JP4497414B2 - Method for preparing alkoxymagnesium-coated solid, method for producing solid catalyst component for olefin polymerization, and method for producing catalyst - Google Patents

Description

  The present invention relates to an alkoxymagnesium-coated solid suitable for a carrier material for a solid catalyst component for olefin polymerization, a method for preparing the same, a solid catalyst component and catalyst for olefin polymerization using the solid, and an olefin polymer using the same. Or it is related with the manufacturing method of a copolymer.

  The main production method of solid catalyst components for polymerizing highly active olefins known as Ziegler-Natta catalysts is to dissolve magnesium compounds such as magnesium chloride with alcohol or alkoxytitanium compounds, and then deposit solids to form spherical solid catalysts Methods for obtaining the components are known.

  For example, according to Patent Document 1 (Japanese Patent Laid-Open No. 62-18405), titanium alkoxy compounds, dialkoxy magnesium, aromatic dicarboxylic acid diesters, halogenated hydrocarbon compounds, titanium halides represented by a specific formula A catalyst component for olefin polymerization that is obtained by contacting and used in combination with a silicon compound and an organoaluminum compound represented by a specific formula is disclosed. According to Patent Document 2 (Japanese Patent Laid-Open No. 3-72503), a magnesium compound represented by a specific formula, a tetraalkyltitanium compound, and a silicon compound represented by a specific formula are subjected to a heat reaction, and then the reaction product. A solid catalyst component for polymerizing olefins obtained by treating with a halogen-containing titanium compound represented by the specific formula and an electron donating compound represented by the specific formula is disclosed. By using these catalysts, a polymer having a high bulk density (BD) with a uniform particle size distribution can be produced.

  However, since the above conventional catalyst is a method for preparing a solid catalyst component by dissolving a magnesium compound with an alkoxytitanium compound and then precipitating the solid component, the process of precipitating the solid component from the magnesium compound solution is complicated. Since a large amount of the alkoxytitanium compound is used in the method for preparing the solid catalyst component, the alkoxytitanium compound remains in the deposited solid component, and as a result, there is a problem that the catalyst performance such as polymerization activity is remarkably lowered.

  In recent years, the need for high value-added polymers such as impact copolymer (impact copolymer, ICP) is increasing in the polypropylene industry. In general, such polymers are prepared by block copolymerization in two or multiple stages, usually by first polymerizing propylene and then copolymerizing ethylene with propylene or other olefins. At this time, in order to improve impact resistance, it is necessary to increase the ratio of the rubber-like polymer (EPR) produced by copolymerization of ethylene and propylene, but the ratio of EPR cannot be increased due to the particle properties of the catalyst component. The produced rubber component flows out from the inside of the polymer particles onto the surface, and accordingly, adhesion between the polymer particles or adhesion to the inner wall of the polymerization apparatus occurs. For this reason, it is difficult to produce a block copolymer that is stable over the long term. Therefore, not only has a high bulk density (BD), but also enables ethylene-propylene rubber (EPR) to be dispersed inside, and has appropriate BD or pores to produce an impact-resistant copolymer. The development of solid catalyst components is also a major issue.

In order to solve such problems, in Patent Document 3 (Japanese Patent Laid-Open No. 8-283329), (a) dialkoxymagnesium having a bulk specific gravity of 0.25 g / ml or more, (b) a general formula Ti (OR ¹⁾ _n X titanium halide represented by the _4-n, discloses olefin polymerization solid catalyst component characterized in that it is prepared by contacting (c) a diester of an aromatic dicarboxylic acid. Even if such a solid catalyst component is used for propylene-ethylene block copolymerization and the production ratio of the rubbery copolymer is increased, good particle properties can be maintained to some extent.
JP-A-62-18405 JP-A-3-72503 JP-A-8-283329

  In recent years, there has been a demand for higher added value of polymers, and it is a problem to produce a polymer with higher EPR component content and higher properties for propylene-ethylene block copolymerization. Therefore, it is desired to control the pore distribution of the solid catalyst component and increase its particle size. However, the above prior art is not sufficient to solve the problem.

  Accordingly, an object of the present invention is to solve the problems remaining in the prior art, and to have a morphology suitable for propylene-ethylene block copolymerization without deteriorating performance such as stereoregularity and polymerization activity. TECHNICAL FIELD The present invention relates to an alkoxymagnesium-coated solid material capable of obtaining components, a preparation method thereof, a solid catalyst component and a catalyst for olefin polymerization using the solid material, and a method for producing an olefin polymer or copolymer using the solid catalyst component. .

  Under such circumstances, the present inventor has intensively studied to solve the problems remaining in the prior art, and as a result, an alkoxymagnesium-coated solid in which a layer made of alkoxymagnesium is formed on the surface of carrier particles such as a magnesium compound. By using the product as a raw material for the solid catalyst component, it has been found that it has an extremely high effect and can solve the above problems, and has completed the present invention.

That is, the present invention is to react the metal alkoxide carrier particles and the metal magnesium and an alcohol, a method of forming a layer consisting of alkoxy magnesium on the metal alkoxide carrier particle surfaces, when to the reaction, a halogen or halogen The present invention provides a method for preparing an alkoxymagnesium-coated solid, which is carried out in the presence of a containing compound .

In the present invention, the alkoxymagnesium-coated solid material (a) obtained by the above-described method for preparing an alkoxymagnesium-coated solid material, and tetravalent titanium contact the halogen compound (b) and the electron-donating compound (c). The present invention provides a method for producing a solid catalyst component for polymerizing olefins.

Further, the present invention is (A) an olefin polymerization solid catalyst component obtained by the above method, (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) The present invention provides a method for producing an olefin polymerization catalyst characterized by contacting an external electron donating compound.

  Moreover, this invention provides the manufacturing method of the olefin polymer or copolymer characterized by performing in presence of said catalyst for olefin polymerization.

  If the alkoxymagnesium-coated solid material of the present invention is used as a component of a solid catalyst component for olefin polymerization, the morphology of the resulting solid catalyst component such as particle size and pores can be controlled, and stereoregularity and polymerization activity can be controlled. Thus, an olefin polymer having a narrow particle size distribution and a particle size and bulk density suitable for the intended use can be obtained without degrading performance such as ethylene propylene rubber component (EPR) when used for propylene-ethylene block copolymerization. ) And a good dispersibility. As a result, a high-performance polymer having a good balance between synthesis and impact resistance can be obtained.

[I] Alkoxymagnesium-coated solid material The alkoxymagnesium-coated solid material of the present invention is obtained by forming a layer made of alkoxymagnesium on the surface of carrier particles. Here, the carrier particles are not particularly limited, and examples thereof include particles of various metal alkoxide compounds, metal oxides, metal salts such as metal chlorides and metal carbonates. Specifically, dimethoxymagnesium, diethoxymagnesium, ethoxymagnesium chloride, diethoxycopper, triethoxyaluminum, etc. as metal alkoxide compounds, magnesium oxide, silica, alumina, titanium oxide etc. as metal oxides, magnesium chloride, carbonic acid as metal salts Examples thereof include magnesium. Among these, metal alkoxide compounds are preferable, and particularly, diethoxymagnesium and ethoxymagnesium chloride. These shapes and particle sizes are not particularly limited, but are preferably spherical and have an average particle size of 1 to 100 μm, preferably 1 to 50 μm, particularly preferably 5 to 30 μm. Here, the spherical shape does not necessarily have to be a perfect spherical shape, and may be an elliptical shape or a potato-shaped subspherical shape, or a surface having irregularities. In addition, in this specification, particle | grains also include a powdery thing and a powder is the meaning also containing a particulate matter.

  An alkoxymagnesium layer is formed on the surface of the carrier particles, and examples of the method include a method of reacting the carrier particles with metallic magnesium and alcohol. Specifically, metal magnesium is reacted under reflux of alcohol in the presence of carrier particles.

  The shape of the metallic magnesium to be used is not particularly limited, and metallic magnesium having an arbitrary shape can be used. For example, granular magnesium, ribbon, powder, etc. are used. Among these, powdery metallic magnesium is preferable, and an average particle diameter is 10-500 micrometers. Further, the surface state of the metallic magnesium is not particularly limited, but it is not preferable that the surface is formed with a film such as magnesium oxide, so it is desirable to remove it beforehand.

  It does not specifically limit as alcohol to be used, It is preferable to use C1-C6 lower alcohol, specifically, methanol, ethanol, propanol, and butanol. In particular, by using ethanol, a layer of ethoxymagnesium is formed on the surface of the carrier particles, and an alkoxymagnesium-coated solid material that significantly improves the expression of catalyst performance can be obtained. The purity and water content of the alcohol are not limited, but the lower the water content, the more preferably 200 ppm or less.

  When an alkoxymagnesium layer is formed on the surface of the carrier particles by reacting the carrier particles with metal magnesium and alcohol, the amount of the carrier particles used varies depending on the specific gravity and particle size of the carrier particles, but 0.5 g or more per 1 g of metal magnesium. Is more preferable, and the weight ratio is preferably 1 to 5 g. When the amount of carrier particles used is too small, fine particles of alkoxymagnesium alone are generated due to contact between metal magnesiums, and the particle size distribution is deteriorated. The generated fine powder prevents the growth of the alkoxymagnesium layer on the support surface. Since the alkoxymagnesium layer grows on the surface of the carrier particles even if the amount of the carrier particles used is excessive with respect to the metal magnesium, the upper limit cannot be set in principle. However, if the amount of the carrier particles is too large relative to the metal magnesium, only a thin alkoxymagnesium layer is formed, so that the particle size of the alkoxymagnesium-coated solid cannot be increased and is not practical. By setting the amount (mass ratio) of the carrier particles to metal magnesium to 1 to 5, the metal magnesium is divided into a plurality of times and subjected to the reaction, whereby an alkoxymagnesium-coated solid with an appropriate particle size can be formed.

  In particular, when diethoxymagnesium is used as the carrier particles, the molar ratio of diethoxymagnesium / metalmagnesium is preferably 0.05 or more, more preferably 0.1 or more, Preferably it is 0.3-1.

  The alkoxymagnesium-coated solid material of the present invention preferably contains a catalyst component such as a halogen or a halogen-containing compound when a carrier particle is reacted with metallic magnesium and alcohol to form an alkoxymagnesium layer on the surface of the carrier particle. By reacting in the presence of such a catalyst, the primary crystal diameter of the formed alkoxymagnesium can be controlled, and an alkoxymagnesium-coated solid with an arbitrary bulk density or pore distribution can be prepared.

Examples of the halogen include chlorine, bromine or iodine, and examples of the halogen-containing compound include MgCl ₂ , MgI ₂ , Mg (OEt) Cl, Mg (OEt) I, MgBr ₂ , CaCl ₂ , NaCl, KBr, and the like. It can be suitably used. Of these, iodine and MgCl ₂ are particularly preferable. The state, shape, particle size, and the like of the halogen and the halogen-containing metal compound are not particularly limited, and any halogen compound may be used. For example, it can be used as a solution in an alcohol solvent such as ethanol.

  About the quantity of alcohol, Preferably it is 3-50 mol with respect to 1 mol of metal magnesium, Most preferably, it is 5-20 mol. When the amount of alcohol is too large, the particle size distribution of the resulting alkoxymagnesium-containing solid material is spread and deteriorated. When the amount is too small, stirring in the reaction vessel becomes uneven and the reaction product aggregates.

  The reaction between magnesium metal and alcohol can be carried out in the same manner as in a known method. That is, a method of obtaining a magnesium compound by usually reacting for 10 to 30 hours until generation of hydrogen gas is not observed can be mentioned. The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen gas or argon gas. The reaction is usually performed at 30 ° C. or higher, preferably 40 ° C. or higher, particularly preferably under reflux of alcohol.

  The catalyst particles such as carrier particles, magnesium metal, alcohol and, if necessary, halogen may be added by a method in which all of them are added from the beginning, or each of them may be divided into several times and reacted. . A particularly preferred form is a method in which the whole amount of alcohol or catalyst is added from the beginning, and the whole amount of carrier particles is added and suspended therein, and then metal magnesium is added in several divided or continuous manners. preferable. In the case of this method, a temporary mass generation of hydrogen gas can be prevented, which is very desirable from the viewpoint of safety. Also, the reaction vessel can be downsized. Furthermore, it becomes possible to prevent entrainment of alcohol and halogen caused by a temporary large amount of hydrogen gas.

  The alkoxymagnesium-coated solid obtained as described above is used for the preparation of the next solid catalyst component (A), and is used after drying or by removing the alcohol by washing with an inert hydrocarbon compound.

The alkoxymagnesium-coated solid material of the present invention obtained as described above can be used for the preparation of an olefin solid catalyst component without performing a pulverization operation or a classification operation for uniforming the particle size distribution. Further, the alkoxymagnesium-coated solid material of the present invention is nearly spherical and has a narrow and sharp particle size distribution. Furthermore, the variation in sphericity of each particle is small. Specifically, the average particle size of the alkoxymagnesium-coated solid material of the present invention is 10 to 200 μm, preferably 10 to 100 μm, particularly preferably 20 to 50 μm. The carrier particles are preferably diethoxymagnesium powder. The particle size distribution of the alkoxymagnesium-coated solid is represented by the following formula: SPAN = (D ₉₀ -D ₁₀ ) / D ₅₀
Is not more than 4, preferably not more than 2, particularly preferably not more than 1.5. The SPAN value indicates the degree of spread of the particle size distribution, and the smaller the value, the narrower and sharper the particle size distribution, and the greater the number of particles having the same particle size.

In the above formula, D ₉₀ represents a particle size corresponding to a cumulative weight fraction of 90% in the particle size distribution of the magnesium compound determined by the light transmission method in a state suspended in hydrocarbon, and D ₁₀ represents the cumulative weight fraction. rate represents a particle diameter corresponding to 10%, D ₅₀ represents a particle diameter corresponding to 50%.

[II] Solid catalyst component for olefin polymerization The solid catalyst component for olefin polymerization of the present invention is the above-mentioned alkoxymagnesium-coated solid (a) (hereinafter sometimes simply referred to as “component (a)”) and 4. It is obtained by contacting a valent titanium halogen compound (b) with an electron donating compound (c).

  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 a compound selected from the group consisting of titanium halides and alkoxytitanium halides. 1 type or 2 types or more. 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 titanium compounds can be used alone or in combination of two or more.

  The electron-donating compound (hereinafter sometimes simply referred to as component (c)) used in the preparation of the solid catalyst component (A) in the present invention is an organic compound containing an oxygen atom or a nitrogen atom, such as alcohols. Phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds containing a Si—O—C bond, 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, methyl p-toluate, ethyl p-toluate, methyl anisate, anisic acid Monocarboxylic acid esters such as chill, diethyl malonate, dipropyl malonate, dibutyl malonate, diisobutyl malonate, dipentyl malonate, dineopentyl malonate, diethyl isopropyl bromomalonate, diethyl butyl bromomalonate, diethyl isobutyl bromomalonate , Diethyl diisopropylmalonate, diethyl dibutylmalonate, diethyl diisobutylmalonate, diethyl diisopentylmalonate, diethyl isopropylisobutylmalonate, dimethyl isopropylisopentylmalonate, diethyl (3-chloro-n-propyl) malonate, bis (3-Bromo-n-propyl) diethyl malonate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, adipine Dibutyl esters such as dibutyl, diisodecyl adipate, dioctyl adipate, phthalate diester, phthalate diester derivatives, 1-cyclohexene-1,2-dicarboxylate dineopentyl, acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, etc. Ketones, acid halides such as phthalic acid dichloride, terephthalic acid dichloride, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, oleic acid Amides such as amide and stearamide, nitriles such as acetonitrile, benzonitrile and tolunitrile, methyl isocyanate, isocyanate Mention may be made of isocyanates such as ethyl acid, organosilicon compounds containing Si—O—C bonds such as phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane and the like.

  Among the above electron donating compounds, esters, particularly aromatic dicarboxylic acid diesters are preferably used, and phthalic acid diesters and phthalic acid diester derivatives are particularly preferable. Specific examples of these phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, and di-iso-butyl phthalate. , Ethyl methyl phthalate, methyl phthalate (iso-propyl), ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate (iso-butyl), di-n-pentyl phthalate, Di-iso-pentyl phthalate, di-neo-pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, phthalic acid Bis (2-ethylhexyl), 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-pentyl undecyl 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), is phthalate 2-ethylhexyl (an iso-nonyl) is exemplified, these phthalic diester one or two or more kinds are used.

  As the phthalic acid diester derivative, one or two hydrogen atoms of the benzene ring to which the two alkoxycarbonyl groups of the above phthalic acid diester are bonded are an alkyl group having 1 to 5 carbon atoms, a chlorine atom, or a bromine atom. And those substituted with a halogen atom such as a fluorine atom. The solid catalyst component prepared by using the phthalic diester derivative as an electron donating compound can further improve the hydrogen activity or hydrogen response, and the polymer melt flow can be performed even when the amount of hydrogen added during polymerization is the same or small. The rate can be improved. Specifically, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, dineopentyl 4,5-dimethylphthalate, dineopentyl 4,5-diethylphthalate, diethyl 4-chlorophthalate, di-n-butyl 4-chlorophthalate , Dineopentyl 4-chlorophthalate, di-iso-butyl 4-chlorophthalate, di-iso-hexyl 4-chlorophthalate, di-iso-octyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n 4-bromophthalate -Butyl, dineopentyl 4-bromophthalate, di-iso-butyl 4-bromophthalate, di-iso-hexyl 4-bromophthalate, di-iso-octyl 4-bromophthalate, diethyl 4,5-dichlorophthalate, 4, Di-n-butyl 5-dichlorophthalate, 4, -Di-iso-hexyl dichlorophthalate, di-iso-octyl 4,5-dichlorophthalate, among which dineopentyl 4-bromophthalate, di-n-butyl 4-bromophthalate and di-4-bromophthalate -Iso-butyl is preferred.

  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 component (A) by this is a preferred embodiment of the preparation method, and as the component (d), specifically, an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C. such as toluene, xylene, ethylbenzene, etc. Is preferably used. Moreover, these may be used independently or may be used in mixture of 2 or more types.

  As a particularly preferred method for preparing the solid product in the present invention, a suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the component (b And a mixed solution formed from the component (d) is brought into contact with the suspension and then reacted.

Solid product formation step in the preparation of the solid catalyst component (A) of the present invention In the solid catalyst component (A), in addition to the above components, polysiloxane (hereinafter also simply referred to as “component (e)”). It is preferable to use polysiloxane. By using polysiloxane, 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 (3 to 500 centistokes), 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, the alkoxymagnesium-coated solid (a) is suspended in a halogenated hydrocarbon compound solvent, a tetravalent titanium halogen compound (b) or an aromatic hydrocarbon compound (d), and a phthalic acid diester or the like is suspended. Examples thereof include a method in which an electron donating compound (c) and / or a tetravalent titanium halogen compound (b) is contacted to obtain a solid component.

  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).

  As a particularly preferred method for preparing the solid product in the present invention, a suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the component (b And a mixed solution formed from the component (d) is brought into contact with the suspension and then reacted.

  The most preferable method for preparing the solid product in the present invention includes the following methods. A suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. A mixed solution is formed from the component (b) and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the suspension is added to the mixed solution. Then, the obtained mixed solution is heated and subjected to a reaction process (first reaction process). After completion of the reaction, the obtained solid substance is washed with a liquid hydrocarbon compound at room temperature, and the solid substance after washing is used as a solid product. Thereafter, the washed solid material is further brought into contact with component (b) and an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. at −20 to 100 ° C., and the temperature is raised. A solid product can also be obtained by repeating the reaction treatment (secondary reaction treatment) and washing with a hydrocarbon compound that is liquid at room temperature after completion of the reaction 1 to 10 times.

  Based on the above, as a particularly preferred method for preparing the solid catalyst component (A) in the present invention, the alkoxymagnesium-coated solid (a) is suspended in an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and then After the tetravalent titanium halogen compound (b) is brought into contact with this suspension, 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 reaction product (2). If necessary, intermediate cleaning and reaction treatment may be repeated a plurality of times. Next, the solid reaction product (2) is washed with a hydrocarbon compound that is liquid at room temperature by decantation 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 per mole of the alkoxymagnesium-coated solid (a) (B) 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 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 0.005 mol. 10 mol, and polysiloxane (e) is 0.01 to 100 g, preferably 0.05 to 80 g, more preferably 1 to 50 g.

  In the present invention, the content of titanium, magnesium, a halogen atom, and an electron donating compound in the solid catalyst component (A) or (A) is not particularly defined, but preferably 1.0 to 8.0% by weight of titanium. , Preferably 2.0 to 8.0 wt%, more preferably 3.0 to 8.0 wt%, magnesium 10 to 70 wt%, more preferably 10 to 50 wt%, particularly preferably 15 to 40 wt%. %, More preferably 15 to 25% by weight, halogen atoms 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 electron donation The total amount of the active compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight, and particularly preferably 2 to 20% by weight.

[III] Method for Producing Olefin Polymer Next, the catalyst for olefin polymerization of the present invention includes the above-described solid catalyst component (A) for olefin polymerization, organoaluminum compound (B), and external electron donating compound (C). And olefins are polymerized or copolymerized in the presence of the catalyst.

The organoaluminum compound (B) (hereinafter sometimes simply referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention is a compound represented by the above general formula (1). As long as R ¹ is not particularly limited, R ¹ is preferably an ethyl group or isobutyl group, Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, and p is preferably 2 or 3, particularly preferably 3. . 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.

  The electron donating compound (C) (hereinafter sometimes simply referred to as “component (C)”) is an organic compound containing oxygen or nitrogen, such as alcohols, phenols, ethers, esters, Examples include ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds containing Si—O—C bonds, and aminosilane compounds.

  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, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate Dicarboxylic acid esters such as dioctyl adipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, and didecyl phthalate , Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, acid halides such as phthalic dichloride, terephthalic dichloride, acetaldehyde, propional Aldehydes such as hydride, octyl aldehyde and benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine, amides such as oleic acid amide and stearic acid amide, nitriles such as acetonitrile, benzonitrile and tolunitrile And isocyanates such as methyl isocyanate and ethyl isocyanate.

  Among these, monocarboxylic acid esters such as ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, etc. An organosilicon compound and an aminosilane compound containing a Si—O—C bond are also preferable.

The organic silicon compound of the general formula _{^{(4); R 2 q Si}} (OR 3) 4-q (4)
(In the formula, R ⁵ is any one of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, and an aralkyl group, and may be the same or different. R ⁶ has 1 carbon atom. And an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group of -4, which may be the same or different, and q is an integer of 0 ≦ q ≦ 3. Is mentioned.

  Examples of such organosilicon compounds include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, and tetraalkoxysilane.

  Specific examples of the organosilicon compounds include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri-iso-butylmethoxy. Silane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-iso-propyldiethoxy Orchid, 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, cyclohexylcyclo Nthyldipropoxysilane, 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, Cyclohexylethyldimethoxysilane, 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, ethyltrimeth Sisilane, 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, tetrapropyl Ropoxysilane and tetrabutoxysilane are preferably used. The organosilicon 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 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 polymerizing an olefin 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 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 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.

  When producing a propylene block copolymer, it is performed by multistage polymerization of two or more stages, usually propylene is polymerized in the presence of a polymerization catalyst in the first stage, and ethylene and propylene are copolymerized in the second stage. Can be obtained. An α-olefin other than propylene can be coexisted or polymerized alone during the second stage or subsequent polymerization. Examples of α-olefins include ethylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, 1-hexene, 1-octene and the like. Specifically, polymerization is carried out by adjusting the polymerization temperature and time so that the PP part ratio is 20 to 80% by weight in the first stage, and then ethylene and propylene or other α-olefins in the second stage. Is introduced and polymerized so that the ratio of the rubber part such as ethylene-propylene rubber (EPR) is 20 to 80% by weight. The polymerization temperatures in the first and second stages are both 200 ° C. or less, preferably 100 ° C. or less, and the polymerization pressure is 10 MPa or less, preferably 5 MPa or less. In the case of polymerization time in each polymerization stage or continuous polymerization, the residence time is usually 1 minute to 5 hours. Examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane and heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas phase polymerization method using substantially no solvent. It is done. Preferred polymerization methods are bulk polymerization and gas phase polymerization.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, these are merely examples, and the present invention is not limited to these examples.

[Preparation of alkoxymagnesium-containing solid]
Metal magnesium powder 5.3g (particle size 50-320μm, average particle size 140μm) and dehydrated ethanol (water content 200ppm) in a 1-liter cylindrical flask fully substituted with nitrogen gas and equipped with stirrer and reflux condenser A suspension was formed by charging 153 ml and 12.9 g of diethoxymagnesium powder (particle size: 20 to 130 μm, average particle size: 40 μm) as carrier particles. In this case, the diethoxymagnesium / metal magnesium molar ratio was 0.52. The suspension was then warmed with stirring to initiate the reaction under ethanol reflux. Under ethanol reflux, the mixture was held for 1 hour with stirring until hydrogen evolution ceased. Then, after cooling to room temperature, vacuum drying was performed to obtain about 30 g of a spherical alkoxymagnesium-coated solid. The particle size distribution of the alkoxymagnesium-coated solid after drying was measured using a laser diffraction particle size distribution analyzer (manufactured by MT3000 Nikkiso Co., Ltd.). D ₅₀ = 55.6 μm, D ₁₀ = 35.9 μm, D ₉₀ = 132 μm and SPAN = 1.74. Moreover, as a result of observing the alkoxymagnesium-coated solid material with a scanning electron microscope (JSM-5310LV, manufactured by JEOL Ltd.) at an acceleration voltage of 5 kV, 300 times, 1000 times, and 5000 times, the shape is spherical and the surface is fine. Primary crystals were in the form of dendrites. The measurement result of bulk specific gravity was 0.264. Here, the bulk specific gravity was measured according to JIS K6721.

[Preparation of solid catalyst component (A)]
A 500 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer was charged with 10 g of the above alkoxymagnesium-coated solid, 3.2 g of di-n-butyl phthalate and 80 ml of toluene in a suspended state. It was. Next, 20 ml of titanium tetrachloride was added to the suspension solution, and the temperature was raised to 90 ° C. Thereafter, the reaction was carried out with stirring for 2 hours while maintaining a temperature of 90 ° C. After completion of the reaction, it was washed 4 times with 90 ml of toluene at 90 ° C., 20 ml of titanium tetrachloride and 40 ml of toluene were newly added, the temperature was raised to 110 ° C., and the reaction was carried out with stirring for 2 hours. After completion of the reaction, it was washed 7 times with 70 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. 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 3.1 weight%.

[Formation and polymerization of polymerization catalyst]
Into an autoclave with a stirrer having an internal volume of 2.0 liters completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and 0.0026 mmol of the solid catalyst component as titanium atoms were charged, A polymerization catalyst was formed. Thereafter, 2.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 1 hour. The polymerization activity per gram of the solid catalyst component at this time, the ratio (HI) of boiling n-heptane insoluble matter in the produced polymer, the melt index value (MI) and bulk specific gravity (BD) of the produced polymer (a) 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. ). Further, the melt index value (MI) of the produced polymer (a) was measured according to ASTM D 1238 and JIS K 7210. Furthermore, the bulk specific gravity (BD) of the produced polymer (a) was measured according to JIS K6721.

The alkoxymagnesium-coated solid material was the same as in Example 1 except that 6.0 g was used instead of 5.3 g of metal magnesium powder and 9.5 g was used instead of 12.9 g of diethoxymagnesium powder. Prepared. In this case, the diethoxymagnesium / metal magnesium molar ratio was 0.33. The particle size distribution of the alkoxymagnesium-coated solid after drying was D ₅₀ = 59.7 μm, D ₁₀ = 40.1 μm, D ₉₀ = 136 μm, and SPAN = 1.61. Further, as a result of observation with a scanning electron microscope, the shape was spherical and the surface form was the same as in Example 1. The measurement result of bulk specific gravity was 0.263. A solid catalyst component and a catalyst were prepared and polymerized in the same manner as in Example 1 except that the alkoxymagnesium-coated solid obtained as described above was used. The obtained results are shown in Table 1.

The alkoxymagnesium-coated solid material was the same as in Example 1 except that diethoxymagnesium having a particle size of 7.7 to 88 μm and an average particle size of 13 μm was used instead of diethoxymagnesium having a particle size of 20 to 130 μm and an average particle size of 40 μm. Prepared. The particle size distribution of the magnesium ethylate after drying was D ₅₀ = 30.2 μm, D ₁₀ = 21.2 μm, D ₉₀ = 60.8 μm, and SPAN = 1.31. Moreover, as a result of observation with a scanning electron microscope, the shape is spherical, and there are many particles in which a plurality of particles are aggregated. The surface form was the same as in Example 1. The measurement result of the bulk specific gravity was 0.224. A solid catalyst component and a catalyst were prepared and polymerized in the same manner as in Example 1 except that the alkoxymagnesium-coated solid obtained as described above was used. The obtained results are shown in Table 1.

An alkoxymagnesium-coated solid was prepared in the same manner as in Example 3 except that the ethanol amount was 153 ml instead of 123 ml. The particle size distribution of the magnesium ethylate after drying was D ₅₀ = 23.2 μm, D ₁₀ = 16.2 μm, D ₉₀ = 66.4 μm, and SPAN = 1.16. Further, as a result of observation with a scanning electron microscope, the shape is spherical and there are few aggregated particles. The surface was a form in which flaky primary crystals of several hundred μm were laminated. The measurement result of the bulk specific gravity was 0.248. A solid catalyst component and a catalyst were prepared and polymerized in the same manner as in Example 1 except that the alkoxymagnesium-coated solid obtained as described above was used. The obtained results are shown in Table 1.

[Preparation of alkoxymagnesium-containing solid]
Metal magnesium powder 5.3g (particle size 50-320μm, average particle size 140μm) and dehydrated ethanol (water content 200ppm) in a 1-liter cylindrical flask fully substituted with nitrogen gas and equipped with stirrer and reflux condenser 153 ml and 12.9 g of diethoxymagnesium powder (particle size: 7.7 to 88 μm, average particle size of 13 μm) as carrier particles and 0.02 g of MgCl ₂ (halogen / Mg molar ratio = 0.0019) as catalyst were suspended. A turbid liquid formed. In this case, the diethoxymagnesium / metal magnesium molar ratio was 0.52. The suspension was then warmed with stirring to initiate the reaction under ethanol reflux. Under ethanol reflux, the mixture was held for 1 hour with stirring until hydrogen evolution ceased. Then, after cooling to room temperature, vacuum drying was performed to obtain about 30 g of a spherical alkoxymagnesium-coated solid. The particle size distribution of the magnesium ethylate after drying was D ₅₀ = 25.4 μm, D ₁₀ = 17.1 μm, D ₉₀ = 49.6 μm, and SPAN = 1.28. Further, as a result of observation with a scanning electron microscope, the shape is spherical and the surface is in the form of fine primary crystals connected in a dendritic shape. The measurement result of bulk specific gravity was 0.214. A solid catalyst component and a catalyst were prepared and polymerized in the same manner as in Example 1 except that the alkoxymagnesium-coated solid obtained as described above was used. The obtained results are shown in Table 1.

Comparative Example 1
(Preparation of alkoxymagnesium)
153 ml of magnesium metal powder 8.0 g (particle size 50-320 μm, average particle size 140 μm) and dehydrated ethanol (water content 200 ppm) in a 1-liter cylindrical flask fully substituted with nitrogen gas and equipped with a stirrer and reflux condenser Was charged to form a suspension. Next, 1.0 g of iodine was added, the temperature of the suspension was increased while stirring, and the reaction was started under reflux of ethanol. Under ethanol reflux, the mixture was held for 1 hour with stirring until hydrogen evolution ceased. Then, after cooling to room temperature, vacuum drying was performed to obtain about 30 g of spherical alkoxymagnesium. Particle size distribution of the alkoxy magnesium after drying was measured with a laser diffraction particle size distribution measuring apparatus (manufactured by MT3000_Nikkiso _{(Ltd.)), D 50 = 38.7μm,} D 10 = 27.7μm, D 90 = 60 0.5 μm and SPAN = 1.86. Moreover, the measurement result of bulk specific gravity was 0.279.

  A solid catalyst component and a catalyst were prepared and polymerized in the same manner as in Example 1 except that the alkoxymagnesium-coated solid obtained as described above was used. The obtained results are shown in Table 1.

(Production of propylene block copolymer)
To an autoclave with a stirrer having an internal volume of 2.0 liters completely substituted with nitrogen gas, triethylaluminum (TEAL), cyclohexylmethyldimethoxysilane (CMDMS) and the solid catalyst component obtained in Example 1 were added as titanium atoms. .0026 mmol was charged to form a polymerization catalyst. At this time, the molar ratio of Ti, TEAL and CMDMS (Ti / TEAL / CMDMS) in the solid catalyst component was 1/400/67. Thereafter, 2.0 liters of hydrogen gas and 1.2 liters of liquefied propylene were charged, and a propylene polymerization reaction was performed at 70 ° C. for 1 hour, so that a PP part ratio was about 70% by weight. Then, while supplying ethylene gas and propylene gas at an ethylene / propylene molar ratio of 0.7, polymerization is carried out in a gas phase at 70 ° C. for 2 hours at a pressure of 1.7 MPa so that the rubber part ratio is about 30% by weight. In addition, a propylene block copolymer was produced. Table 2 shows the rubber part ratio (block ratio), ethylene content, EPR content, MI, flexural modulus and Izod impact strength of the resulting propylene block copolymer.

Here, ethylene content and EPR content were measured as follows.
The ethylene content in the propylene block copolymer was quantified by ¹³ C-NMR. Further, the content of ethylene propylene rubber component (EPR) in the propylene block copolymer was measured by the following method. To a 1 liter flask equipped with a stirrer and a condenser tube, about 2.5 g of the copolymer, 8 mg of 2,6-di-t-butyl-p-cresol, and 250 ml of p-xylene were charged, Stir until the polymer is completely dissolved. Next, the flask was cooled to room temperature and left for 15 hours to precipitate a solid. This was separated into a solid and a liquid phase part by a centrifuge. Thereafter, the separated solid was taken into a beaker, 500 ml of acetone was poured in, stirred for 15 hours at room temperature, the solid was filtered and dried, and the weight was measured (this weight is designated as A). Further, the same operation was performed on the separated liquid phase portion to precipitate a solid, and the weight was measured (this weight is designated as B). The content (% by weight) of the ethylene propylene rubber component (EPR) in the copolymer was calculated by the formula [B (g) / [A (g) + B (g)] × 100].

  The flexural modulus was blended with a heat stabilizer in the polymer, pelletized with an extruder, molded with an injection molding machine to prepare a measurement sample, and measured at 23 ° C. according to ASTM D790.

  The Izod impact strength was determined by blending a heat-resistant stabilizer with a polymer, pelletizing with an extruder, molding this with an injection molding machine to prepare a measurement sample, and measuring 23 ° C. for an injection molded test piece with a notch according to ASTM D256. Measured with

Comparative Example 2
A propylene block copolymer was produced in the same manner as in Example 6 except that the solid catalyst component obtained in Comparative Example 1 was used. The obtained results are shown in Table 2.

  From the above results, when propylene block copolymerization was performed using the solid catalyst component prepared using the alkoxymagnesium-containing solid material of the present invention, the particle size of the solid catalyst component was large to some extent, moderate bulk specific gravity and pores Therefore, even under the same polymerization conditions, the EPR component did not precipitate on the polymer surface, and a high content and finely dispersed block copolymer was obtained. As a result, the balance between rigidity and impact resistance was improved. I understand.

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

Claims (8)

A method of reacting metal alkoxide support particles, metal magnesium and alcohol to form a layer made of alkoxymagnesium on the surface of the metal alkoxide support particles , in the presence of halogen or a halogen-containing compound. A process for preparing an alkoxymagnesium-coated solid material, characterized in that it is carried out. 2. The method for preparing an alkoxymagnesium-coated solid material according to claim 1, wherein the metal alkoxide carrier particles have an average particle diameter of 1 to 100 μm and are spherical. The method for preparing an alkoxymagnesium-coated solid material according to claim 1 or 2 , wherein the metal alkoxide carrier particles are ethoxymagnesium powder. The method for preparing an alkoxymagnesium-coated solid according to claim 1 , wherein the alcohol is ethanol. The alkoxymagnesium-coated solid material (a) obtained by the method according to any one of claims 1 to 4 and tetravalent titanium are in contact with a halogen compound (b) and an electron donating compound (c). A process for producing a solid catalyst component for polymerizing olefins. The method for producing a solid catalyst component for olefin polymerization according to claim 5 , wherein the electron donating compound (c) is an aromatic carboxylic acid ester. (A) Solid catalyst component for olefin polymerization obtained by the method according to claim 5 or 6 , (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) A method for producing an olefin polymerization catalyst, which comprises contacting an external electron donating compound. The (C) external electron donating compound is represented by the following general formula (2):
R ² _q Si (OR ³ ) _4-q (2)
(In the formula, R ² is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and may be the same or different. R ³ has 1 carbon atom. Represents an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and q is an organic group represented by 0 ≦ q ≦ 3. The method for producing a catalyst for olefin polymerization according to claim 7 , which is a silicon compound.

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