogen containing mixed steam mixed with water vapor. When the vapor is contained in the inert gas, it is desirable that the inert gas contains alcohol or ether and water so that each of the water is saturated. The saturated water vapor amount and saturated alcohol at the temperature of the inert gas at that time By measuring the amount or the amount of saturated ether, the component (e) in contact with the solid product can be quantified. The steam can be obtained by heating or depressurizing water, alcohol or ether. The method of filling a container with a solid product, adding a solvent containing a mixture of alcohol or ether and water, and stirring does not improve the fracture strength of the particle surface of the solid product. The generation of the so-called ultrafine particle polymer cannot be suppressed.

  The contact condition between the solid product and the inert gas containing the vapor is -20 to 150 ° C, preferably 10 to 130 ° C, particularly preferably 30 to 110 ° C. At this time, it is desirable to contact at a temperature higher than the dew point of the inert gas containing the component (e), particularly when using an inert gas saturated with the component (e), set the temperature higher than the dew point, Be careful not to condense the component (e) in the inert gas supply pipe or the container in contact. Further, it is preferable that the inert gas is not present in a liquid state such as a mist of the component (e). The contact time is 1 minute to 10 hours, preferably 10 minutes to 5 hours, particularly preferably 30 minutes to 3 hours. The component (e) in contact with the solid product is 0.0001 g to 0.5 g, preferably 0.005 g to 0.5 g, particularly preferably 0, relative to 1 g of the solid product. 0.001 g to 0.2 g.

  Further, the surfactant may be brought into contact with the solid product before, during or after contacting the moisture, alcohol compound and ether compound with the solid product. As the surfactant, one or two selected from cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants, fluorosurfactants and reactive surfactants. More than seeds can be used.

  Specifically, examples of the cationic surfactant include aliphatic primary to tertiary amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolium salts, and the like. Examples of the anionic surfactant include fatty acid soaps, N-acylamino acids or salts thereof, carboxylates such as polyoxyethylene alkyl ether carboxylates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, dialkylsulfosuccinates. Salts, sulfonates such as alkyl disulphates of sulfosuccinates, alkylsulfoacetates, sulfated oils, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, monoglyculates, etc. Examples thereof include phosphoric acid ester salts such as sulfate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene phenyl ether phosphates, and alkyl phosphates.

  Examples of the amphoteric surfactant include carboxybetaine type, aminated rubonate, inidazilinium betaine, lecithin, alkylamine oxide and the like. Examples of the nonionic surfactant include polyoxyethylene mono- or dialkyl ethers having 1 to 18 carbon atoms in the alkyl group, polyoxyethylene secondary alcohol ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene sterol ethers, Ether type such as polyoxyethylene lanolin derivative, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, and other ether esters, Polyethylene glycol fatty acid ester, ethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester , Propylene glycol fatty acid esters, ester type such as sucrose fatty acid esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides, nitrogen-containing type such as polyoxyethylene alkyl amines, and the like.

  Examples of the fluorosurfactant include fluoroalkyl carboxylic acid, perfluoroalkyl carboxylic acid, and N-perfluorooctanesulfonyl glutamate disodium. Examples of the reactive surfactant include polyoxyethylene allyl glycidyl nonyl phenyl ether and polyoxyethylene propenyl phenyl ether.

  The above surfactants can be used alone or in combination of two or more. Among these, nonionic surfactants having an HLB (hydrophilic / lipophilic balance) value of usually 3 to 20 are preferably used, and nonionic surfactants that are sufficiently soluble in the solvent to be used vary depending on the treatment method. It is desirable to select an agent. For example, when processing in polar organic solvents, such as alcohol, ethers, and acetone, the hydrophilic nonionic surfactant whose HLB value is 10-20 is used preferably. Moreover, when processing in organic solvents, such as hydrocarbons, such as hexane and heptane, the slightly lipophilic nonionic surfactant whose HLB value is 3 to 15 is used preferably.

  As mentioned above, after making alcohol vapor | steam or ether vapor | steam and water vapor | steam contact a solid product, a component (b) is contacted again and a solid catalyst component (A) is obtained. It is also desirable to contact not only component (b) but also component (b) and component (c) again. At this time, it is desirable to carry out the suspension in the aromatic hydrocarbon compound (d) as in the preparation of the solid product. Thus, by contacting again, the performance of the solid catalyst component such as activity can be improved.

  Further, when the component (b) or the component (b) and the component (c) are contacted again as described above, the solid catalyst component is again contacted with a surfactant in an inert solvent to form a suspension. Thereafter, the solvent in the suspension can be removed. The solid catalyst component (A) obtained by contacting the solid product with alcohol vapor or ether vapor and an inert gas containing water vapor and then contacting the component (b) again is the solid product after contact with the inert gas. Similarly, the number of fine particles still existing on the particle surface and particles that are easily peeled off remain small. Moreover, the fracture strength of the particle surface of the solid catalyst component remains high. Therefore, the amount of fine powder polymer produced when olefins are polymerized can be remarkably suppressed.

  Based on the above, a particularly preferred method for preparing the solid catalyst component (A) in the present application is to suspend dialkoxymagnesium (a) in an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. After bringing the tetravalent titanium halogen compound (b) into contact with the liquid, a reaction treatment is performed. At this time, before or after the tetravalent titanium halogen compound (b) is brought into contact with the suspension, one or more electron donating compounds (c) such as phthalic acid diesters are added at −20 to 20 A contact treatment is performed at 130 ° C. to carry out a reaction treatment to obtain a solid product (1). In this case, it is desirable to carry out the aging reaction at a low temperature before or after contacting one or more electron donating compounds. After washing this solid product (1) with a hydrocarbon compound that is liquid at room temperature (intermediate washing), the tetravalent titanium halogen compound (b) is again added in the presence of the aromatic hydrocarbon compound in the range of -20 to 100. The mixture is contacted at 0 ° C. and subjected to a reaction treatment to obtain a solid product (2). If necessary, intermediate cleaning and reaction treatment may be repeated a plurality of times. Next, the solid product (2) is washed with a hydrocarbon compound that is liquid at room temperature, and the washed solid product (2) is suspended in an aromatic hydrocarbon compound, and alcohol or ether and Blowing water, preferably alcohol, ether and nitrogen gas saturated with water, the component (e) is brought into contact with the solid product (2) while stirring. Thereafter, after washing with a liquid hydrocarbon compound at room temperature by decantation, the tetravalent titanium halogen compound (b) is brought into contact at −20 to 100 ° C. in the presence of the aromatic hydrocarbon compound to carry out the reaction treatment. And finally washed with a hydrocarbon compound to obtain the solid catalyst component (A).

  The amount of each component used in preparing the solid catalyst component (A) varies depending on the preparation method and cannot be specified unconditionally. For example, a tetravalent titanium halogen compound (b) per mole of the magnesium compound (a) Is 0.5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the electron donating compound (c) is 0.01 to 10 mol, preferably 0.01 to 1 mol. More preferably, it is 0.02 to 0.6 mol, and the aromatic hydrocarbon compound (d) is 0.001 to 500 mol, preferably 0.001 to 100 mol, more preferably 0.005 to 10 mol. It is.

  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 defined, but preferably 0.5 to 8.0% by weight of titanium, preferably 1.0 to 6.0 wt%, more preferably 1.5 to 4.0 wt%, magnesium is 10 to 70 wt%, more preferably 10 to 50 wt%, particularly preferably 15 to 40 wt%, and further Preferably 15 to 25% by weight, halogen atom 20 to 85% 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 electron donating compound is The total is 0.5 to 30% by weight, more preferably 1 to 25% by weight, and particularly preferably 2 to 20% by weight.

The solid catalyst component obtained by the above method has a mean particle size of 10 to 150 μm and a particle size of 2 μm or less as measured with a laser diffraction particle size distribution analyzer of 0.1% by weight or less, preferably 0% by weight. The specific surface area measured by the BET method is 5 to 10,000 m ² / g, and the apparent bulk density is 0.1 or more.

  As the organoaluminum compound (B) used in forming the olefin polymerization catalyst of the present invention, a compound represented by the above general formula (1) can be used. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide and diethylaluminum hydride, and one or more can be used. Triethylaluminum and tri-iso-butylaluminum are preferable.

  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 compounds that can be used, and alcohols and ethers are used. Examples of alcohols include methanol, ethanol, n-propanol, and 2-ethylhexanol. Examples of ethers include methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, and 9,9-bis (methoxy). Methyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and the like. Among the components (C), ethers, esters or 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 (2)
R ⁶ _q Si (NR ⁷ R ⁸ ) _r (OR ⁹ ) _{4- (q + r)} (2)
(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 ⁶ , R ⁷ or R ⁸ is a hydrogen atom, a carbon number of 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 ⁹ 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 ⁷ And R ⁸ may combine to form a ring.).

In general formula (2), R ⁶ 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 ⁷ or R ⁸ 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 ⁷ and R ⁸ are combined to form a ring (NR ⁷ R ⁸ ), preferably a perhydroquinolino group or a perhydroisoquinolino group. R ⁹ 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, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane Bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane Bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexyl Pentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5 -Dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldi Ethoxysilane, cyclo Xylethyldimethoxysilane, cyclohexylethyldiethoxysilane, 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, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxy Silane, phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysila , Ethyltriethoxysilane, n-propyltrimethoxysilane, iso-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, t -Butyltrimethoxysilane, n-butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxy Examples thereof include orchid and tetrabutoxysilane.

  Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldi Ethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxy Silane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylsilane B pentyl dimethoxy silane, cyclohexyl cyclopentyl distearate triethoxysilane, 3-methyl-cyclohexyl cyclopentyl dimethoxy silane, 4-methylcyclohexyl cyclopentyl dimethoxysilane, 3,5-dimethyl-cyclohexyl cyclopentyl dimethoxysilane is preferable.

  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.

  Next, the catalyst for olefin polymerization of the present invention contains the above-described solid catalyst component (A), component (B), and component (C) for olefin polymerization, and polymerization of olefins in the presence of the catalyst. Copolymerization is performed. 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 contact of each component is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the organosilicon compound (C) is contacted, and the solid catalyst component (A) for olefin polymerization is further added. It is desirable to contact.

  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.

  Furthermore, in polymerizing olefins using the catalyst containing the solid catalyst component (A), the component (B), and the component (C) for olefin polymerization in the present invention (also referred to as main polymerization), the catalyst activity and the steric properties are determined. In order to further improve the regularity and the particle properties of the polymer to be produced, it is desirable to perform prepolymerization 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 into 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.

  When the olefins are polymerized in the presence of the olefin polymerization catalyst formed according to the present invention, the resulting polymer has very little fine powder and a large particle size compared to the conventional catalyst. And a high degree of stereoregularity and yield of the polymer. The catalyst for olefin polymerization of the present invention is very advantageous particularly for a polyolefin production process by a gas phase method.

(Example)
EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.

[Preparation of solid catalyst component (A)]
Suspension in which 10 g of diethoxymagnesium, 50 ml of toluene and 2.4 ml of di-n-butyl phthalate were charged into a 500-milliliter round bottom flask which was sufficiently replaced with nitrogen gas and equipped with a stirrer and a reflux condenser. Formed. On the other hand, 30 ml of titanium tetrachloride and 20 ml of toluene were charged into a 500 ml round bottom flask which was sufficiently replaced with nitrogen gas and equipped with a stirrer to form a mixed solution, and the above suspension was suspended in this mixed solution. The liquid was added. Thereafter, the mixed solution was heated and reacted at 90 ° C. with stirring for 2 hours. After completion of the reaction, the obtained solid product was washed with 100 ml of toluene at 90 ° C. three times, then 30 ml of titanium tetrachloride and 70 ml of toluene were newly added, and the temperature was raised to 112 ° C. and reacted for 2 hours with stirring. . Thereafter, the supernatant was removed by decantation, washed 5 times with 100 ml of 40 ° C. n-heptane and dried. Next, 10 g of solid material and 70 ml of toluene were added to a 500 ml round bottom flask which was sufficiently replaced with nitrogen gas and equipped with a stirrer to obtain a suspension. Under a nitrogen atmosphere, this suspension was bubbled with a mixed saturated nitrogen gas of water, dibutyl ether and ethanol so as to be 0.03 g- (water-dibutyl ether-ethanol) / g-solid, so that the solid product and water Was brought into contact. The contact temperature was 25 ° C. and the contact time was 5 minutes. After stopping the bubbling, 30 ml of titanium tetrachloride was added to the suspension after contact, and the temperature was raised to 112 ° C., and the reaction was carried out with stirring for 2 hours. Thereafter, the supernatant was removed by decantation and then washed 5 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. In addition, it was 3.1 weight% when the titanium content rate in this solid catalyst component was measured.

[Formation and polymerization of polymerization catalyst]
700 ml of n-heptane was charged into a stainless steel autoclave with a stirrer having an internal volume of 1800 ml that had been sufficiently dried with nitrogen gas and then replaced with propylene gas, and maintained in a propylene gas atmosphere. The polymerization catalyst was formed by charging 0.21 mmol of cyclohexylmethyldimethoxysilane and 0.0053 mmol of the solid catalyst component as Ti. Next, a preliminary polymerization was carried out at 20 ° C. for 30 minutes while applying a propylene pressure of 0.2 MPa and maintaining stirring. Thereafter, 150 ml of hydrogen was charged, and the polymerization was continued for 2 hours at 70 ° C. with a propylene pressure in the system of 0.7 MPa. In addition, the pressure which falls as superposition | polymerization advances was supplemented by supplying only propylene continuously, and was kept at the constant pressure during superposition | polymerization. According to the above polymerization method, propylene was polymerized, and the produced polymer was filtered and dried under reduced pressure to obtain a solid polymer. On the other hand, the filtrate is condensed to obtain a polymer dissolved in the polymerization solvent, the amount of which is (M), and the amount of the solid polymer is (N). The obtained solid polymer is extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and this amount is defined as (P). The polymerization activity (Y) per solid catalyst component is represented by the following formula.
(Y) = [(M) + (N)] (g) / solid catalyst component amount (g)

Further, the total polymer (HI) insoluble in n-heptane is represented by the following formula.
(HI) = {(P) (g) / [(M) + (N)] (g)} × 100

  Further, melt flow rate (MFR), bulk specific gravity (BD) of the produced solid polymer, fine powder (44 μm or less, 105 μm or less) of the produced solid polymer, average particle size and particle size distribution [(D90-D10) / D50] When measured, the results shown in Table 1 were obtained.

  The melt flow rate value (MFR) of the produced solid polymer (N) was measured in accordance with ASTM D 1238 and JIS K 7210. In Table 1, the added amount (g-alcohol etc./g-solid) means (g-water-ether-alcohol / g-solid).

Example 2 to Example 4
Instead of 0.03 g- (water-dibutyl ether-ethanol) / g-solid material, 0.05 g- (water-dibutyl ether-ethanol) / g-solid material (Example 2), 0.001 g- (water content) -Dibutyl ether-ethanol) / g-solid (Example 3) and 0.2 g- (water-dibutyl ether-ethanol) / g-solid (Example 4). Preparation of the solid catalyst component, formation of the polymerization catalyst and polymerization were carried out. The polymerization results are shown in Table 1.

Example 5 to Example 7
2-butanol was used instead of ethanol (Example 5), diethyl ether was used instead of dibutyl ether (Example 6), 2-ethyl-1-hexanol was used instead of ethanol, and dibutyl ether was used instead. A solid catalyst component was prepared, a polymerization catalyst was formed, and polymerization was carried out in the same manner as in Example 1, except that diisoamyl ether was used (Example 7). The polymerization results are shown in Table 1.

Comparative Example 1
A solid catalyst component was prepared in the same manner as in Example 1 except that the contact between the solid product and the alcohol-saturated nitrogen gas was not performed, and the titanium tetrachloride after the contact was not added. Went. The results are shown in Table 1.

Comparative Example 2
A 200-ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer was charged with 5 g of diethoxymagnesium, 1.8 g of dibutyl phthalate and 25 ml of methylene chloride, suspended, and stirred at reflux for 1 hour. did. The suspension was then pumped into 200 ml of room temperature TiCl ₄ in a 500 ml round bottom flask equipped with a stirrer, heated to 110 ° C. and allowed to react for 2 hours with stirring. After completion of the reaction, it was washed 10 times with 200 ml of n-heptane at 40 ° C. to obtain a solid composition. Next, 3 g of the solid composition was put into a 500 ml round bottom flask, added with 100 ml of n-heptane containing 10 ppm of water, treated with stirring at room temperature for 1 hour, and then washed 5 times with 200 ml of room temperature n-heptane. Then, 200 ml of TiCl ₄ was newly added and reacted at 120 ° C. with stirring for 2 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. and then repeatedly washed with 200 ml of n-heptane. When chlorine was no longer detected in the washing solution, the washing was terminated and used as a catalyst component. At this time, the titanium content in the catalyst component was measured and found to be 3.2% by weight.

Comparative Example 3
<Preparation of solid catalyst component>
A 2000-ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 150 g of diethoxymagnesium and 750 ml of toluene to form a suspension. The suspended solution was then charged into a solution of 450 ml of toluene and 300 ml of titanium tetrachloride previously charged in a 3000 ml round bottom flask equipped with a stirrer and thoroughly replaced with nitrogen gas. Next, 54 ml of di-n-butyl phthalate was added, the temperature was raised to 110 ° C., and 60 ml of dimethylpolysiloxane was added along the way. After raising the temperature to 110 ° C., the mixture was reacted for 2 hours with stirring. After completion of the reaction, the product was washed with toluene, and 1200 ml of toluene and 300 ml of titanium tetrachloride were newly added, and contact reaction was conducted with stirring at 100 ° C. for 2 hours. The product was then washed with heptane, filtered and dried to obtain a powdery solid component. The titanium content in the solid component was measured and found to be 1.4% by weight.

(Alcohol treatment of solid components)
Next, 10 g of the above solid component and 50 ml of heptane were charged into a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas to obtain a suspended solution. Next, the entire amount of the prepared mixed solution prepared by adding 0.01 ml of ethanol to 50 ml of heptane is added to the suspension solution and brought into contact with stirring at 50 ° C. for 1 hour to obtain a solid catalyst component. It was. The solid catalyst component was separated into solid and liquid, and the titanium content in the solid was measured and found to be 1.4% by weight.

  A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component prepared as described above was used. The polymerization results are shown in Table 1.

Comparative Example 4
<Preparation of solid components>
A 2000 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 150 g of diethoxymagnesium and 750 ml of toluene to form a suspended state. The suspension was then added to a solution of 450 ml of toluene and 300 ml of titanium tetrachloride pre-charged in a 2000 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. Next, the suspension was reacted at 5 ° C. for 1 hour (low temperature aging treatment). Thereafter, 22.5 ml of di-n-butyl phthalate was added, the temperature was raised to 90 ° C., and a reaction treatment (first treatment) was performed for 2 hours with stirring. After completion of the reaction, the product was washed four times with 1300 ml of toluene at 80 ° C. (intermediate washing), and 1200 ml of toluene and 300 ml of titanium tetrachloride were newly added, and the reaction treatment was performed at 112 ° C. for 2 hours (second treatment). ) Thereafter, the intermediate washing and the second treatment were repeated once more. The product was then washed 7 times with 1300 ml of 40 ° C. heptane, filtered and dried to obtain a powdered solid component. The titanium content in the solid component was measured and found to be 2.9% by weight.

(Ether treatment of solid components)
10 g of the solid component obtained as described above was suspended in 100 ml of heptane, and 0.6 ml of dibutyl ether was added to this suspension. Thereafter, the mixture was treated with stirring at 40 ° C. for 1 hour, and then washed 7 times with 1300 ml of heptane at 40 ° C. to obtain a solid catalyst component (A). The titanium content in the solid catalyst component was measured and found to be 2.2% by weight.

A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component prepared as described above was used. The polymerization results are shown in Table 1.
Example 8
0.03 g- (moisture-dibutyl ether-ethanol) / g-solid instead of using saturated nitrogen gas mixed with water, dibutyl ether and ethanol so as to become a solid substance The same procedure as in Example 1 was conducted except that saturated nitrogen gas mixed with water and ethanol was used so as to obtain a product.
Example 9
0.03 g- (moisture-dibutyl ether-ethanol) / g- Instead of using saturated nitrogen gas mixed with water, dibutyl ether and ethanol so as to become a solid substance, 0.03 g- (water-dibutyl ether) / g- The same procedure as in Example 1 was performed except that a mixed saturated nitrogen gas of water and dibutyl ether was used so as to become a solid substance.

  From the results of Table 1, it can be seen that by polymerizing propylene using the solid catalyst component and catalyst of the present invention, a polymer that maintains high activity and high stereoregularity and generates very little fine polymer can be obtained. Recognize.

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

Claims (7)

  A magnesium compound (a), a tetravalent titanium halogen compound (b), and an electron donating compound (c) other than alcohol and ether are contacted to form a solid product, and then the alcohol vapor or ether vapor is added to the solid product. A solid catalyst component for olefin polymerization, which is obtained by bringing the solid product after the vapor contact into contact with the tetravalent titanium halogen compound (b).   The solid catalyst component for olefin polymerization according to claim 1, wherein the magnesium compound is dialkoxymagnesium. The solid catalyst component of claim 1, wherein the tetravalent titanium halide compound characterized in that it is a titanium tetrachloride.   The contact of the solid product, alcohol vapor or ether vapor, and water vapor is contact of the solid product, alcohol or ether, and an inert gas saturated with water, according to claim 1. The solid catalyst component for olefin polymerization as described.   A magnesium compound (a), a tetravalent titanium halogen compound (b), and an electron donating compound (c) other than alcohol and ether are contacted to form a solid product, and then the alcohol vapor or ether vapor is added to the solid product. And a solid product after the vapor contact is further brought into contact with the tetravalent titanium halogen compound (b). (A) Solid catalyst component for olefin polymerization according to any one of claims 1 to 4, (B) the following general formula (1); R ¹ _p AlQ _3-p (1)
(Wherein R ¹ 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) and ( C) Olefin polymerization catalyst characterized by being formed by an external electron donating compound.   A method for producing an olefin polymer or copolymer, wherein olefins are polymerized in the presence of the olefin polymerization catalyst according to claim 6.

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