JP2009209310A - Solid catalytic component for polymerization of olefins, catalyst, and process for producing olefin polymer using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalytic component and a catalyst for polymerization of olefins producing a polymer with little dust while retaining high tacticity and high yield of the polymer. <P>SOLUTION: The particulate solid catalytic component for polymerization of olefins comprises magnesium, titanium, a halogen atom, and an electron donating compound, and has a monomodal particle size distribution, wherein particles having particle sizes of 10 to 80 μm comprise 90 wt.% or more of the entire particles. The solid catalytic component for polymerization of olefins has an average particle diameter of 10 to 100 μm, and particle of 5 μm or less is increased by 20 wt.% or less upon ultrasonic treatment with high-frequency output of 80 W at oscillating frequency of 40 KHz for 30 minutes. A catalyst for polymerization of olefins is formed from the solid catalytic component, an organoaluminum compound and an organosilicon compound. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a solid catalyst component and a catalyst for olefin polymerization, which 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.

  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 3 (Japanese Patent Laid-Open No. 6-287225), a suspension of spherical dialkoxymagnesium, an aromatic hydrocarbon compound and a 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.

Further, in Patent Document 4 (Japanese Patent Laid-Open No. 6-306116), in the solid catalyst component for olefin polymerization in which at least magnesium, titanium and / or vanadium, and halogen are supported on silicon oxide and / or aluminum oxide, the silicon A solid catalyst component for olefin polymerization has been proposed in which the oxide and / or the aluminum oxide satisfy the following characteristics (A) to (E).
(A) The average particle diameter measured by the sieving method is 20 to 150 μm.
(B) The specific surface area measured by BET method is 150-600 m < ² > / g.
(C) The pore volume between the pore radii of 18 to 1,000 angstroms measured by the mercury intrusion method is 0.3 to 2.0 cm ³ / g.
(D) Apparent specific gravity measured by JIS-K6220-6.8 is 0.32 or more.
(E) Particles classified in the range of 53 μm or more and 75 μm or less by the sieving method are subjected to ultrasonic destruction treatment at 40 KHz and 35 W for 20 minutes, and the ratio of particles (ultrasonic destruction degree) of 50 μm or less is 30% or less. It is.

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-6-287225 (Claims) JP-A-6-306116 (Claims)

  That is, the object of the present invention is to polymerize 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 catalyst component and a catalyst for olefin polymerization.

  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. In addition, when the ultrasonic fracture strength is a predetermined value or more, and the particle size distribution of the particulate solid catalyst component is sharp, it is found that a polymer having a small particle size and a sharp particle size distribution can be obtained. The invention has been completed.

  That is, the present invention is a particulate solid catalyst component containing magnesium, titanium, a halogen atom and an electron donating compound, wherein 5-100 μm particles are 90% by weight or more in all particles, and the average particle size is 10-10. An object of the present invention is to provide a solid catalyst component for olefin polymerization, characterized in that the increase amount of particles of 5 μm or less is 20% by weight or less when subjected to ultrasonic treatment for 30 minutes at a high frequency output of 80 W and an oscillation frequency of 40 KHz. It is.

Further, the present invention provides (A) a solid catalyst component for olefin polymerization according to claim 1,
(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, wherein the olefin is polymerized 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, the solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”) is a solid containing magnesium, titanium, a halogen atom and an electron donating compound. The catalyst component does not include a carrier material such as silicon oxide and aluminum oxide such as silica and alumina, and is a particulate material in which a titanium compound and an electron donating compound are supported on a magnesium compound.

  In the solid catalyst component (A) of the present invention, 5 to 100 μm particles are 90% by weight or more, preferably 95% by weight or more, more preferably 100% by weight, and more preferably 10 to 80 μm particles in all particles. It is 95 weight% or more in particle | grains. That is, the component (A) preferably has a monomodal and sharp particle size distribution and has few fine particles. The component (A) is preferably free from fine particles of 1.0 μm or less. In the present specification, the particulate form means a powder form. By polymerizing using the solid catalyst component having the above particle size distribution, a polymer having a sharp particle size distribution with very few fines can be obtained. The particle size distribution of the component (A) can be measured by a laser diffraction particle size distribution measuring method.

  (A) The average particle diameter of a component is 10-100 micrometers, Preferably it is 10-50 micrometers, More preferably, it is 15-40 micrometers. When the average particle size is less than 10 μm, it is not preferable in that the produced polymer is finely divided, and when it exceeds 100 μm, it is not preferable in that the bulk density of the polymer is lowered. The average particle diameter can be measured by a laser diffraction particle size distribution measurement method.

  When the solid catalyst component (A) of the present invention is subjected to ultrasonic treatment for 30 minutes at a high-frequency output of 80 W and an oscillation frequency of 40 KHz, the increase amount of particles of 5 μm or less is 20% by weight or less, preferably 10% by weight or less. Preferably it is 5 weight% or less. The amount of increase in particles of 5 μm or less due to such ultrasonic treatment is also referred to as “ultrasonic breaking strength”.

  The ultrasonic breaking strength is obtained by the following method. In the sample for ultrasonic treatment, 10 g of the solid catalyst component is introduced into a container sufficiently substituted with an inert gas, and then 100 ml of an organic solvent such as n-heptane is introduced so that the sample in the container does not come into contact with the outside air. Seal to. Next, after setting the container so that the water tank liquid level position of the ultrasonic processing apparatus is higher than the solvent liquid level position in the container, ultrasonic treatment may be performed under the above-mentioned ultrasonic wave transmission conditions. After the ultrasonic treatment, the amount of particles of 5 μm or less is measured by a laser diffraction particle size distribution measurement method, and is displayed as the incidence of particles of 5 μm or less.

  In addition, solid catalyst component (A) confirms beforehand the presence of particles of 5 μm or less before ultrasonic treatment. When there are no particles of 5 μm or less, ultrasonic treatment may be performed as it is. In addition, when particles of 5 μm or less are included, particles of 5 μm or less are removed in advance by a sieving method, a predetermined amount is sampled, and then ultrasonic treatment is performed, or a particle amount of 5 μm or less is measured in advance. Thereafter, ultrasonic treatment is performed, and the amount of particles of 5 μm or less before treatment may be subtracted from the amount of particles of 5 μm or less after treatment. The quantification of the particles of 5 μm or less in the component (A) can be obtained by a method by laser diffraction particle size distribution measurement. After the ultrasonic treatment, if the increase amount of the particles of 5 μm or less exceeds 20% by weight, that is, if the ultrasonic breaking strength is weak, the particles of the component (A) are broken by the stirring force or reaction during the polymerization and become fine powder. And a polymer with a large amount of fine powder is obtained.

Moreover, the specific surface area of the solid catalyst component (A) of this invention is 10-500 m < ² > / g, Preferably it is 100-400 m < ² > / g, More preferably, it is 200-400 m < ² > / g. If the specific surface area is less than 10 m ² / g, the reaction during polymerization does not proceed and the activity and the like are lowered, and this is not preferred. If it exceeds 500 m ² / g, the reaction during polymerization becomes excessive and fine powder is generated, which is not preferred. The specific surface area can be determined by the BET method.

  The pore volume of the solid catalyst component (A) is 0.08 or more and less than 0.3 ml / g, preferably 0.1 or more and less than 0.3 ml / g, particularly preferably 0.1 to 0.2 ml. / G. If the pore volume is less than 0.08 ml / g, the reaction during polymerization does not proceed and the activity and the like are lowered, and this is not preferable, and if it is 0.3 ml / g or more, the reaction during polymerization becomes excessive and fine powder is generated. It is not preferable. The pore volume can be determined by the BET method.

  The bulk specific gravity of the solid catalyst component (A) is 0.3 to 0.8 g / ml, preferably 0.5 to 0.7 g / ml. If the bulk specific gravity is less than 0.3 g / ml, the bulk specific gravity of the polymer will be low due to the replica phenomenon, which is not preferred, and if it exceeds 0.8 g / ml, the activity will decrease, which is not preferred. Bulk specific gravity can be calculated | required by the measuring method of JISK6721.

  The content of titanium, magnesium, halogen atom and electron donating compound in the solid catalyst component (A) in the present invention is not particularly limited, but preferably 0.5 to 8.0% by weight of titanium, preferably 1. 0-6.0 wt%, more preferably 1.5-4.0 wt%, magnesium 10-70 wt%, more preferably 10-50 wt%, particularly preferably 15-40 wt%, still more 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 total amount of electron donating compounds is 0. 0.5 to 30% by weight, more preferably 1 to 25% by weight, particularly preferably 2 to 20% by weight.

  The solid catalyst component (A) is contacted with the magnesium compound (a), the tetravalent titanium halogen compound (b) and the electron donating compound (c) to form a solid product. It can be prepared by contacting an inert gas containing alcohol or ether, and further contacting a tetravalent titanium halogen compound (b) with the solid product after the vapor contact.

  Magnesium compounds used in this preparation (hereinafter sometimes referred to simply as “component (a)” include dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium or fatty acids. Among these magnesium compounds, dialkoxymagnesium is preferable, and specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, etc. Diethoxymagnesium is particularly preferred, and these dialkoxymagnesiums are The genus magnesium, in the presence of a halogen or halogen-containing metal compound may be one obtained by reacting an alcohol. Also, dialkoxy magnesium may be used either individually 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 (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 Si—O—C bonds and Si—N—C bonds Etc. can be used, and one type or a combination of two or more types can be used. In the subsequent step, when the compound contained in the inert gas that comes into contact with the solid product is an alcohol or ether, the electron-donating compound is other than the alcohol or ether used.

  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 esters such as chill, dicarboxylic esters such as diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, phthalate diester , Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, acid halides such as phthalic acid dichloride, terephthalic acid dichloride, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, methylamine, ethylamine, triphenyl Amines such as butylamine, piperidine, aniline, pyridine, amides such as oleic acid amide, stearic acid amide, acetonitrile, benzoic acid Nitriles such as ril and tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, Si-O-C such as phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane And organic silicon compounds containing Si—N—C bonds such as (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, alkyl (alkylamino) silane, and alkylaminosilane.

  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. , 4-bromophthalate di-n-butyl, 4-bromophthalate diisobutyl, 4-methylphthalate dineopentyl, 4,5-dimethylphthalate dineopentyl, 4-methylphthalate dineopentyl, 4-ethylphthalate dineopentyl, 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).

  In the present invention, an inert gas containing water, alcohol or ether (hereinafter also referred to as “water etc.”), preferably an inert gas containing water, to the solid product obtained as described above. It is desirable to contact the gas. By bringing the moisture into contact, fine particles existing on the particle surface of the solid catalyst component or particles that are easily broken or peeled off can be removed, and the ultrasonic breaking strength can be within the above range. Nitrogen gas, argon gas, or the like is used as the inert gas.

  As the alcohol, those having a relatively high vapor pressure at normal temperature are preferable, and methanol, ethanol, 2-butanol, and 2-ethyl-1-hexanol are preferable. Alcohol can be used 1 type or in combination of 2 or more types. The ether preferably has a relatively high vapor pressure at room temperature, and is diisoamyl ether, diethyl ether or 2-ethylglycidyl ether. Ethers can be used alone or in combination of two or more.

  As a contact method, a container in an inert gas atmosphere is filled with a solid product, and a predetermined amount of an inert gas such as nitrogen that is preliminarily mixed with moisture is filled in the container, or an inert gas atmosphere is contacted. The solid product is filled in a container, and an inert organic solvent is further filled to form a suspension, and a predetermined amount of an inert gas such as nitrogen previously containing moisture is blown into the suspension. The method of contacting is mentioned. When water is included in the inert gas, it is desirable to include the water in the inert gas so that the water is saturated. By measuring the amount of saturated water vapor at the temperature of the inert gas at that time, solids are generated. Moisture etc. that come into contact with an object can be quantified. The water vapor or the like can be obtained by heating or depressurizing water or the like. The method of filling a container with a solid product, adding a solvent containing a liquid such as water, and stirring does not improve the ultrasonic breakdown strength of the particles of the solid product. The production of the fine particle polymer cannot be suppressed.

  The contact condition between the solid product and moisture is -20 to 150 ° C, preferably 10 to 130 ° C, particularly preferably 30 to 110 ° C. At this time, it is desirable to make the contact at a temperature higher than the dew point of the inert gas containing moisture, and particularly when using an inert gas saturated with moisture or the like, the temperature is set higher than the dew point. Be careful not to condense moisture in the supply pipe or in the container that comes into contact. Further, it is desirable that moisture or the like be contained in an inert gas in a vapor state, and it is preferable that the inert gas is not present in the form of a liquid such as a mist of moisture or the like. The contact time is 1 minute to 10 hours, preferably 10 minutes to 5 hours, particularly preferably 30 minutes to 3 hours. The amount of water or the like that comes into contact with the solid product is 0.0001 g to 0.5 g, preferably 0.005 g to 0.3 g, and particularly preferably 0.001 g to 0.5 g, with respect to 1 g of the solid product. 0.1 g.

  In addition, a known surfactant may be brought into contact with the solid product before, during or after contact with moisture. 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.

  After contacting the solid product with moisture as described above, the component (b) is contacted again to obtain the solid catalyst component (A). 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 in a state suspended in the aromatic hydrocarbon compound (d). 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 surfactant is contacted again in an inert solvent to form a suspension, and then the suspension The solvent in the liquid can also be removed. The solid catalyst component (A), which is brought into contact with the component (b) again after contacting the solid product with an inert gas containing moisture or the like, remains in the same manner as the solid product after contact with the inert gas. There are still few fine powders on the surface and easy-to-peel particles. In addition, the ultrasonic fracture strength 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, the washed solid product (2) is suspended in an aromatic hydrocarbon compound, and water and the like are saturated in this suspension. Nitrogen gas is blown in, and moisture or the like 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. is there.

  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 are used, and among them, 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.

  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 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.

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

[Preparation of solid catalyst component (A)]
Suspension in which 10 g of diethoxymagnesium, 50 ml of toluene and 2.0 ml of di-n-butyl phthalate were charged into a 500-ml round bottom flask equipped with a stirrer and a reflux condenser and sufficiently substituted with nitrogen gas. Formed. On the other hand, 30 ml of titanium tetrachloride and 50 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 three times with 120 ml of toluene at 90 ° C., and then 20 ml of titanium tetrachloride and 80 ml of toluene were newly added, and the temperature was raised to 110 ° C. and reacted with stirring for 2 hours. . Thereafter, the supernatant was removed by decantation, washed 5 times with 120 ml of n-heptane at 40 ° C., and dried. Next, 10 g of a solid substance 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, water-saturated nitrogen gas was bubbled through the suspension so as to be 0.02 g-water / g-solid, thereby bringing the solid product into contact with water. The contact temperature was 25 ° C. and the contact time was 4 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 140 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. In addition, it was 3.5 weight% when the titanium content rate in this solid catalyst component was measured. Further, when the particle size distribution of the solid catalyst component was measured, it had a monomodal particle size distribution, and 5 to 100 μm particles were 90% by weight or more in all particles, and 3 to 110 μm particles were 100% in all particles. %Met. The average particle diameter was 38 μm, and the ultrasonic fracture strength obtained by the following method was 3% by weight.

[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, the propylene pressure in the system was 0.7 MPa, and polymerization was continued at 70 ° C. for 2 hours. 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 diameter 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.

(Measurement of ultrasonic fracture strength of solid catalyst components)
Into a round bottom eggplant-shaped flask having a capacity of 200 milliliters sufficiently substituted with nitrogen gas, 10 g of the solid catalyst component was introduced, and then 100 ml of n-heptane was introduced, and finally the round-bottomed eggplant-shaped flask was not brought into contact with outside air. The top was plugged. Next, using an ultrasonic device, set the round bottom eggplant-shaped flask containing the solid catalyst component and n-heptane so that the liquid level position in the water tank is higher than the heptane liquid level position in the round bottom eggplant-shaped flask, and then output high frequency. Ultrasonic treatment was performed at 80 W and an oscillation frequency of 40 KHz for 30 minutes. After ultrasonic treatment, the particle size distribution of the catalyst was measured by a laser diffraction particle size distribution measuring method, and the amount of increase in particles of 5 μm or less was examined. In Table 1, “US” indicates sonication.

Example 2 to Example 5
Instead of 0.02 g-water / g-solid, 0.06 g-water / g-solid (Example 2), 0.1 g-water / g-solid (Example 3), 0.005 g- Preparation of solid catalyst component, formation of polymerization catalyst and polymerization in the same manner as in Example 1 except that water / g-solid (Example 4) and 0.001 g-water / g-solid (Example 5) were used. Went. 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 solid product was not contacted with water-saturated nitrogen gas, and the titanium tetrachloride after the contact was not added. Went. The results are shown in Table 1. Further, when the particle size distribution of the solid catalyst component was measured, it had a monomodal particle size distribution, and particles of 2 to 110 μm were 90% by weight or more in all particles, and particles of 0.1 to 140 μm were in all particles. It was 100% by weight. The average particle size was 32 μm, and the ultrasonic fracture strength was 35% by weight.

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, the solid composition was obtained by washing 10 times with 200 ml of n-heptane at 40 ° C. 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.

  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. Further, when the particle size distribution of the solid catalyst component of Comparative Example 2 was measured, it had a monomodal particle size distribution, and particles of 1 to 140 μm were 90% by weight or more, and particles of 0.1 to 160 μm were all particles. It was 100% by weight in the particles. The average particle size was 33 μm, and the ultrasonic fracture strength was 34% by weight.

Comparative Example 3
Instead of contacting the solid product with an inert gas containing water-saturated nitrogen gas, a solid catalyst was obtained in the same manner as in Example 1 except that the solid product was contacted with 100 ml of n-heptane containing 10 ppm of water. Components were prepared and polymerization catalyst formation and polymerization were performed. The results are shown in Table 1. Further, when the particle size distribution of the solid catalyst component was measured, it had a monomodal particle size distribution, and particles of 3 to 105 μm were 90% by weight or more in all particles, and particles of 0.5 to 130 μm were in all particles. It was 100% by weight. The average particle size was 35 μm, and the ultrasonic breaking strength was 23% by weight.

  From the results of Table 1, high activity and high stereoregularity are maintained by polymerizing propylene using a solid catalyst component having a predetermined particle size distribution and an ultrasonic fracture strength of 20% by weight or less, and a catalyst. It can be seen that the generation of the fine powder polymer is extremely small. On the other hand, the comparative example using the solid catalyst component and the catalyst having an ultrasonic fracture strength exceeding 20% by weight could not suppress the generation of the fine powder polymer.

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

Claims (3)

  Particulate solid catalyst component containing magnesium, titanium, halogen atom and electron donating compound, 5-100 μm particles are 90% by weight or more in all particles, average particle size is 10-100 μm, high frequency output A solid catalyst component for olefin polymerization, wherein an increase in particles of 5 μm or less is 20% by weight or less when subjected to ultrasonic treatment at 80 W and an oscillation frequency of 40 KHz for 30 minutes. (A) The solid catalyst component for olefin polymerization according to claim 1,
(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, which comprises polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 2.

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