JP2012077148A - Solid catalyst component for olefin polymerization, method of producing the solid catalyst component, catalyst, and method of producing polyolefin using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a solid catalyst component for olefin polymerization, which can maintain the powder shape of a polymer to be produced and can prevent fine microparticles from being generated; a method of producing the solid catalyst component; a catalyst; and a method of producing polyolefin using the catalyst.SOLUTION: The solid catalyst component for olefin polymerization contains magnesium, titanium, a halogen atom, and a polyolefin that can be solved in an inert hydrocarbon solvent.

Description

  The present invention provides a solid catalyst component for olefin polymerization that maintains good particle properties even under severe polymerization conditions, has few by-product fine particles, and can suppress coagulation of the copolymer, its production method, catalyst, and The present invention relates to a method for producing polyolefin using the same.

  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 dialkoxymagnesium compounds have high performance and are widely used industrially.

  For example, in Patent Document 1 (JP-A-6-287217), a suspension of spherical dialkoxymagnesium, aromatic hydrocarbon compound and phthalic acid diester is mixed with an aromatic hydrocarbon compound and titanium tetrachloride. In addition to the solution, the reaction product is washed with an aromatic hydrocarbon compound, the solid component obtained by reacting with titanium tetrachloride again is dried, subjected to fine powder removal treatment, and then powdered. A solid catalyst component for olefin polymerization obtained through a treatment step of adding a nonionic surfactant is proposed.

  In Patent Document 2 (Japanese Patent Application Laid-Open No. 2007-146065), a magnesium compound is reacted with a tetravalent titanium halogen compound and an electron donor in the presence of an inert organic solvent containing a surface active component and an alcohol. There has been proposed a solid catalyst component for olefin polymerization, which can be obtained by producing a polyolefin polymer having a high pore volume with almost no fine powder polymer having a particle size of 45 μm or less during polymerization.

  Further, in Patent Document 3 (Japanese Patent Laid-Open No. 2009-209305), an inert gas containing water is added to a solid product obtained by contacting a magnesium compound, a tetravalent titanium halogen compound and an electron donating compound. After the contact, the solid product is obtained by further contacting with a tetravalent titanium halogen compound, and a polymer having a fine powder can be obtained while maintaining a high degree of polymer stereoregularity and yield. Proposed solid catalyst components for olefin polymerization have been proposed.

  Although all of the above prior arts have the effect of removing the fine powder derived from the raw material magnesium compound or the solid catalyst component itself and reducing the amount of fine powder of the resulting polymer to some extent, There is still generation of polymer fine particles generated depending on particle destruction, particularly microfine polymer called microfine, and development of a catalyst with less generation of fine polymer has been desired. It was not enough to solve.

  On the other hand, in Patent Document 4 (Japanese Patent Laid-Open No. 09-165414), magnesium chloride dissolved in an aliphatic alcohol and a hydrocarbon solvent is represented by a diester of an aromatic dicarboxylic acid, a halogenated hydrocarbon compound, and a specific formula. Production of solid catalyst component obtained by contacting titanium halide, catalyst obtained by prepolymerization of the solid catalyst component, and olefin polymer used in combination with silicon compound and organoaluminum compound represented by specific formula A method is disclosed.

  Since the above prior art is a preparation method in which a magnesium compound is dissolved with an alkoxy-containing compound and then a solid catalyst component is precipitated, the process of depositing a solid from a solution of the magnesium compound is complicated. In addition, although the alkoxytitanium compound used or produced in the method for preparing the solid catalyst component is halogenated and removed, there is a problem that a part of the alkoxytitanium compound remains in the deposited solid and the performance such as activity is lowered. It was. Further, the generation of fine particles during polymerization has not been greatly improved. Further, although an improvement for suppressing the particle collapse of the catalyst particles by prepolymerization has been proposed, the suppression of the generation of fine particles is still insufficient.

JP-A-6-287217 JP 2007-146065 A JP 2009-209305 A JP 09-165414 A

  Although the effect of reducing the amount of fine particles of the polymer produced to some extent by the above-mentioned conventional technology is recognized, all of them are insufficient, and the active sites are already formed by the prepolymerization, so that they are poisoned. There is a drawback that it easily deteriorates with time during storage, and improvement has been desired.

  Accordingly, an object of the present invention is to provide a solid catalyst component for olefin polymerization capable of maintaining the powder shape of a polymer to be produced and suppressing generation of fine particles, a production method thereof, a catalyst, and a polyolefin using the same. It is in providing the manufacturing method of.

  In such a situation, the present inventors have conducted intensive studies, and as a result, impregnated a specific polyolefin with particles that are solid components containing conventional titanium, magnesium, and halogen atoms. The inventors have found that it is possible to maintain the shape and suppress the generation of fine particles, and have completed the present invention.

  That is, the present invention provides a solid catalyst component for olefin polymerization characterized by containing a polyolefin soluble in magnesium, titanium and halogen atoms and an inert hydrocarbon solvent.

  The present invention also includes an impregnation step in which a polyolefin dissolved in an inert organic solvent is brought into contact with and mixed with a solid component containing magnesium, titanium, and a halogen atom to impregnate the polyolefin solubilized in the solid component particles. The present invention provides a method for producing a solid catalyst component for olefin polymerization characterized by comprising:

The present invention also provides the solid catalyst component (A) for polymerizing olefins and 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 an integer of 0 <p ≦ 3) (B The catalyst for polymerization of olefins formed by (1) is provided.

  The present invention also provides a method for producing a polyolefin using the olefin polymerization catalyst.

  According to the solid catalyst component and the catalyst of the present invention, the shape of the polymer to be produced can be maintained and the generation of fine particles can be suppressed. In particular, by using a solid catalyst component containing a polyolefin soluble in an inert hydrocarbon solvent at 70 ° C. having a specific molecular weight and stereoregularity, good particle properties can be maintained even under severe polymerization conditions. Less particulates are produced. When the production of polymer fine particles as a by-product is suppressed, there is no adhesion in the polymerization reactor, and the operational stability of the polymer separation process is increased.

  The solid catalyst component (A) for olefin polymerization of the present invention (hereinafter sometimes referred to as “component (A)”) contains magnesium, titanium, a halogen atom, and a polyolefin soluble in an inert hydrocarbon solvent. . That is, the component (A) is a polyolefin (hereinafter referred to as “component (A)” that is soluble in an inert hydrocarbon solvent in a solid component containing magnesium, titanium, and a halogen atom (hereinafter sometimes referred to as “component (a1)”). a2) ”, which may be called).

  Component (a1) is prepared by contacting a magnesium compound (i), a titanium halide compound (ii) and, if necessary, an electron donating compound (iii). In the present invention, the magnesium compound (i) (hereinafter sometimes simply referred to as “component (i)”) used for the preparation of the component (a1) includes dihalide magnesium, dialkylmagnesium, halogenated alkylmagnesium, Examples thereof include alkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium and fatty acid magnesium. Among these magnesium compounds, magnesium dihalide, a mixture of magnesium dihalide and dialkoxymagnesium, and dialkoxymagnesium are preferable, and dialkoxymagnesium is particularly preferable.

  Examples of dialkoxymagnesium include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium. These dialkoxymagnesium may be obtained by reacting metal magnesium with alcohol in the presence of halogen or a halogen-containing metal compound. Moreover, said dialkoxy magnesium can also be used individually or in combination of 2 or more types.

  Furthermore, the magnesium compound used for the preparation of the solid component (a1) 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 reduced.

  The spherical magnesium compound is not necessarily spherical, 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 average particle size of the magnesium compound is not particularly limited, but those having a 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 size is 1 to 100 μm, preferably 5 to 80 μm, more preferably 10 to 60 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, the particle size distribution is expressed as a particle size distribution index [(D90-D10) / D50] (where D90 is a particle size (μm) of 90% of the integrated particle size in the integrated particle size distribution, and D50 is a particle of 50% of the integrated particle size in the integrated particle size distribution. The diameter (μm), D10 is a particle diameter (μm) of 10% of the accumulated particle size in the accumulated particle size distribution.) Is 3 or less, preferably 2.5, more preferably 2 or less.

  Further, the bulk specific gravity of the magnesium compound is not particularly defined, but those having a particularly high bulk specific gravity are preferably used, preferably 0.20 to 0.40 g / ml, more preferably 0.23 to 0.37 g / ml. Particularly preferably, an olefin polymer having a high bulk specific gravity and a good particle shape can be obtained by using a polymer having a particle size in the range of 0.25 to 0.35 g / ml. The bulk specific gravity here is measured according to JIS K6721 (1977).

  For example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, and JP-A-8-73388 can be used to produce spherical dialkoxymagnesium as described above. It is exemplified in the publication.

In the present invention, the titanium compound (ii) used for the preparation of the titanium source of component (a1) and the halogen atom is represented by the general formula (2);
^{_{Ti (OR 2) 4-P}} X p (2)
(Wherein R ² is a hydrocarbon residue, preferably about 1 to 10 carbon atoms, X represents a halogen, and p represents a number of 0 ≦ p ≦ 4). . Of these, tetravalent titanium compounds are preferable, and tetravalent titanium compounds containing halogen are more preferable.

Specific examples include TiCl ₄ , TiBr ₄ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₃ Cl, Ti (O—iC ₃ H ₇ ) Cl ₃ , Ti (O—nC ₄ H ₉ ) Cl ₃ , Ti (O—nC ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OC ₂ H ₅ ) (OC ₄ H _{9) 2 Cl, Ti (O} -nC 4 H 9) 3 Cl, Ti (OC 6 H 5) Cl 3, Ti (O-iC 4 H 9) 2 Cl 2, Ti (OC 5 H 11) Cl ₃ , Ti (OC ₆ H ₁₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) ₄ , Ti (O—nC ₃ H ₇ ) ₄ , Ti (O—nC ₄ H ₉ ) ₄ , Ti (O—iC ₄ H) _{9) 4, Ti (O-} nC 6 H 13) 4, Ti (O-nC 8 H 17) 4, i _{[OCH 2 CH (C 2 H 5} ) C 4 H 9 ] _4, and the like.

In addition, a molecular compound obtained by reacting TiX ₄ (where X represents halogen) with an electron donor described later can also be used as a titanium source. Specific examples of such molecular compounds include TiCl ₄ · CH ₃ COC ₂ H ₅ , TiCl ₄ · CH ₃ CO ₂ C ₂ H ₅ , TiCl ₄ · C ₆ H ₅ NO ₂ , TiCl ₄ · CH ₃ COCl, TiCl ₄ · C ₆ H ₅ COCl, TiCl ₄ · C ₆ H ₅ CO ₂ C ₂ H ₅ , TiCl ₄ · ClCOC ₂ H ₅ , TiCl ₄ · C ₄ H ₄ O and the like can be mentioned.

Further, titanium compounds such as TiCl ₃ , TiBr ₃ , Ti (OC ₂ H ₅ ) Cl ₂ , TiCl ₂ , dicyclopentadienyl titanium dichloride can be used. TiCl ₃ can be obtained, for example, by reducing TiCl ₄ with hydrogen, metallic aluminum, or an organometallic compound. Among these titanium compounds, TiCl ₄ , Ti (OC ₄ H ₉ ) ₄ , Ti ( OC ₂ H ₅ ) Cl ₃ is preferable, and TiCl ₄ and Ti (OC ₄ H ₉ ) ₄ are particularly preferably used. Moreover, these titanium compounds may be used alone or in combination of two or more.

As the halogen source, in addition to using the halogen represented by X of Ti (OR ² ) _{4 -P} X _p described above, other halogen sources, for example, halogens such as Br ₂ , I ₂ and ICl ₃ , interhalogen compounds, Aluminum halides such as AlCl ₃ , AlBr ₃ , and AlI ₃ , boron halides such as BCl ₃ , BBr ₃ , and BI ₃ , silicon halides such as SiCl _4, and phosphorus halides such as PCl ₃ and PCl ₅ , Tungsten halides such as WCl ₆ , molybdenum halides such as MoCl _{5, and the} like. The halogen contained in the catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

  The electron donating compound (iii) used as necessary 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- Bis (methoxymethyl) fluorene, 2,3-dimethoxybutane, 1,2-dimethoxycyclopropane, 1,2-dimethoxycyclohexane, 2,2′-dimethoxydibenzyl, 2,2-dimethyl-1,3-dimethoxypropane 2,2-diethyl-1,3-dimethoxypropane, 2,2-diisoprotyl-1,3-dimethoxypropane, 2-t-butyl-2-methyl-1,3-dimethoxypropane, 2-isopropyl-2 -Isopentyl-1,3-dimethoxypropane Ethers and diethers such as methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoate Monocarboxylic acid esters such as octyl acid, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, dimethyl adipate, Diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, Diheptyl phosphate, dioctyl phthalate, dinonyl phthalate, didecyl phthalate, diethyl cyclohexane-1,2-dicarboxylate, diethyl 3,6-dimethyl-cyclohexane-1,2-dicarboxylate, 3,6-diisopropyl-cyclohexane- Diethyl 1,2-dicarboxylate, diethyl 1-cyclohexene-1,2-dicarboxylate, diethyl 4-cyclohexene-1,2-dicarboxylate, diethyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate, Dicarboxylic acid esters such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone and other ketones, acid halides such as phthalic dichloride, terephthalic dichloride, acetaldehyde, propionaldehyde, octyl aldehyde Aldehydes such as 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, methyl isocyanate And isocyanates such as ethyl isocyanate.
In addition, examples of the organosilicon compound containing a Si—O—C bond include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

  Among the above electron donating compounds, diethers, especially 2,2-disubstituted 1,3-dimethoxypropanes, alicyclic carboxylic esters, especially cyclohexane carboxylic diester, cyclohexene carboxylic diester, 3, 6 -Disubstituted cyclohexanecarboxylic acid diesters, substituted cyclohexenecarboxylic acid diesters, aliphatic carboxylic acid diesters, especially succinic acid diesters such as diethyl succinate, diisobutyl succinate, bis (2-ethylhexyl) succinate, diethyl maleate, maleic acid Maleic acid diesters such as diisopropyl and di-n-butyl maleate, Malonic acid diesters such as dimethyl malonate, diethyl malonate, dimethylethyl malonate and diisobutyl malonate, substituted succinic acid diesters, substituted Rainic acid diesters, substituted malonic acid diesters, aromatic dicarboxylic acid diesters, especially diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethyl phthalate (n -Butyl), dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate and the like are preferably used, and one or more of these may be used. used. In addition, said ester can also be used in combination of 2 or more type.

  The component (a1) can be prepared by bringing the magnesium compound, titanium halide compound and, if necessary, an electron donating compound into contact with each other, and this contact can be made without using a solvent or the like. However, considering the ease of operation, it is preferable to perform the treatment in the presence of an inert organic solvent.

  Examples of the inert organic solvent used for the preparation of the component (a1) include saturated hydrocarbon compounds such as hexane, heptane, and cyclohexane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene, orthodichlorobenzene, and chloride. Halogenated hydrocarbon compounds such as methylene, carbon tetrachloride, dichloroethane, and the like. Among these, aromatic hydrocarbon compounds in a liquid state at room temperature having a boiling point of about 90 to 150 ° C., specifically, toluene and xylene Ethylbenzene is preferably used.

  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 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 obtained, a temperature range of 40 to 130 ° C. is preferable because the reaction can be easily controlled, the reaction can proceed sufficiently, and evaporation of the solvent used can be suppressed. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer. When the above-mentioned specific magnesium compound is used as a carrier, it is necessary to prepare a solid catalyst component by contacting with a halogenated titanium compound and an electron donating compound while maintaining the particle characteristics as it is, and particularly diethoxymagnesium is used. In this case, when a halogenated titanium compound such as titanium tetrachloride is brought into contact at 0 ° C. or more, a rapid halogenation reaction proceeds, and the heat of reaction destroys the particles of diethoxymagnesium and atomizes them to primary particle units. Particularly in the contact reaction in the initial stage, it is necessary to pay attention to the contact conditions such as removing the heat of reaction and further cooling to 0 ° C. or lower.

  Preferred methods for preparing the component (a1) include the following methods. For example, a suspension is formed by suspending dialkoxymagnesium in an aromatic hydrocarbon compound that is liquid at room temperature such as toluene, and this suspension is then placed in titanium tetrachloride at a reaction temperature of −20. Add while maintaining a low temperature of ~ 20 ° C. The preferable temperature range at this time is -15-15 degreeC, More preferably, it is -15-10 degreeC. After completion of the addition, the aging reaction is carried out at a low temperature of -20 to 20 ° C. The preferable temperature range at this time is also -15-15 degreeC, More preferably, it is -15-10 degreeC. Thereafter, the temperature is raised and the reaction is carried out at 70 to 120 ° C. At this time, before or after contacting titanium tetrachloride with the above suspension, an electron donating compound such as phthalic acid diester is contacted at −20 to 130 ° C. to obtain a solid reaction product. After washing the solid reaction product with a liquid aromatic hydrocarbon compound at room temperature, titanium tetrachloride is added again in the presence of the aromatic hydrocarbon compound, and contact reaction is performed at 70 to 120 ° C., and further at room temperature. Wash with a liquid hydrocarbon compound to obtain a solid component. Furthermore, repeated contact with titanium tetrachloride is also a preferred embodiment for improving the activity of the catalyst.

  The amount ratio of each compound varies depending on the preparation method and cannot be defined unconditionally. For example, 0.5 to 100 mol, preferably 0.5 to 50 mol, of titanium halide compound per mol of magnesium compound Preferably it is 1-10 mol, and an electron-donating compound is 0.01-10 mol, Preferably it is 0.01-1 mol, More preferably, it is 0.02-0.6 mol.

  The component (a2) contained in the catalyst component for olefin polymerization of the present invention is a polyolefin that is soluble in an inert hydrocarbon solvent, particularly an inert hydrocarbon solvent of 70 ° C. or less. Polyolefins soluble in an inert hydrocarbon solvent at 70 ° C. or lower include all polyolefins as long as they exhibit the properties. Component (a2) is generally an ethylene-α olefin copolymer having a melting point of 110 ° C. or less, a crystalline propylene polymer having a melting point of 130 ° C. or less, a propylene-α olefin copolymer, an amorphous olefin type A polymer is mentioned. In addition, although the polypropylene obtained by conventional prepolymerization or normal polymerization has high stereoregularity and can be dissolved in a solvent such as xylene by heating to 130 ° C or higher, at 70 ° C or lower, It can hardly be dissolved in a solvent such as toluene.

  A polyolefin soluble in an inert hydrocarbon solvent at 70 ° C. or lower does not exclude that a part of the polyolefin insoluble in the inert hydrocarbon solvent at 70 ° C. or lower, but preferably at a temperature of 70 ° C. or lower. The solubility of the polyolefin per liter of the inert hydrocarbon solvent is 1 g or more, more preferably 5 g or more, and particularly preferably 10 g or more. Needless to say, polyolefins soluble at 70 ° C. or lower are soluble even at higher temperatures.

  Inert hydrocarbon solvents include hexane, heptane, octane, nonane, decane, dodecane, decalin and other aliphatic hydrocarbons, cyclohexane, methylcyclohexane, ethylcyclohexane and other alicyclic hydrocarbons, benzene, toluene, xylene, etc. It is an aromatic hydrocarbon. Of these, inert hydrocarbons having 7 to 10 carbon atoms such as heptane, octane, methylcyclohexane, toluene and xylene are preferable, and aromatic hydrocarbons such as toluene and xylene are particularly preferable.

  The molecular weight of the polyolefin of component (a2) is not particularly limited, but in the dry state from the ease of operation of allowing a predetermined amount to exist inside the particles of solid component (a1) while maintaining the particle properties of the solid catalyst component. The weight molecular weight is 500 or more and 100,000 or less, preferably 1000 or more and 100,000 or less, particularly preferably 1000 or more and 80,000 or less, which is solid or close to a solid.

  In the present invention, the soluble polyolefin (a2) is preferably present in an amount of 1% by weight or more in the solid catalyst component. The component (a2) is preferably 1% by weight or more and 50% by weight or less in the solid catalyst component from the viewpoint of preventing the adhesion of the solid catalyst components and obtaining the effect of suppressing the formation of fine particles. More preferably, the content is in the range of from 5% by weight to 35% by weight, and particularly preferably in the range of from 5% by weight to 25% by weight. As long as it contains a predetermined amount of soluble polyolefin as a main component and exhibits the effect of suppressing the formation of fine particles, a solid catalyst component partially containing insoluble polyolefin is not excluded as an additional component.

  When the polyolefin of component (a2) is a propylene polymer (polypropylene or a copolymer of propylene and another α-olefin), its stereoregularity is not particularly limited, but propylene measured by C13-NMR The mesotriad is preferably 0.6 or more, more preferably 0.6 or more and 0.99 or less, and particularly preferably 0.65 or more and 0.98 or less. By setting it within this range, the solubility in an inert hydrocarbon solvent is excellent, and the operation of allowing a predetermined amount of polyolefin to be present inside the solid component is facilitated while maintaining the particle properties of the solid catalyst component.

  The method for producing a polyolefin soluble in an inert hydrocarbon solvent of 70 ° C. or lower of the component (a2) is not particularly limited as long as it has the property. For example, a pulverized titanium trichloride catalyst component or a dissolved type A catalyst comprising a spherical titanium trichloride catalyst component and an organic aluminum halide; magnesium, titanium, a solid catalyst component containing halogen, an organoaluminum compound, and, if necessary, an olefin polymerization using a specific electron donating compound Catalyst: transition metal compound represented by metallocene complex and organoaluminum compound (cocatalyst component) capable of activating transition metal compound such as methylalumoxane, organoaluminum and Lewis acid, or organoaluminum compound and anionic compound, etc. Examples of known polyolefin synthesis methods using soluble complex catalysts combined with It is. Among these, the method using a soluble complex catalyst using a transition metal compound typified by a metallocene complex is preferable in that a highly homogeneous soluble polyolefin can be produced.

  As the soluble complex catalyst, a transition metal compound represented by the following general formula (3) or general formula (4) can be used.

_{Q m (C 5 H 5-} m-a R 3 a) (C 5 H 5-m-b R b 4) MeXY (3)
^{_{Q (C 5 H 4-a}} R 3 a) N (C n H p) MeXY (4)
(In the formula, Q represents a divalent linking group that bridges two conjugated five-membered ring ligands, Me represents a metal atom selected from titanium, zirconium, and hafnium, and X and Y represent a hydrogen atom, a halogen atom, An atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group is shown, and X and Y may be independently, that is, the same or different. R ³ and R ⁴ are hydrogen atoms, hydrocarbon groups, halogenated hydrocarbon groups, silicon-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups, oxygen-containing hydrocarbon groups, boron-containing hydrocarbon groups, or phosphorus-containing hydrocarbon groups. M represents 0 or 1, n represents the number of carbon atoms of the hydrocarbon residue bonded to the N atom, p corresponds to the number of hydrogen atoms of the hydrocarbon residue, and in the case of a chain saturated hydrocarbon, 2n + 1, for ring n-1, an integer decreased further by 2 if having an unsaturated bond, a and b are the number of substituents on the five-membered ring.)

  Examples of Q include a divalent hydrocarbon group, a silylene group, an oligosilylene group, or a silylene group or oligosilylene group having a hydrocarbon group as a substituent, or a germylene group having a hydrocarbon group as a substituent. Among these, preferred is a silylene group having a divalent hydrocarbon group and a hydrocarbon group as a substituent.

  X and Y are preferably a hydrogen atom, chlorine, bromine, iodine, methyl group, isobutyl group, phenyl group, benzyl group, dimethylamide group, diethylamide group or the like.

Specific examples of the hydrocarbon group in R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, and a butadienyl group. Is done. In addition, as halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing hydrocarbon group, boron-containing hydrocarbon group, or phosphorus-containing hydrocarbon group, methoxy group, ethoxy group, phenoxy group Typical examples include trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group, and dimethoxyboron group. In these, it is preferable that it is a C1-C20 hydrocarbon group, and it is especially preferable that they are a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. By the way, adjacent R ³ and R ⁴ may combine to form a ring, on which a hydrocarbon group, halogenated hydrocarbon group, silicon-containing hydrocarbon group, nitrogen-containing hydrocarbon group, oxygen-containing You may have a substituent which consists of a hydrocarbon group, a boron containing hydrocarbon group, or a phosphorus containing hydrocarbon group.

  Preferred examples of Me include zirconium and hafnium in the case of the general formula (3), and titanium and hafnium in the case of the general formula (4).

  Among the metallocene compounds described above, preferred for the production of the soluble polyolefin of the present invention is a substituted cyclopentadienyl group or substituted indenyl group crosslinked with a hydrocarbon-substituted silylene group, germylene group or alkylene group. A metallocene compound comprising a ligand having a substituted fluorenyl group or a substituted azulenyl group, and particularly preferably a substituted indenyl group crosslinked with an ethylene group, an isopropylidene group, a silylene group having a hydrocarbon substituent, or a germylene group. , A metallocene compound comprising a ligand having a substituted azulenyl group and a substituted fluorenyl group.

  Specific examples of the general formula (3) include dicyclopentadienylzirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, ethylenebisindenylzirconium dichloride, dimethylsilylene. Bis (indenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylenebis (2- Methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylenebis (2-methylbenzoindenyl) zirconium dichloride, dimethyl Lucylylene bis {2-isopropyl-4- (3,5-diisopropylphenyl) indenyl} zirconium dichloride, dimethylsilylene bis (2-isopropyl-4-phenanthrylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4- Phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-methyl-4- (4-chlorophenyl) azurenyl} zirconium dichloride, dimethylsilylenebis (2-ethyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis (2- Isopropyl-4-phenylazurenyl) zirconium dichloride, dimethylsilylenebis {2-ethyl-4- (2-fluorobiphenyl) azurenyl} zirconium dichloride, dimethylsilyle Bis {2-ethyl-4- (4-t-butyl-3-chlorophenyl) azurenyl} zirconium dichloride, dimethylsilylene (2-methylindenyl) (2-methylbenzoindenyl) zirconium dichloride, dimethylsilylene (2-methylazurenyl) ) (2-methylbenzoindenyl) zirconium dichloride, dimethylsilylene (2-methyl, 4-phenylindenyl) (2-methylbenzoindenyl) zirconium dichloride, dimethylsilylene (2-methyl-4-phenylazurenyl) (2 -Methylbenzoindenyl) zirconium dichloride, dimethylsilylene (2-methylindenyl) (2,7-dimethylfluorenyl) zirconium dichloride, dimethylsilylene (2-methylcyclopentadienyl) (2,7-dimethylfluorene) Nil) Di Benzalkonium dichloride and the like. A compound in which the silylene group of these specific examples is replaced with a germylene group and zirconium is replaced with hafnium is also exemplified as a suitable compound.

  Specific examples of the general formula (4) include dimethylsilylene (tetramethylcyclopentadienyl) t-butylamidotitanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) cyclohexylamidetitanium dichloride, and dimethylsilylene (2 -Methylindenyl) t-butylamido titanium dichloride, dimethylsilylene (fluorenyl) cyclohexylamido titanium dichloride,) diphenylsilylene (indenyl) t-butylamido titanium dichloride, dimethylsilylene (benzoindenyl) t-butylamido titanium dichloride, etc. The transition metal compound. In these compounds, compounds in which dichloride is substituted with an alkyl substituent such as dimethyl can also be used.

  Specific examples of organoaluminum compounds capable of activating transition metal compounds include trialkylaluminums such as methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum butylboronate tetraisobutyl, triethylaluminum, and triisobutylaluminum. , Triphenylborane, tris (3,5-difluorophenyl) borane, tris (pentafluorophenyl) borane, triphenylcarbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate An activatable organoaluminum compound in combination with clay minerals. These soluble catalysts can also be used in a state of being supported on a carrier material such as silica, alumina, silica alumina, and magnesium chloride.

  As a method for increasing the solubility of polyolefin, a method for controlling stereoregularity, specifically, a method for changing the structure of the soluble complex, a method for changing the polymerization temperature, a method for changing the polymerization pressure, an assistant such as organic aluminum, etc. Examples thereof include a method of changing the catalyst component and a method of adding an additional component. In addition to ethylene and propylene, which are main monomers, a method of copolymerizing with other α-olefins, specifically, ethylene and propylene, ethylene and 1-butene, 1-hexene, 1-octene and higher olefins such as Examples thereof include copolymerization, copolymerization of ethylene and butadiene, terpolymerization of these, and copolymerization with higher olefins such as propylene and ethylene, propylene and 1-butene, 1-hexene, and 1-octene. Moreover, the method of controlling molecular weight using chain transfer agents, such as organic metal compounds, such as hydrogen, organosilane, and diethyl zinc, is performed.

  As a method for quantifying the component (a2) in the solid catalyst component of the present invention, a known method can be applied. For example, the solid catalyst component is dispersed in an inert organic solvent, and soluble polyolefin is dissolved at a temperature of 70 ° C. or higher. The eluate is filtered, and the filtrate is collected and dried. The weight can be calculated from the weight (g) of the recovered soluble polyolefin and the weight (g) of the solid catalyst component used.

  In the case of a conventional solid catalyst component, for example, in the prepolymerized catalyst, when the polymer grows inside the solid catalyst during polymerization, the catalyst particles expand, the strength of the catalyst particles decreases, and polymer fine particles are generated. In addition, the solid catalyst component using the polymer as a carrier easily peels off the fine catalyst component from the surface of the particle due to collision of the catalyst particles during the polymerization, and the fine catalyst component is a source of polymer fine particles. Become. According to the solid catalyst component of the present invention, since the soluble polyolefin (a2) is deposited as liquid, semi-solid or solid particles inside the solid component particles containing magnesium, titanium and halogen atoms, the particle strength is high. improves. Accordingly, there is no reduction in strength due to such expansion of the catalyst particles and separation of fine catalyst components, and generation of polymer fine particles during polymerization can be suppressed. In the solid catalyst component of the present invention, the component (a2) is liquid, semi-solid on the particle surface of the solid component (a1) as long as the component (a2) is impregnated and deposited inside the particles of the solid component (a1). Alternatively, it may be deposited as solid particles.

  Next, the manufacturing method of the solid catalyst component of this invention is demonstrated. The solid catalyst component of the present invention is in contact with and mixed with a solubilized polyolefin and a solid component containing magnesium, titanium, and a halogen atom in an inert organic solvent, and impregnated with the solubilized polyolefin in solid component particles. A step of impregnating. Thereby, the solubilized polyolefin (a2) can be impregnated in the particles of the solid component (a1).

  Further, after the impregnation step, the inert organic solvent is removed, and a separation step of the solid catalyst component and the solvent is performed.

  In the impregnation step, as a method of contacting and mixing the component (a1) and the component (a2), for example, a mixture of the component (a1), the component (a2) and an inert solvent is heated as necessary, Method of continuing mixing until (a2) is dissolved in the solvent, component (a2) is previously dissolved in an inert solvent, component (a1) is added to this solution, and then heated as necessary to mix And a method of suspending the component (a1) in an inert solvent in advance, adding the component (a2) to the suspension, and then heating and mixing as necessary.

  In the separation step, as the method for removing the inert organic solvent, for example, a known drying method such as heat drying, drying under reduced pressure, drying under reduced pressure, airflow drying, spray drying, or the like can be used. Among these, vacuum drying or airflow drying while heating to a temperature of about 50 to 100 ° C. is preferable in that soluble polyolefin is easily deposited inside solid component particles. In this method, since the soluble polyolefin is deposited inside the solid component particles while removing the solvent, the solid component particles are preferably stirred and fluidized to the extent that the solid component particles do not adhere to each other during drying.

  As a method for removing the solvent, the solubilized component (a2) is impregnated in the particles of the component (a1), and then precipitated as solid polyolefin in the particles of the component (a1). And a method of separating the solvent from the solvent. Examples of the method for precipitating the component (a2) in the particles of the component (a1) include a method of cooling the temperature of the solvent to the crystallization temperature of the polyolefin or lower. Examples of the method for removing the solvent after the component (a2) is precipitated (deposited) in the component (a1) include methods such as filtration and sedimentation separation in addition to the above drying. In the separation step, the inert organic solvent may not be completely removed but may partially remain.

  As described in the solid catalyst component of the present invention, the solid catalyst component obtained by the production method of the present invention has a soluble polyolefin (a2) in the form of a solid component containing magnesium, titanium and a halogen atom. , Deposited as semi-solid or solid particles.

  The catalyst for olefin polymerization of the present invention comprises the above-described solid catalyst component (A), organoaluminum compound (B) (hereinafter sometimes referred to as “component (B)”), external electron donating compound component (C). (Hereinafter sometimes referred to as “component (C)”).

  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-isobutylaluminum, diethylaluminum bromide, and diethylaluminum halide, and one or more can be used. Triethylaluminum and tri-isobutylaluminum are preferable.

In addition to the above components, an external electron donating compound (C) can be used when forming the olefin polymerization catalyst of the present invention. As the external electron-donating compound, the same electron-donating compounds as those constituting the solid catalyst component described above are used. Among them, 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1 Ethers such as 1,3-dimethoxypropane, esters such as methyl benzoate and ethyl benzoate, and organosilicon compounds.
Among the above components (C), as the organosilicon compound, the following general formula (5);
R ⁵ _q Si (OR ⁶ ) _4-q (5)
(In the formula, R ⁵ represents 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, and R ⁶ has 1 to 4 carbon atoms. An alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, wherein R ⁵ and R ⁶ may be the same or different, and q is an integer of 0 ≦ q ≦ 3.) The compound represented by these is used. Examples of such an organosilicon compound include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

  Furthermore, specific examples of the organosilicon compounds are trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri-isobutylmethoxy. Silane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, di-n-propyldimethoxysilane, di-isopropyldimethoxysilane, di-n-propyldiethoxysilane, di-isopropyldiethoxysilane Di-n-butyldimethoxysilane, di-isobutyldimethoxysilane, 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, cyclohexylcyclopentyldi Ropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexyl Cyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (isopropyl) dimethoxysilane, cyclopentyl (isobutyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyl Dimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (isopropyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (isobutyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxy Silane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxy Silane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltrieth Sisilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxy Silane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane , Phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc. It can be mentioned. Among the above, di-n-propyldimethoxysilane, di-isopropyldimethoxysilane, di-n-butyldimethoxysilane, di-isobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t -Butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyl Dimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopente Rudimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used. These can be used in combination. Moreover, what used the amino group instead of said alkoxide as an organosilicon compound is illustrated. Specifically, cyclohexylmethylbismethylaminosilane, dicyclohexylbismethylaminosilane, dicyclopentylbismethylaminosilane, tert-butylmethylbismethylaminosilane, diisopropylbismethylaminosilane, cyclohexylmethylbisethylaminosilane, dicyclohexylbisethylaminosilane, dicyclopentylbisethyl Examples include aminosilane, tert-butylmethylbisethylaminosilane, diisopropylbisethylaminosilane, and the like.

The olefin polymerization catalyst of the present invention comprises the aforementioned component (A), component (B), and component (C), and performs polymerization or copolymerization of olefins in the presence of the catalyst. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene, propylene and 1-butene are preferably used, and ethylene and propylene are particularly preferable. The catalyst for olefin polymerization of the present invention is, in particular, ethylene homopolymerization, copolymerization of ethylene with α-olefin such as 1-butene, 1-hexene, 1-octene, propylene homopolymerization, propylene and other olefins. Suitable for copolymerization. Other olefins copolymerized with propylene include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like. These olefins are used alone or in combination of two or more. can do. In particular, ethylene and 1-butene are preferably used.
The use amount ratio of each component (A) to (C) is arbitrary as long as it does not affect the effects of the present invention, and is not particularly limited. Usually, the organoaluminum compound (B) is a solid. It is used in the range of 1 to 2000 mol, preferably 50 to 1000 mol, per 1 mol of titanium atom in the catalyst component (A). The external electron donating compound (C) is in the range of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per mol of the organoaluminum compound (B). Used.

  The order of contacting the components is arbitrary, but it is desirable to first introduce the organoaluminum compound into the polymerization system, then contact the external electron donating compound, and then contact the solid catalyst component.

  The polymerization method can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as ethylene and 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. In addition, either a continuous polymerization method or a batch polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Further, when the olefin is polymerized using the above catalyst (also referred to as main polymerization), prepolymerization is performed prior to the main polymerization in order to further improve the catalytic activity, stereoregularity, particle properties of the polymer to be formed, and the like. It is desirable. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used. In conducting the prepolymerization, the order of contacting each component and the monomer is arbitrary, but preferably, an organoaluminum compound is first charged into a prepolymerization system set to an inert gas atmosphere or a gas atmosphere for performing polymerization such as propylene. Then, after contacting the solid catalyst component, an olefin such as propylene and / or one or more other olefins are contacted.

  When prepolymerization is performed by combining an external electron-donating compound component such as an organosilicon compound, an organoaluminum compound is first charged into a prepolymerization system set to an inert gas atmosphere or a gas atmosphere for polymerization of propylene. Then, after contacting the organosilicon compound and further contacting the solid catalyst component, a method of contacting an olefin such as propylene and / or one or other two or more olefins 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. To polymerize the rubber part ratio to 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 an inert hydrocarbon solvent 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. . Preferred polymerization methods are bulk polymerization and gas phase polymerization.

(Example)
EXAMPLES Next, the present invention will be described more specifically with reference to examples, but this is merely illustrative and does not limit the present invention. The characteristics of the magnesium compound and the solid catalyst component were evaluated by the following methods.

<Measurement method of specific surface area (N ₂ SA)>
The specific surface area and pore distribution were automatically measured using the BET method with an Automatic Surface Area Analyzer HM model-1230 manufactured by Mountaintech. The measurement sample was previously vacuum dried at 50 ° C. for 2 hours, and a mixed gas of nitrogen and helium was used for the measurement.

<Measurement method of sphericity (l / w)>
The sphericity of the magnesium compound was automatically measured by a Particle Size Distribution Analysis Software Mac-View manufactured by Mounttech.

<Method for measuring particle diameter and particle size distribution>
The particle size and particle size distribution of the magnesium compound, solid component, and catalyst particles were measured using a laser light scattering diffraction particle size analyzer (MICROTRAC-HRA) manufactured by Nikkiso Co., Ltd. From the particle size distribution of volume statistic values obtained by automatic measurement, charged in a solvent so as to be included in the optimum range indicated by the device in the range of 05 g to 0.20 g, integrated 10% particle size (D10), integrated 90% particle The diameter (D90) and the average particle diameter (D50) were determined, and the particle size distribution index (SPAN) was calculated by the following formula.
Particle size distribution index (SPAN) = (D90−D10) / D50

<Titanium content in catalyst component>
The titanium content in the catalyst component was measured according to the method of JIS M 8301.

<Soluble polyolefin content in solid catalyst component>
The soluble polyolefin content in the solid catalyst component was obtained by dispersing 5.0 g of the solid catalyst component from which the remaining inert organic solvent had been completely removed in 20 ml of toluene and stirring the mixture at 80 ° C. for 2 hours to elute the soluble polyolefin. The solution was filtered while maintaining a liquid temperature of 70 ° C. or higher, a certain amount of filtrate was collected and dried, and the total weight (g) of the soluble polyolefin obtained from the weight of the recovered soluble polyolefin and the solid catalyst component used. From the weight (g), it was calculated by the following formula.
Soluble polyolefin content (wt%) =
[Total weight of soluble polyolefin (g) × 100] / [Weight of solid catalyst component (g)]

Each characteristic of the polymer was evaluated by the following methods.
<Method for calculating polymerization activity>
The polymerization activity per gram of the solid catalyst component was calculated by the following formula.
Polymerization activity (g-pp / g-cat) = product polymer (g) / solid catalyst component (g)

<Method for measuring xylene solubles (XS)>
The xylene-soluble matter (XS) of the produced polymer was charged with 4.0 g of this produced polymer and 200 ml of p-xylene in a 500 ml flask equipped with a reflux apparatus and a stirrer, and the external temperature was higher than the boiling point of xylene. (About 150 ° C.), while maintaining the temperature of p-xylene at the boiling point (137 to 138 ° C.), the mixture was refluxed for 2 hours with stirring to completely dissolve the polymer, then at 23 ° C. After holding for 1 hour and separating the insoluble component and the dissolved component by filtration, a certain amount of the above solution is collected, p-xylene is distilled off by heating under reduced pressure, and the resulting residue is dissolved in the xylene-soluble component. (XS), and the weight was determined as a relative value (% by weight) to the produced polymer.

<Melt flow rate (MFR) measurement method>
The melt flow rate (MFR) value of the produced polymer was measured according to the methods of ASTM D1238 and JIS K 7210.

<Method for Measuring Particle Size Distribution of Generated Solid Polymer>
The average particle size, particle size distribution index and fine powder amount of 106 μm or less of the produced solid polymer were measured according to JIS K0069, the particle size distribution and the fine powder amount of 106 μm or less. Thereafter, the particle size corresponding to 10%, 50%, and 90% by weight was obtained from the particle size distribution, and the particle size distribution index (SPAN) was calculated by the following formula.
Particle size distribution index (SPAN) = (D90−D10) / D50
D90: 90% particle size (μm) in the cumulative particle size distribution in the weight cumulative particle size distribution
D50: 50% of the particle size (μm) in the integrated particle size distribution in the weight integrated particle size distribution
D10: 10% particle diameter (μm) in the integrated particle size distribution in the weight integrated particle size distribution

  The amount of fine powder of 45 μm or less of the produced solid polymer can be obtained by flowing ethanol through the produced polymer placed on a 330 mesh sieve and centrifuging the ethanol suspension containing the fine particles that have passed through the sieve (PP The fine particles were collected and further dried under reduced pressure. Then, the dry weight was measured, and the dry weight (g) was divided by the amount of polymer produced (g) used for the measurement.

<Measuring method of 13C-NMR propylene mesotriad fraction PPP (mm)>
The propylene mesotriad fraction of the propylene-based polymer is the ratio in which the direction of the methyl branch is the same when any three head-to-tail bonded propylene unit chains in the polymer chain are expressed in a planar zigzag structure. And was determined from the ¹³ C-NMR spectrum by the following formula.

  The chemical shift was set such that the methyl group of the third unit of the 5-chain propylene unit having a head-to-tail bond was 21.593 ppm, and the chemical shifts of other carbon peaks were based on this.

  The peak region was classified into a first region (21.1 to 21.9 ppm), a second region (20.3 to 21.0 ppm), and a third region (19.5 to 20.3 ppm). In the first region, the methyl group of the second unit in the three propylene unit chains represented by PPP (mm) resonates.

  In the second region, the methyl group of the second unit of the three-chain propylene unit represented by PPP (mr) and the methyl group of the propylene unit (PPE-methyl group) in which the adjacent unit is a propylene unit and an ethylene unit are resonant. To do.

  In the third region, the methyl group of the second unit of the three propylene units chain represented by PPP (rr) and the methyl group of the propylene unit whose adjacent units are all ethylene units (EPE-methyl group) resonate. .

In addition, the ¹³ C-NMR spectrum of the produced polymer was measured under the following conditions using JNM-ECA400 manufactured by JEOL.
<13C-NMR measurement conditions>
Measurement mode: Proton decoupling method
Pulse width: 7.25 μsec
Pulse repetition time: 7.4 sec
Integration count: 10,000 times
Solvent: Tetrachloroethane-d2
Sample concentration: 200 mg / 3.0 ml

<Measuring method of melting point>
The temperature at the position of the maximum peak in the endothermic curve of differential scanning calorimetry (DSC) was defined as the melting point (Tm) of the polymer. In the measurement, the sample was packed in an aluminum pan, heated to 250 ° C. at 10 ° C./min by differential scanning calorimetry (DSC) (manufactured by SII, EXSTAR 6000), held at 250 ° C. for 20 minutes, then 5 ° C. / The endothermic curve when the temperature was lowered to 20 ° C. in minutes and then raised at 10 ° C./minute was measured, and the temperature at the position of the maximum peak in the endothermic curve was defined as the melting point (Tm) of the polymer.

<Method of measuring mass average molecular weight (Mw) and number average molecular weight (Mn)>
The mass average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC) (manufactured by GPCV2000 Waters) to determine the molecular weight distribution (Mw / Mn). As a column, three UT-806M (manufactured by Shodex) and one HT-803 (manufactured by Shodex) were used, and a sample having a concentration of 1 mg / 1 mL was introduced at 140 ° C. using o-dichlorobenzene as a solvent. Measurements were made. A calibration curve was prepared using standard polystyrene manufactured by Shodex.

Production Example 1
<Preparation of solid component (C-1)>
A 200 ml round bottom flask equipped with a stirrer and fully substituted with nitrogen gas has a bulk specific gravity of 0.31 g / ml, a specific surface area of 19.8 m ² / g, a sphericity (l / w) of 1.10, and an average particle size. A suspension was formed by charging 20 g of diethoxymagnesium having a diameter of 25 μm and a particle size distribution index SPAN [(D90-D10) / D50] of 1.05 and 100 ml of toluene. Next, a suspension of the suspension in the mixed solution in which 40 ml of titanium tetrachloride and 60 ml of toluene were previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and the liquid temperature was kept at 10 ° C. The liquid was added. Thereafter, 7.2 ml of di-n-butyl phthalate was added while maintaining the liquid temperature at 10 ° C., then the liquid temperature was raised from 10 ° C. to 90 ° C. over 80 minutes, and the reaction was allowed to proceed with stirring for 2 hours. It was. After completion of the reaction, the obtained solid product was washed 4 times with 200 ml of toluene at 90 ° C., 60 ml of titanium tetrachloride and 140 ml of toluene were newly added, and then the temperature was raised to 112 ° C. and reacted with stirring for 2 hours. . After completion of the reaction, it was washed 10 times with 200 ml of n-heptane at 40 ° C. to obtain a solid component. After the above operation was performed twice in total, all the obtained solid components were mixed to obtain a solid component (C-1). The titanium content in the obtained solid component (C-1) was measured and found to be 2.86% by weight. The average particle size and particle size distribution index of the solid component (C-1) were also evaluated. The results are shown in Table 1.

Production Example 2
<Preparation of solid component (C-2)>
Bulk specific gravity 0.35 g / ml, specific surface area (N ₂ SA) 17.5 m ² / g, sphericity (l / w) 1.05, average particle size 41 μm, particle size distribution index SPAN [(D90-D10) / D50 The solid component (C-2) was produced and evaluated in the same manner as in Production Example 1 except that diethoxymagnesium of 0.95 was used. The results are shown in Table 1.

Production Example 3
<Preparation of solid component (C-3)>
A round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas having a volume of 200 ml was filled with a bulk specific gravity of 0.35 g / ml, a specific surface area (N ₂ SA) of 17.5 m ² / g, and a sphericity (l / w) 1.05, average particle size 41 μm, particle size distribution [(D90-D10) / D50] 0.95 diethoxymagnesium 20 g, toluene 100 ml and di-n-butyl phthalate 7.2 ml It became cloudy. The suspension was then continuously added over 1 hour in a solution of 60 ml toluene and 40 ml titanium tetrachloride pre-charged in a 500 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. Added to. At that time, the temperature of the reaction system was kept at -5 ° C. The mixture was stirred for 1 hour while maintaining at −5 ° C., then heated to 100 ° C. over 4 hours, and reacted for 2 hours with stirring. After completion of the reaction, the obtained solid product was washed four times with 200 ml of toluene at 90 ° C., 40 ml of titanium tetrachloride and 160 ml of toluene were newly added, and then the temperature was raised to 100 ° C. and reacted with stirring for 2 hours. . Subsequently, the product was washed 7 times with 200 ml of heptane at 40 ° C., filtered and dried to obtain a powdery solid component. After the above operation was performed twice in total, all the obtained solid components were mixed to obtain a solid component (C-3). The solid content was evaluated for titanium content, average particle size, and particle size distribution index. The results are shown in Table 1.

Production Example 4
<Production of soluble polyolefin component (D-1)>
750 ml of dehydrated and deoxygenated toluene was introduced into an autoclave with a stirrer having an internal volume of 2 liters, and 3 mmol of methylalumoxane and 0.3 μmol of ethylenebistetrahydroindenylzirconium dichloride were introduced under a 20 ° C. propylene atmosphere. The polymerization temperature was set to 70 ° C. and the propylene pressure was 0.5 MPa, and slurry polymerization was carried out for 1 hour. After polymerization, after purging propylene, the slurry was transferred to a 1 L eggplant-shaped flask, and toluene was distilled off at 70 ° C. with an evaporator. As a result, 41 g of propylene polymer was obtained, and the weight molecular weight of the polymer component (D-1) Mw, quantity molecular weight Mn, molecular weight distribution Mw / Mn, melting point and propylene mesotriad were evaluated. The results are shown in Table 2. Further, 5 g of this polyolefin was charged into a flask equipped with a stirrer together with 200 ml of toluene, and stirred at 70 ° C. for 60 minutes under atmospheric pressure. As a result, all the polymers were dissolved.

Production Example 5
<Production of soluble polyolefin component (D-2)>
Into an autoclave equipped with a stirrer with an internal volume of 2 liters, 750 ml of dehydrated and deoxygenated toluene was introduced. Next, after setting the polymerization temperature to 40 ° C. and the propylene pressure to 0.5 MPa, and further adding 0.03 MPa of ethylene, continuously feeding propylene at 70 cc / min and ethylene at 5 cc / min. Slurry polymerization was carried out for 1 hour. After polymerization, after purging propylene and ethylene, the slurry was transferred to a 1 L eggplant-shaped flask, and toluene was distilled off at 70 ° C. with an evaporator. As a result, 50 g of propylene-ethylene copolymer component (D-2) was obtained, The polymer component was evaluated in the same manner as in Production Example 4. The results are shown in Table 2. In addition, as a result of dissolving 5 g of the present polyolefin component in toluene by the same method as in Production Example 4, all the polymers were dissolved.

Production Example 6
<Manufacture of soluble polyolefin component (D-3)>
700 ml of dehydrated and deoxygenated toluene and 50 ml of 1-hexene were introduced into an autoclave equipped with a stirrer with an internal volume of 2 liters, and 1 mmol of triethylaluminum, triphenylcarbinium tetrakispentafluorophenylborate, 0. 01 mmol, 1 micromol of commercially available dimethylsilylenebis (tetramethylcyclopentadienyl) t-butylamidotitanium dichloride was introduced, then the polymerization temperature was set to 90 ° C., ethylene pressure 0.7 MPa, and 1 L of hydrogen was added. Slurry polymerization was carried out for 0.5 hours. After polymerization, after purging ethylene, the slurry was transferred to a 2 L container, 500 ml of ethanol was added to precipitate the polymer, and the polymer and the solvent were separated by filtration. As a result of drying at 70 ° C. overnight, 45 g of an ethylene-hexene copolymer polymer component (D-3) was obtained, and the polymer component was evaluated in the same manner as in Production Example 4. The results are shown in Table 2. In addition, as a result of dissolving 5 g of the present polyolefin component in toluene by the same method as in Production Example 4, all the polymers were dissolved.

Example 1
<Manufacture of solid catalyst component>
10 g of the component (C-1) produced in Production Example 1 and 40 ml of toluene and 1 g of the soluble polyolefin component (D-1) obtained in Production Example 4 were introduced into a nitrogen-substituted eggplant-shaped flask with a three-way cock, and 70 ° C. The temperature was maintained at 70 ° C. for 30 minutes with stirring. Component (D-1) was completely dissolved in toluene. Next, after connecting to the evaporator, the eggplant-shaped flask is immersed in an oil bath maintained at 70 ° C., the pressure is reduced to 15,000 Pa using a vacuum pump, and the contents are flowed at a rotational speed of 100 rpm, and dried for 1 hour. went. 11.4 g of a powdery solid catalyst component (1) impregnated with the component (D-1) in the particles of the component (C-1) is recovered, and depending on the observation of the solid catalyst component in the flask by visual observation, agglomeration may occur. No lumps were detected. In this solid catalyst component, 5.0 wt% of toluene remained. The titanium content of this solid catalyst component was 2.63 wt%, and 8 wt% of soluble polyolefin was contained. When the particle size distribution of the solid catalyst component was measured, the average particle size was 25.2 μm and the particle size distribution [(D90-D10) / D50] was 0.85.

  Further, when the surface and the cross section of the solid catalyst component were observed with a scanning electron microscope (Field Emission Scanning Electron Microscope JSM-7500F manufactured by JEOL Ltd.), the component (D-1) was deposited in the voids inside the particles. It was confirmed that a small amount was deposited on the surface of the solid catalyst particles.

<Formation of polymerization catalyst and evaluation of polymerization>
An autoclave with a stirrer with an internal volume of 2 liters, completely replaced with nitrogen gas, was charged with 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and 0.0033 mmol of the solid catalyst component as titanium atoms. A polymerization catalyst was formed. Thereafter, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, and a polymerization reaction was performed at 70 ° C. for 1 hour. About the obtained solid polymer, polymerization activity per 1 g of the solid catalyst component, xylene-soluble content (XS), MFR, bulk specific gravity, average particle size, particle size distribution [(D90-D10) / D50], fine powder content As an index, evaluation was made on the weight% of fine powder of 106 μm or less and the weight% of fine powder of 45 μm or less. The results are shown in Table 3.

Comparative Example 1
A polymerization catalyst was formed and evaluated for polymerization under the same conditions as in Example 1 except that the component (C-1) was used in place of the solid catalyst component (1). That is, Comparative Example 1 uses the solid component (C-1) as a solid catalyst component. The results are shown in Table 3.

Example 2
<Production of solid catalyst component (2)>
For olefin polymerization in the same manner as in Example 1 except that the soluble propylene-ethylene copolymer component (D-2) produced in Production Example 5 was used instead of the soluble polyolefin component (D-1). 11.8 g of solid catalyst component (2) was produced. In the solid catalyst component, 5.5 wt% of toluene remained. The titanium content of the solid catalyst component (2) was 2.46 wt%, and the soluble polyolefin was 14 wt%.

<Formation and polymerization of polymerization catalyst>
A polymerization catalyst was formed and evaluated for polymerization under the same conditions as in Example 1, except that the solid catalyst component (2) was used instead of the solid catalyst component (1). The results are shown in Table 1.

Example 3
<Manufacture of solid catalyst component>
Instead of 10 g of the component (C-1), 10 g of the solid component (C-2) obtained in Production Example 2 was used, and instead of 1.0 g of the component (D-1), 3.0 g of the component (D-2) A solid catalyst component (3) was synthesized under the same conditions as in Example 1 except that. The results are shown in Table 3. When the particle size distribution of the solid catalyst component was measured, the average particle size was 40.8 μm and SPAN was 0.84. Moreover, when the particle | grain surface and cross section of the solid catalyst component were observed with the same apparatus as Example 1, it has confirmed that the component (D-2) deposited in the particle | grain inside and particle | grain surface. As a result of observing the agglomerates in the same manner as in Example 1 for the obtained solid catalyst particles, no agglomerates were detected.

<Formation and polymerization of polymerization catalyst>
The polymerization reaction and catalyst performance were evaluated under the same conditions as in Example 1 except that the solid catalyst component (3) was used instead of the solid catalyst component (1). The results are shown in Table 3.

Example 4
<Manufacture of solid catalyst component>
A solid catalyst component (4) was prepared under the same conditions as in Example 3 except that 6 g of the component (D-2) was used instead of 3 g of the component (D-2). The results are shown in Table 3.

<Formation and polymerization of polymerization catalyst>
The polymerization reaction and catalyst performance were evaluated under the same conditions as in Example 1 except that the solid catalyst component (4) was used instead of the solid catalyst component (1). The results are shown in Table 3.

Example 5
<Manufacture of solid catalyst component>
A solid catalyst component (5) was produced in the same manner as in Example 3 except that 1 g of the component (D-3) produced in Production Example 6 was used instead of 3 g of the component (D-2). The results are shown in Table 3.

<Formation and polymerization of polymerization catalyst>
The polymerization reaction and catalyst performance were evaluated under the same conditions as in Example 1 except that the solid catalyst component (5) was used instead of the solid catalyst component (1). The results are shown in Table 3.

Example 6
<Manufacture of solid catalyst component>
A solid catalyst component (6) was produced under the same conditions as in Example 1 except that 10 g of the solid component (C-3) obtained in Production Example 3 was used instead of 10 g of the component (C-1). The results are shown in Table 3.

<Formation and polymerization of polymerization catalyst>
The polymerization reaction and catalyst performance were evaluated under the same conditions as in Example 1 except that the solid catalyst component (6) was used instead of the solid catalyst component (1). The results are shown in Table 3.
Comparative Examples 2-3

<Formation and polymerization of polymerization catalyst>
A polymerization catalyst was formed and evaluated under the same conditions as in Example 1 except that the solid component (C-2) obtained in Production Example 2 was used instead of the solid catalyst component (1) (Comparison) Example 2). Moreover, it replaced with the solid catalyst component (1), and formed the polymerization catalyst and superposition | polymerization evaluation on the conditions similar to Example 1 except having used the solid component (C-3) obtained by manufacture example 3. (Comparative Example 3). That is, Comparative Example 2 uses the solid component (C-2), and Comparative Example 3 uses the solid component (C-3) as the solid catalyst component. The results are shown in Table 3.

Comparative Example 4
<Manufacture of solid catalyst component>
A solid catalyst component (7) was produced under the same conditions as in Example 1, except that 2 g of the polymer obtained in Comparative Example 1 was used instead of 1 g of Component (D-1). The polymer obtained in Comparative Example 1 had a molecular weight Mw = 170,000, Mn = 36,000, Mw / Mn = 4.72, and a melting point of 161.7 ° C. Further, when 5 g of the polymer obtained in Comparative Example 1 was dissolved in toluene by the same method as in Production Example 4, the polymer remained granular. That is, the PP particles remained as other particles in the catalyst as they were, and some of the solid components adhered to the PP particles and were agglomerated. As a result of separating only solids estimated as solid catalyst components and measuring the contents of titanium and soluble polyolefin, the titanium content was 2.84 wt% and the soluble polyolefin component was contained by 0.7 wt%. Further, 3.0 wt% of toluene remained in the solid catalyst component.

<Formation and polymerization of polymerization catalyst>
The polymerization reaction and catalyst performance were evaluated under the same conditions as in Example 1 except that the solid catalyst component (7) was used instead of the solid catalyst component (1). The results are shown in Table 3.

Example 7
<Manufacture of solid catalyst component>
Instead of 10 g of component (C-1), 10 g of the solid component (C-3) produced in Production Example 3 was used, and instead of 1 g of Component (D-1), Component (D-3) produced in Production Example 6 was used. The solid catalyst component (8) was produced under the same conditions as in Example 1 except that 4 g) was used. The results are shown in Table 3.

<Formation of polymerization catalyst and ethylene polymerization>
A stainless steel autoclave with a stirrer with an internal volume of 1.8 liters, sufficiently substituted with nitrogen gas, was charged with 700 ml of n-heptane and maintained at an ethylene gas atmosphere, and 0.88 mmol of triethylaluminum at 20 ° C. Then, 0.0088 mmol of the solid catalyst component (8) as a titanium atom was charged to form a polymerization catalyst. Thereafter, the temperature was raised to 80 ° C., hydrogen was charged to 0.4 MPa, then ethylene was supplied so that the pressure in the system became 0.9 MPa, and polymerization was continued at 80 ° C. for 2 hours.

In addition, the pressure which falls as superposition | polymerization progressed was supplemented by supplying ethylene gas continuously, and the constant pressure was maintained during superposition | polymerization. After the polymerization of ethylene according to the above polymerization method, the produced polymer was separated by filtration and dried under reduced pressure to obtain a solid polymer. On the other hand, the filtrate was condensed to obtain a polymer dissolved in the polymerization solvent.
About the obtained solid polymer, bulk specific gravity, average particle diameter, particle size distribution [(D90-D10) / D50], evaluation of weight percentage of fine powder of 106 μm or less and weight percentage of fine powder of 45 μm or less as an index of fine powder content rate Was done. The results are shown in Table 3.

Comparative Example 5
<Formation and polymerization of polymerization catalyst>
A polymerization catalyst was formed and evaluated for polymerization under the same conditions as in Example 7 except that the solid component (C-3) obtained in Production Example 3 was used instead of the solid catalyst component (8). The results are shown in Table 3.

Claims (10)

  A solid catalyst component for olefin polymerization, comprising a polyolefin soluble in magnesium, titanium, a halogen atom and an inert hydrocarbon solvent.   2. The solid catalyst component for olefin polymerization according to claim 1, wherein the polyolefin is soluble in an inert hydrocarbon solvent at a temperature of 70 [deg.] C. or less.   The solid catalyst component for olefin polymerization according to claim 1 or 2, wherein the polyolefin has a weight average molecular weight of 500 or more and 100,000 or less.   4. The solid catalyst component for olefin polymerization according to claim 1, wherein the content of the polyolefin is 1 to 50% by weight in the solid catalyst component for olefin polymerization.   The solid catalyst component for olefin polymerization according to any one of claims 1 to 3, further comprising an electron donating compound.   It has an impregnation step in which a polyolefin dissolved in an inert organic solvent is brought into contact with and mixed with a solid component containing magnesium, titanium, and a halogen atom to impregnate the solid component particles with the solubilized polyolefin. A method for producing a solid catalyst component for olefin polymerization.   7. The method for producing a solid catalyst component for olefin polymerization according to claim 6, wherein after the impregnation step, the inert organic solvent is removed and a separation step of the solid catalyst component and the solvent is performed. The solid catalyst component (A) for olefin polymerization according to any one of claims 1 to 5, and 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 an integer of 0 <p ≦ 3) (B The catalyst for olefin polymerization characterized by the above-mentioned. The solid catalyst component according to any one of claims 1 to 5 (A), 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 an integer of 0 <p ≦ 3) (B And an external electron donating compound (C).   A method for producing a polyolefin, wherein the solid catalyst for olefin polymerization according to claim 8 or 9 is used.