JP2006199739A - Solid catalyst component and catalyst for polymerization of olefins and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid catalyst component for the polymerization of olefins which is prepared in a simple step and comes to a component of a catalyst for the polymerization of olefins capable of highly maintaining the steroregularity of a polymer and the yield in the polymerization of an olefin, and furthermore capable of obtaining a polymer having a reduced amount of fine powders, a catalyst, and a method for producing olefin polymers using the catalyst. <P>SOLUTION: The solid catalyst component for the polymerization of olefins is obtained by bringing a magnesium compound (a), a tetravalent titanium halide compound (b), and an electron-donating compound (c) into contact with one another in the presence of a mixed solvent of an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound, and the catalyst contains the same. The method for producing olefin polymers uses this catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides a solid catalyst component and a catalyst for olefin polymerization, which can maintain a high degree of stereoregularity and yield of the polymer, and can obtain a polymer with less fine powder, and an olefin polymer using the same. It relates to the manufacturing method.

  Conventionally, in the polymerization of olefins, olefins are present in the presence of a solid catalyst component containing magnesium, titanium, an electron donating compound, and halogen as essential components, an organoaluminum compound and an organosilicon compound. Many olefin polymerization methods for polymerizing or copolymerizing olefins have been proposed.

  For example, Patent Document 1 (Japanese Patent Laid-Open No. 57-63310) and Patent Document 2 (Japanese Patent Laid-Open No. 57-63311) disclose a solid catalyst component containing a magnesium compound, a titanium compound and an electron donor, and an organic compound. There has been proposed a method of polymerizing an olefin having 3 or more carbon atoms using a catalyst comprising a combination of an aluminum compound and an organosilicon compound having a Si—O—C bond. However, these methods are not always satisfactory to obtain a highly stereoregular polymer in a high yield, and further improvement has been desired.

  On the other hand, in Patent Document 3 (Japanese Patent Laid-Open No. 63-3010), a product obtained by contacting dialkoxymagnesium, aromatic dicarboxylic acid diester, aromatic hydrocarbon and titanium halogen compound is heated in a powder state. A solid catalyst component prepared by doing so, a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound, and a method for polymerizing olefins in the presence of the catalyst have been proposed.

  Moreover, in patent document 4 (Unexamined-Japanese-Patent No. 1-315406), titanium tetrachloride is made to contact the suspension formed with diethoxymagnesium and alkylbenzene, and it is made to react by adding phthalic acid dichloride then. A solid catalyst component prepared by obtaining a solid product and further contacting the solid product with titanium tetrachloride in the presence of an alkylbenzene; and a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound; A method for polymerizing olefins in the presence of the catalyst has been proposed.

  Furthermore, in Patent Document 5 (Japanese Patent Laid-Open No. 2-84404), a solid titanium catalyst component, an organoaluminum compound, containing magnesium, titanium and halogen as essential components produced by bringing a magnesium compound into contact with a titanium compound. Olefin polymerization catalyst formed from catalyst component and organosilicon compound catalyst component containing cyclopentyl group, cyclopentenyl group, cyclopentadienyl group or derivatives thereof, and olefin for polymerizing or copolymerizing olefin in the presence of the catalyst A polymerization method has been proposed.

  Each of the above prior arts has a high activity capable of omitting the so-called demineralization step for removing catalyst residues such as chlorine and titanium remaining in the produced polymer, and also has a stereoregularity weight. The focus is on improving the yield of coalescence and increasing the sustainability of the catalytic activity during polymerization, each with excellent results. However, when polymerization of olefins is carried out using a polymerization catalyst having a composition comprising this type of highly active catalyst component and an electron donating compound typified by an organoaluminum compound and a silicon compound, the solid catalyst component itself is finely divided. In addition, due to particle destruction due to reaction heat at the time of polymerization, a large amount of fine powder was contained in the produced polymer, and the particle size distribution tended to be broadened. 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 a method for solving this problem, in Patent Document 6 (Japanese Patent Laid-Open No. 6-157659), a spherical dialkoxymagnesium, an aromatic hydrocarbon compound, and phthalate are added to a mixed solution of an aromatic hydrocarbon compound and titanium tetrachloride. A catalyst for olefin polymerization using a solid catalyst component obtained by adding a suspension of an acid diester, reacting it, and further reacting with titanium tetrachloride has been proposed.

  In Patent Document 7 (JP-A-6-287225), a suspension of a spherical dialkoxymagnesium, an aromatic hydrocarbon compound and a phthalic diester is mixed with an aromatic hydrocarbon compound and titanium tetrachloride. Olefin compounds obtained by adding to the solution and reacting, washing the resulting reaction product with an aromatic hydrocarbon compound, drying the solid component obtained by reacting again with titanium tetrachloride, and subjecting to a fine powder removal process Solid catalyst components for polymerization have been proposed.

  Further, in Patent Document 8 (Japanese Patent Application Laid-Open No. 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 above, the reaction product obtained is washed with an aromatic hydrocarbon compound, the solid component obtained by reacting again with titanium tetrachloride is dried, subjected to fine powder removal treatment, and then powdered. A solid catalyst component for polymerizing olefins obtained through a treatment process of adding a nonionic surfactant has been proposed.

  On the other hand, as a conventional technique, there is known a method of preparing a solid catalyst component by dissolving a magnesium compound such as magnesium chloride or diethoxymagnesium with an alkoxytitanium compound to form a uniform solution and then depositing it.

  For example, in Patent Document 9 (Japanese Patent Laid-Open No. 62-18405), a titanium alkoxy compound, dialkoxymagnesium, a diester of an aromatic dicarboxylic acid, a halogenated hydrocarbon compound, and a titanium halide represented by a specific formula are contacted. A catalyst component for polymerization of olefins, which is obtained by the above process and used in combination with a silicon compound and an organoaluminum compound represented by a specific formula, has been proposed.

  In Patent Document 10 (Japanese Patent Laid-Open No. 3-72503), a magnesium compound represented by a specific formula, a tetraalkyltitanium compound, and a silicon compound represented by a specific formula are subjected to a heat reaction, and then the reaction product. A solid catalyst component for polymerizing olefins obtained by treating with a halogen-containing titanium compound represented by the specific formula and an electron donating compound represented by the specific formula is disclosed.

  However, any of these conventional methods is a preparation method in which a magnesium compound is dissolved with an alkoxytitanium compound and then a solid catalyst component is precipitated, so that the process of depositing a solid from a solution of the magnesium compound is complicated. In addition, since a large amount of the alkoxytitanium compound is used in the method for preparing the solid catalyst component, there is a problem in that the alkoxytitanium compound remains in the precipitated solid, and the performance such as activity is significantly reduced.

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-A-57-63310 (Claims) JP-A-57-63311 (Claims) JP 63-3010 A (Claims) JP-A-1-315406 (Claims) JP-A-2-84404 (Claims) JP-A-6-157659 (Claims) JP-A-6-287225 (Claims) JP-A-6-287217 (Claims) JP-A-62-18405 (Claims) Japanese Patent Laid-Open No. 3-72503 (Claims)

  That is, the object of the present invention is to prepare olefins that can be prepared in a non-complex process and can maintain a high degree of polymer stereoregularity and yield when subjected to polymerization of olefins, and also can obtain a polymer with less fine powder. An object of the present invention is to provide a solid catalyst component for polymerization of olefins and a catalyst which are components of a polymerization catalyst, and a method for producing an olefin polymer using the same.

  Under such circumstances, the present inventors have made extensive studies and obtained the magnesium compound, titanium compound, and electron donating compound in contact with each other in a mixed solvent of an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound. It was found that the obtained solid catalyst component can maintain a high degree of polymer stereoregularity and yield as compared with the above-mentioned conventional catalyst, and obtain a polymer with less fine powder, and has completed the present invention. Although it has been conventionally known that aromatic hydrocarbons and aliphatic hydrocarbons can be used, the effect obtained by mixing them has not been known, but the present inventors are surprisingly complicated. The present inventors have found that the effect of the solid catalyst component can be improved by using a specific mixed solvent without adding an additional step and without using a highly toxic compound.

  That is, the present invention contacts the magnesium compound (a), the tetravalent titanium halogen compound (b) and the electron donating compound (c) in the presence of a mixed solvent of an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound. The solid catalyst component for olefin polymerization is provided.

The present invention also provides: (A) the above solid catalyst component, and (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 r is a real number of 0 <p ≦ 3). The present invention provides a catalyst for olefin polymerization.

  Furthermore, the present invention provides an olefin formed from (A) the above solid catalyst component, (B) an organoaluminum compound represented by the general formula (1) and (C) an electron donating compound. A polymerization catalyst is provided.

  Furthermore, the present invention provides a method for producing an olefin polymer, which is carried out in the presence of the above olefin polymerization catalyst.

  The present invention exhibits high activity when used as a component of a catalyst for polymerization of olefins, and a stereoregular polymer can be obtained in high yield. Furthermore, a polymer with few fine powders can be obtained. Therefore, usefulness is expected in polyolefin production.

  Among the catalysts for olefin polymerization of the present invention, the solid catalyst component (A) (hereinafter sometimes simply referred to as “component (A)”) comprises a magnesium compound (a), a tetravalent titanium halogen compound (b) and It is obtained by contacting the electron donating compound (c) in the presence of a mixed solvent of an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound. A magnesium compound (hereinafter simply referred to as “component (a)”) Examples of “some” include magnesium dihalide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, fatty acid magnesium, etc. Among these magnesium compounds, dihalogenated magnesium, dihalogenated Magnesium and dialkoxymers A mixture of nesium and dialkoxymagnesium are preferable, dialkoxymagnesium is particularly preferable, and specific examples include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium and the like. Diethoxymagnesium is particularly preferred.

These dialkoxymagnesium may be obtained by reacting metal magnesium with alcohol in the presence of a halogen-containing organic metal or the like. The above dialkoxymagnesium can be used alone or in combination of two or more.
Furthermore, dialkoxymagnesium that is preferably used is in the form of granules or powder, and the shape thereof may be indefinite or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution is obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as filter clogging in the polymer separation apparatus due to the fine powder contained are solved.

  The spherical dialkoxymagnesium does not necessarily need to be a true sphere, and an elliptical or potato-shaped one can also be used. Specifically, the particle shape is such that the ratio (L / W) of the major axis diameter L to the minor axis diameter W is 3 or less, preferably 1 to 2, more preferably 1 to 1.5. .

  The dialkoxymagnesium having an average particle size of 1 to 200 μm can be used. Preferably it is 5-150 micrometers. In the case of spherical dialkoxymagnesium, the average particle size is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. In addition, as for the particle size, it is preferable to use one having a small amount of fine powder and coarse powder and a narrow particle size distribution. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, when the particle size distribution is represented by D90 / D10 (where D90 is the integrated particle size at 90%, D10 is the integrated particle size at 10%), it is 3 or less, preferably 2 or less. .

  For example, JP-A-58-4132, 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 simply referred to as “component (b)”) used for the preparation of the component (A) in the present invention is represented by the general formula (2); Ti (OR ² ). a titanium halide represented by _n X _4-n (wherein R ² represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and n is an integer of 0 ≦ n <4); One or more compounds selected from the group of alkoxytitanium halides.

  Specifically, titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide are exemplified as the titanium halide, and methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n- Butoxy titanium trichloride, 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, etc. Is exemplified. Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.

  The electron donating compound (hereinafter sometimes simply referred to as “component (c)”) used for the preparation of the solid catalyst component 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 or Si—N—C bonds, etc. Is mentioned.

  Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, 9,9- Ethers such as bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate , Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, anisic acid Monocarboxylic acid esters such as chill, malonic acid diester, malonic acid diester derivative, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, maleic acid diester derivative, maleic acid diester derivative , Dicarboxylic acid diesters such as phthalic acid diester and phthalic acid diester derivatives, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone and benzophenone, acid halides such as phthalic dichloride and terephthalic acid dichloride, acetaldehyde, propionaldehyde, Aldehydes such as octyl aldehyde and benzaldehyde, methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, etc. Amines, amides such as oleic acid amide and stearic acid amide, nitriles such as acetonitrile, benzonitrile and tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane And organosilicon compounds containing Si—O—C bonds such as cycloalkylalkoxysilane and cycloalkylalkylalkoxysilane. Of these compounds, carboxylic acid esters and ether compounds are preferred.

  Among the above electron donating compounds, esters, particularly monocarboxylic acid monoesters and dicarboxylic acid diesters are preferably used, and dicarboxylic acid diesters are particularly preferably used. As the dicarboxylic acid diesters, maleic acid diesters and maleic acid diesters are used. Derivatives, malonic acid diesters, malonic acid diester derivatives, phthalic acid diesters and derivatives thereof are preferred. 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.

  Further, as the phthalic acid diester derivative, one or two hydrogen atoms of the benzene ring to which the two ester groups of the above phthalic acid diester are bonded are an alkyl group having 1 to 5 carbon atoms, or a chlorine atom, bromine atom and fluorine. Examples thereof include those substituted with a halogen atom such as an atom. Specifically, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, 4,5, dineopentyl dimethylphthalate, dineopentyl 4,5-diethylphthalate, diethyl 4-chlorophthalate, di-n-chlorochlorophthalate Butyl, dineopentyl 4-chlorophthalate, diisobutyl 4-chlorophthalate, diisohexyl 4-chlorophthalate, diisooctyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n-butyl 4-bromophthalate, dineopentyl 4-bromophthalate, 4- Diisobutyl bromophthalate, diisohexyl 4-bromophthalate, diisooctyl 4-bromophthalate, diethyl 4,5-dichlorophthalate, di-n-butyl 4,5-dichlorophthalate, diisohexyl 4,5-dichlorophthalate 4,5-dichloro phthalic acid diisooctyl, can be mentioned, of which 4-bromophthalic acid dineopentyl, 4-bromophthalic di -n- butyl, and 4-bromophthalic acid diisobutyl are preferred.

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

  Malonic acid diester derivatives include diethyl isopropyl bromomalonate, diethyl butyl bromomalonate, diethyl isobutyl bromomalonate, diethyl diisopropyl malonate, diethyl dibutyl malonate, diethyl diisobutyl malonate, diethyl diisopentyl malonate, isopropyl isobutyl malon Examples include diethyl acid, isopropyl isopentyl malonate dimethyl, diethyl (3-chloro-n-propyl) malonate, diethyl bis (3-bromo-n-propyl) malonate, and among these, diisobutylmalon Particularly preferred are diethyl acid and diethyl dibutylmalonate.

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

  Maleic acid diester derivatives include diethyl isopropyl bromomaleate, diethyl butyl bromomaleate, diethyl isobutyl bromomaleate, diethyl diisopropyl maleate, diethyl dibutyl maleate, diethyl diisobutyl maleate, diethyl diisopentyl maleate, isopropyl isobutyl maleate Illustrative examples include diethyl acid, isopropyl isopentyl maleate dimethyl, diethyl (3-chloro-n-propyl) maleate, diethyl bis (3-bromo-n-propyl) maleate, dibutyl dimethyl maleate, dibutyl diethyl maleate and the like. Among these, dibutyl dimethyl maleate, dibutyl diethyl maleate and diethyl diisobutyl maleate are particularly preferred.

  In addition, it is also preferable to use a combination of two or more of the above-mentioned esters. In this case, a combination of the esters in which the total carbon number of the alkyl group of the ester used is 4 or more compared to that of other esters. Is desirable.

The monocarboxylic acid monoester is an aliphatic monocarboxylic acid ester or an aromatic monocarboxylic acid ester, specifically, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, Ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl anisate, methyl anisate and the following general formula (3); (R ³ ) ₃ CCOOR ⁴ (3)
(Wherein R ³ represents an alkyl group having 1 to ³ carbon atoms, which may be the same or different, and R ⁴ represents an alkyl group having 1 to 12 carbon atoms). And the like.

In the above general formula (3), R ³ is a methyl group, an ethyl group, a propyl group or an isopropyl group, preferably a methyl group. The compound in which R ³ is a methyl group is an ester of pivalic acid (or an ester of trimethylacetic acid). R ⁴ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a t-butyl group, particularly preferably a methyl group or an ethyl group. Specific compounds include methyl trimethyl acetate (methyl pivalate), ethyl trimethyl acetate (ethyl pivalate), propyl trimethyl acetate (propyl pivalate), isopropyl trimethyl acetate (isopropyl pivalate), butyl trimethyl acetate (butyl pivalate) ), Isobutyl trimethyl acetate (isobutyl pivalate), t-butyl trimethyl acetate (t-butyl pivalate), methyl triethyl acetate, ethyl triethyl acetate, propyl triethyl acetate, isopropyl triethyl acetate, butyl triethyl acetate, isobutyl triethyl acetate, triethyl acetate t-butyl, methyl tripropyl acetate, ethyl tripropyl acetate, propyl tripropyl acetate, isopropyl tripropyl acetate, butyl tripropyl acetate, isobutyl tripropyl acetate, tripropyl acetate Propyl acetate t- butyl, triisopropyl methyl acetate, triisopropyl ethyl acetate, triisopropyl propyl acetate, triisopropyl isopropyl acetate, butyl triisopropyl acid, triisopropyl isobutyl acetate, tri isopropyl acetate t- butyl.

  Among the above monocarboxylic acid esters, ethyl benzoate, ethyl p-ethoxybenzoate, ethyl anisate, methyl trimethyl acetate (methyl pivalate) and ethyl trimethyl acetate (ethyl pivalate) are preferred. These monocarboxylic acid esters can be used alone or in combination of two or more.

  In the present invention, the above (a), (b), and (c) may be substituted with an aromatic hydrocarbon compound (hereinafter sometimes simply referred to as “component (d1)”) and an aliphatic hydrocarbon compound (hereinafter referred to as “component (d1)”). Component (A) is prepared by contacting in the presence of a mixed solvent (hereinafter sometimes simply referred to as “component (d)”) with “component (d2)”. Examples of the aromatic hydrocarbon compound include benzene and alkylbenzene, and specifically, benzene, toluene, xylene, ethylbenzene, ethyltoluene, propylbenzene, butylbenzene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, decylbenzene. , Dodecylbenzene, allylbenzene, trimethylbenzene, diethylbenzene and the like are used. Among these aromatic hydrocarbon compounds, benzene, toluene, xylene, ethylbenzene, ethyltoluene and the like are preferably used. Moreover, these may be used independently or may be used in mixture of 2 or more types. In particular, a mixture of an alkylbenzene having one alkyl group such as toluene or ethylbenzene and an alkylbenzene having two or more alkyl groups such as xylene or ethyltoluene is preferable. Furthermore, as for the alkylbenzene having two or more alkyl groups, an alkylbenzene having two or more alkyl groups having different carbon numbers such as ethyltoluene is preferable. As the aliphatic hydrocarbon compound, a saturated aliphatic hydrocarbon compound that is liquid at 25 ° C. is preferably used. Specifically, pentane, hexane, heptane, octane, decane, dodecane, undecane, tridecane, tetradecane, kerosene and the like are used. Among these aliphatic hydrocarbon compounds, hexane, heptane, octane, decane and the like are preferable, and straight chain having 6 to 10 carbon atoms such as n-hexane, n-heptane, n-octane, n-nonane and n-decane. A chain saturated aliphatic hydrocarbon compound is particularly preferably used. Moreover, these may be used independently or may be used in mixture of 2 or more types.

  The mixing ratio of the component (d1) and the component (d2) is preferably a mixing ratio in such a range that the weight of the component (d2) does not exceed the weight of the component (d1). Further, the amount of the component (d1) and the amount of the component (d2) is preferably in the range of 99: 1 to 52:48 by weight ratio, particularly preferably 99: 1 to 80:20. By increasing the amount of component (d2), the amount of fine powder generated can be reduced. However, if the amount of the component (d2) is excessively increased, the activity and the bulk specific gravity (BD) of the polymer are lowered, and further, the particles are aggregated and fixed, so that a solid catalyst component cannot be obtained. These problems can be reduced by using a mixed solvent of the alkylbenzene having one alkyl group and the alkylbenzene having two alkyl groups as the component (d1). Regarding the mixing ratio of alkylbenzene having one alkyl group and alkylbenzene having two or more alkyl groups, the mixing ratio is such that the weight of alkylbenzene having two or more alkyl groups does not exceed the weight of alkylbenzene having one alkyl group. A ratio is preferred. Furthermore, the amount of alkylbenzene having one alkyl group and the amount of alkylbenzene having two alkyl groups is particularly preferably in the range of 99: 1 to 80:20 by weight.

In the preparation of the solid catalyst component (A) of the present invention, it is preferable to use a polysiloxane (hereinafter sometimes simply referred to as “component (e)”) in addition to the above components. Thus, the stereoregularity or crystallinity of the produced polymer can be improved, and further the fine powder of the produced polymer can be reduced. Polysiloxane is a polymer having a siloxane bond (—Si—O bond) in the main chain, but is also collectively referred to as silicone oil, and has a viscosity at 25 ° C. of 0.02 to 100 cm ² / s ( ^{2 to} 10,000 centistokes). It is a liquid or viscous chain-like, partially hydrogenated, cyclic or modified polysiloxane at room temperature.

  As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used. As the partially hydrogenated polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylcyclotrimethyl is used. Siloxane, octamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid groups. Examples thereof include substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable, and decamethylcyclopentasiloxane is particularly preferable.

  In the present invention, the above components (a), (b), (c) and, if necessary, (e) are contacted in the presence of a mixed solvent (d) of components (d1) and (d2) to bring component (A) into contact. The method for preparing component (A) of the present invention will be described below. Specifically, the magnesium compound (a) is suspended in a mixed solvent (d) of the aromatic hydrocarbon compound (d1) and the aliphatic hydrocarbon compound (d2), and a tetravalent titanium halogen compound (b) is added thereto. ). At any point in time, an electron donating compound (c) such as a carboxylic acid ester is contacted to obtain component (A). Further, a method of obtaining the component (A) by contacting the tetravalent titanium halogen compound (b) is also a preferred embodiment. In this method, by using a spherical magnesium compound, a spherical component (A) having a sharp particle size distribution can be obtained, and without using the spherical magnesium compound, for example, a solution or suspension can be obtained using a spray device. By forming particles by a so-called spray-drying method in which a turbid liquid is sprayed and dried, a spherical component (A) having 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 a state where moisture and the like are removed under an inert gas atmosphere. The contact temperature is the temperature at the time of contact of each component 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 is 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 catalyst component, and if it exceeds 130 ° C, evaporation of the solvent used becomes remarkable. Therefore, it becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

  As a method for preparing the preferred component (A) of the present invention, the magnesium compound (a) is suspended in a mixed solvent of an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound, and then the titanium compound (b) is contacted. A method in which the electron donating compound (c) is brought into contact at any point in time can be mentioned.

  A preferred method for preparing component (A) of the present invention is to suspend component (a) in component (d), then contact component (b), and then contact component (c) and react. Method of preparing component (A) or component (A) by suspending component (a) in component (d) and then contacting component (c) and then contacting and reacting with component (b) ) Can be mentioned. Moreover, the performance of the final solid catalyst component can be improved by bringing the component (A) thus prepared into contact with the component (b) or the component (b) and the component (c) again or multiple times. it can. At this time, it is desirable to carry out in the presence of component (d) or component (d1).

  As a preferred method for preparing component (A) in the present invention, a suspension was formed from component (a), component (c) and component (d), and formed from component (b) and component (d). The preparation method by making a mixed solution contact this suspension and making it react after that can be mentioned.

  Another preferred method for preparing the component (A) in the present invention includes the following methods. A suspension is formed from the component (a), the component (c) and the component (d). A mixed solution is formed from component (b) and component (d), and the suspension is added to the mixed solution. Then, the obtained mixed solution is heated and subjected to a reaction treatment (first reaction treatment). After completion of the reaction, the obtained solid substance is washed with a liquid hydrocarbon compound at room temperature, and the solid substance after washing is used as a solid product. After that, the washed solid material is further brought into contact with component (b) and component (d) at -20 to 100 ° C., and the temperature is raised to carry out a reaction treatment (secondary reaction treatment). And after completion | finish of reaction, the component (A) which repeated the operation | movement wash | cleaned with the liquid hydrocarbon compound at normal temperature 1 to 10 times can also be obtained.

  Based on the above, as a particularly preferred method for preparing the solid catalyst component (A) in the present invention, dialkoxymagnesium (a) is suspended in a mixed solvent (d), and then a tetravalent titanium halogen compound is suspended in this suspension. After contacting (b), 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 a carboxylic acid ester are added at −20 to 20 Contact at 130 ° C. and contact with component (e) as necessary to carry out a reaction treatment to obtain a solid product (1). At this time, it is desirable to perform the aging reaction at a low temperature before or after contacting one or more of the electron donating compounds. The solid product (1) is washed (intermediate washing) with a liquid hydrocarbon compound at room temperature, preferably a mixed solvent (d), and then the tetravalent titanium halogen compound (b) is added again to the presence of the mixed solvent (d). Below, it is made to contact at -20-100 degreeC, a reaction process is performed, and a solid product (2) is obtained. 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 by decantation to obtain the solid catalyst component (A).

  The amount of each component used in preparing the solid catalyst component (A) varies depending on the preparation method and cannot be determined unconditionally. For example, a tetravalent titanium halogen compound (b) per 1 mol 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 0.02 to 0.6 mol, mixed solvent (d) is 0.001 to 500 mol, preferably 0.001 to 100 mol, more preferably 0.005 to 10 mol, Siloxane (e) is 0.01 to 100 g, preferably 0.05 to 80 g, more preferably 1 to 50 g.

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

The organoaluminum compound (B) (hereinafter sometimes simply referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention is a compound represented by the general formula (1). if is not particularly limited, examples of R ^1, an ethyl group, isobutyl group are preferable, as the Q, hydrogen atom, a chlorine atom, preferably a bromine atom, p is preferably 2 or 3, most preferably 3. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and triisobutylaluminum are preferable.

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

  Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, 9,9- Ethers such as bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate , Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, p-toluyl Monocarboxylic acid esters such as methyl, ethyl p-toluate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate Dicarboxylic acid esters such as dioctyl adipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, and didecyl phthalate , Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, acid halides such as phthalic dichloride, terephthalic dichloride, acetaldehyde, propional Aldehydes such as hydride, octyl aldehyde and benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine, amides such as oleic acid amide and stearic acid amide, nitriles such as acetonitrile, benzonitrile and tolunitrile And isocyanates such as methyl isocyanate and ethyl isocyanate.

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

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

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

  Specific examples of the organosilicon compound include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri-iso-butylmethoxy. Silane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxy Silane, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-iso-propyldiethoxy Orchid, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane Bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane Bis (3,5-dimethylcyclohexyl) dimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclo Nthyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5 -Dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldi Ethoxysilane, Cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (iso-propyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, cyclohexyl ( n-butyl) diethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxy Silane, phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimeth Sisilane, ethyltriethoxysilane, n-propyltrimethoxysilane, iso-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane, t -Butyltrimethoxysilane, n-butyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropyl Ropoxysilane and tetrabutoxysilane are preferably used. The organosilicon compounds can be used alone or in combination of two or more.

As the aminosilane compound, the following general formulas (5) to (8);
R ⁷ R ⁸ Si (OR ⁹ ) ₂ (5)
(R ¹⁰ R ¹¹ N) Si (OR ¹² ) ₃ (6)
(R ¹³ NH) ₂ Si (OR ¹⁴ ) ₂ (7)
(R ¹⁵ NH) R ¹⁶ Si (OR ¹⁷ ) ₂ (8)
The compound represented by these is mentioned, The 1 type (s) or 2 or more types chosen from these compounds can be used.

The aminosilane compound of the general formula (5) is a compound in which the N atom of the perhydroquinolino group or the perhydroisoquinolino group is directly bonded to the Si atom. In the general formula (5), R ⁷ is a perhydroquinolino group or R ⁸ represents a perhydroisoquinolino group, and R ⁸ represents a perhydroquinolino group, a perhydroisoquinolino group, 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. R ⁷ and R ⁸ may be the same or different, and 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, and is the same or different. It may be. Examples of such aminosilane compounds include bis (perhydroquinolino) dialkoxysilane, bis (perhydroisoquinolino) dialkoxysilane, perhydroquinolinoalkyl dialkoxysilane, and perhydroisoquinolinoalkyldialkoxysilane. Of the compounds represented by the general formula (5), compounds in which R ⁷ and R ⁸ are the same are preferable, and R ⁷ and R ⁸ are the same and R ⁹ is particularly preferable. . R ⁷ is particularly preferably a perhydroisoquinolino group. Furthermore, as R < ⁹ >, a C1-C4 alkyl group is preferable and a methyl group is especially preferable.

  Specific compounds of the general formula (5) include bis (perhydroquinolino) dimethoxysilane, bis (perhydroquinolino) diethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, and bis (perhydroisoquino). Lino) diethoxysilane, ethyl (perhydroquinolino) dimethoxysilane, ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydroquinolino) dimethoxysilane, n-propyl (perhydroisoquinolino) dimethoxysilane, Isopropyl (perhydroquinolino) dimethoxysilane, isopropyl (perhydroisoquinolino) dimethoxysilane, butyl (perhydroquinolino) dimethoxysilane, butyl (perhydroisoquinolino) dimethoxysilane, isopropyl (perhydroquinolino) dimethyl Toxisilane, isopropyl (perhydroisoquinolino) dimethoxysilane, t-butyl (perhydroquinolino) dimethoxysilane, t-butyl (perhydroisoquinolino) dimethoxysilane, pentyl (perhydroquinolino) dimethoxysilane, pentyl (perhydro Isoquinolino) dimethoxysilane, isopentyl (perhydroquinolino) dimethoxysilane, isopentyl (perhydroisoquinolino) dimethoxysilane, cyclopentyl (perhydroquinolino) dimethoxysilane, cyclopentyl (perhydroisoquinolino) dimethoxysilane, cyclohexyl (per Hydroquinolino) dimethoxysilane, cyclohexyl (perhydroisoquinolino) dimethoxysilane, phenyl (perhydroquinolino) dimethoxysilane, phenyl (perhydride) Roisoquinolino) dimethoxysilane and the like can be used, and one or more can be used. Among these, bis (perhydroquinolino) dimethoxysilane and bis (perhydroisoquinolino) dimethoxysilane are preferable.

The aminosilane compound of the general formula (6) is a compound in which an N atom is directly bonded to an Si atom, and in the formula, R ¹⁰ represents a linear or branched alkyl group having 1 to 12 carbon atoms or a hydrogen atom, R ¹¹ represents a linear or branched alkyl group having 1 to 12 carbon atoms, R ¹⁰ and R ¹¹ may be the same or different, and R ¹² represents a linear or branched alkyl group having 1 to 4 carbon atoms. It is a group. Examples of such aminosilane compounds are monoalkylaminotrialkoxysilanes and dialkylaminotrialkoxysilanes.

  Specific compounds of the general formula (6) include dimethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, methyl (n -Propyl) aminotriethoxysilane, t-butylaminotriethoxysilane, ethyl (n-propyl) aminotriethoxysilane, ethyl (iso-propyl) aminotriethoxysilane, and methylethylaminotriethoxysilane. Species or two or more can be used. Among these, diethylaminotriethoxysilane is preferable.

The aminosilane compound of the general formula (7) is a compound in which an N atom is directly bonded to an Si atom, and the N atom is a compound containing a secondary amino group bonded to a hydrogen atom and an R ¹³ group. R ^{13 in the} general formula (7) is preferably an alkyl group having 1 to 12 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, Examples include a pentyl group, an isopentyl group, a neo-pentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group, and an isooctyl group. Among these, an ethyl group, a propyl group, an isopropyl group, and a butyl group , Isobutyl group, t-butyl group, and neo-pentyl group are preferable.

R ¹³ is preferably a cycloalkyl group having 3 to 12 carbon atoms, specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2- Ethylcyclopentyl group, 3-propylcyclopentyl group, 3-isopropylcyclopentyl group, 3-butylcyclopentyl group, 3-isobutylcyclopentyl group, 3-t-butylcyclopentyl group, 2,2-dimethylcyclopentyl group, 2,3-dimethylcyclopentyl Group, 2,5-dimethylcyclopentyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 2-ethylcyclohexyl group, 3-propylcyclohexyl group, 3-isopropylcyclohexyl group, 3-butylcyclohexyl group, 3 -Isobutylcyclohexyl group, 3-t-butylcyclohexyl group, 2,2-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 1-cyclopentylmethyl group, cyclopentylmethyl group, 1-cyclopentyl An ethyl group, 1-cyclopentylpropyl group, menthyl group, mentenyl group, 2-chlorocyclopentyl group, 2-bromocyclopentyl group, 2-chlorocyclohexyl, 2-bromocyclohexyl group and the like can be mentioned. Among these, a cyclopentyl group and a cyclohexyl group are particularly preferable.

R ^{14 in the} general formula (7) is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group. , T-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like, among which methyl group and ethyl group are particularly preferable.

  Examples of the aminosilane compound represented by the general formula (7) include bis (alkylamino) dialkoxysilane, bis (cycloalkylalkylamino) dialkoxysilane, bis (alkyl-substituted cycloalkylamino) dialkoxysilane, and bis (halogen). Substituted cycloalkylamino) dialkoxysilanes, bis (cycloalkylalkylamino) dialkoxysilanes and the like are mentioned, and among these, bis (alkylamino) dialkoxysilanes and bis (cycloalkylalkylamino) dialkoxysilanes are preferred.

  Specific examples of such aminosilane compounds include bis (methylamino) dimethoxysilane, bis (methylamino) diethoxysilane, bis (ethylamino) dimethoxysilane, bis (ethylamino) diethoxysilane, and bis (propylamino). ) Dimethoxysilane, bis (propylamino) diethoxysilane, bis (isopropylamino) dimethoxysilane, bis (isopropylamino) diethoxysilane, bis (butylamino) dimethoxysilane, bis (butylamino) diethoxysilane, bis (isobutyl) Amino) dimethoxysilane, bis (isobutylamino) diethoxysilane, bis (t-butylamino) dimethoxysilane, bis (t-butylamino) diethoxysilane, bis (cyclopentylamino) dimethoxysilane, bis (si Lopentylamino) diethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (cyclohexylamino) diethoxysilane, bis (2-methylcyclopentylamino) dimethoxysilane, bis (2-methylcyclopentylamino) diethoxysilane, bis ( 2-ethylcyclopentylamino) dimethoxysilane, bis (2-ethylcyclopentylamino) diethoxysilane, bis (2-chlorocyclopentylamino) dimethoxysilane, bis (2-chlorocyclopentylamino) diethoxysilane, bis (2-bromocyclopentyl) Amino) dimethoxysilane, bis (2-bromocyclopentylamino) diethoxysilane, bis (2-methylcyclohexylamino) dimethoxysilane, bis (2-methylcyclohexyla) B) Diethoxysilane, bis (2-ethylcyclohexylamino) dimethoxysilane, bis (2-ethylcyclohexylamino) diethoxysilane, bis (2-chlorocyclohexylamino) dimethoxysilane, bis (2-chlorocyclohexylamino) diethoxy Silane, bis (2-bromocyclohexylamino) dimethoxysilane, bis (2-bromocyclohexylamino) diethoxysilane, bis (cyclopentylmethylamino) dimethoxysilane, bis (cyclopentylmethylamino) diethoxysilane, bis (1-cyclopentylethyl) Amino) dimethoxysilane, bis (1-cyclopentylethylamino) ditriethoxysilane and the like can be mentioned, and one or more can be used. Among these, bis (ethylamino) dimethoxysilane, bis (propylamino) dimethoxysilane, dis (isopropyl) dimethoxysilane, bis (butylamino) dimethoxysilane, bis (isobutylamino) dimethoxysilane, bis (t-butyl) are preferable. Amino) dimethoxysilane, bis (cyclopentylamino) dimethoxysilane, and bis (cyclohexylamino) dimethoxysilane.

The aminosilane compound of the general formula (8) is a compound in which an N atom is directly bonded to a Si atom, and the N atom is bonded to a hydrogen atom and R ¹⁵ . In the general formula (8), R ¹⁵ and R ¹⁶ represent a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group and derivatives thereof, a vinyl group, an allyl group, and an aralkyl group, and are the same or different. R ¹⁷ is a linear or branched alkyl group having 1 to 12 carbon atoms and may be the same or different.

As R < ¹⁵ >, R < ¹⁶ > of the said General formula (8), a C1-C8 alkyl group and a C3-C8 cycloalkyl group are preferable, and, specifically, a methyl group, an ethyl group, n-propyl group , Isopropyl, butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, isooctyl, 2-methylhexyl, 2-ethylhexyl Group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like, and R ¹⁵ and R ¹⁶ may be the same or different. Among these, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, n-pentyl group, neopentyl group, hexyl group, cyclopentyl group, cyclohexyl group, 2-methylhexyl Groups are preferred.

R ¹⁵ is preferably an alkyl group having 1 to 5 carbon atoms, particularly an alkyl group having 1 to 5 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, A t-butyl group, an n-pentyl group and a neopentyl group are preferred.

R ^{17 in the} general formula (8) is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, isopropyl group, butyl group, isobutyl group, t-butyl. Group, pentyl group, hexyl group, heptyl group, octyl group and the like. Among these, a methyl group and an ethyl group are particularly preferable.

  Examples of such aminosilane compounds include alkyl (alkylamino) dialkoxysilanes, alkyl (cycloalkylamino) dialkoxysilanes, alkyl (alkyl group-substituted cycloalkylamino) dialkoxysilanes, and the like. Of these, alkyl (alkylamino) dialkoxysilane and alkyl (cycloalkylamino) dialkoxysilane are preferable.

  Specific examples of such aminosilane compounds include methyl (isopropylamino) dimethoxysilane, ethyl (isopropylamino) dimethoxysilane, n-propyl (isopropylamino) dimethoxysilane, isopropyl (isopropylamino) dimethoxysilane, sec-butyl ( Isopropylamino) dimethoxysilane, t-butyl (isopropylamino) dimethoxysilane, cyclopentyl (isopropylamino) dimethoxysilane, cyclohexyl (isopropylamino) dimethoxysilane, 2-methylcyclohexyl (isopropylamino) dimethoxysilane, 2,6-dimethylcyclohexyl ( Isopropylamino) dimethoxysilane, methyl (n-butylamino) dimethoxysilane, ethyl (n-butylamino) dimethoxy Run, n-propyl (n-butylamino) dimethoxysilane, isopropyl (n-butylamino) dimethoxysilane, Sec-butyl (n-butylamino) dimethoxysilane, t-butyl (n-butylamino) dimethoxysilane, cyclopentyl ( n-butylamino) dimethoxysilane, cyclohexyl (n-butylamino) dimethoxysilane, 2-methylcyclohexyl (n-butylamino) dimethoxysilane, 2,6-dimethylcyclohexyl (n-butylamino) dimethoxysilane, methyl (sec- Butylamino) dimethoxysilane, ethyl (sec-butylamino) dimethoxysilane, n-propyl (sec-butylamino) dimethoxysilane, isopropyl (sec-butylamino) dimethoxysilane, t-butyl (sec-butylamino) dimethoxy Lan, cyclopentyl (sec-butylamino) dimethoxysilane, 2-methylcyclopentyl (sec-butylamino) dimethoxysilane, cyclohexyl (sec-butylamino) dimethoxysilane, 2-methylcyclohexyl (sec-butylamino) dimethoxysilane, 2, 6-dimethylcyclohexyl (sec-butylamino) dimethoxysilane, methyl (t-butylamino) dimethoxysilane, ethyl (t-butylamino) dimethoxysilane, n-propyl (t-butylamino) dimethoxysilane, isopropyl (t-butyl) Amino) dimethoxysilane, n-butyl (t-butylamino) dimethoxysilane, sec-butyl (t-butylamino) dimethoxysilane, t-butyl (t-butylamino) dimethoxysilane, cyclopentyl (t-butylamino) ) Dimethoxysilane, cyclohexyl (t-butylamino) dimethoxysilane, 2-methylcyclohexyl (t-butylamino) dimethoxysilane, 2,6-dimethylcyclohexyl (t-butylamino) dimethoxysilane, methyl (cyclopentylamino) dimethoxysilane, Ethyl (cyclopentylamino) dimethoxysilane, n-propyl (cyclopentylamino) dimethoxysilane, isopropyl (cyclopentylamino) dimethoxysilane, sec-butyl (cyclopentylamino) dimethoxysilane, t-butyl (cyclopentylamino) dimethoxysilane, cyclopentyl (cyclopentylamino) ) Dimethoxysilane, cyclohexyl (cyclopentylamino) dimethoxysilane, 2-methylcyclohexyl (cyclopentylamino) ) Dimethoxysilane, methyl (cyclohexylamino) dimethoxysilane, ethyl (cyclohexylamino) dimethoxysilane, n-propyl (cyclohexylamino) dimethoxysilane, isopropyl (cyclohexylamino) dimethoxysilane, sec-butyl (cyclohexylamino) dimethoxysilane, t- Butyl (cyclohexylamino) dimethoxysilane, cyclopentyl (cyclohexylamino) dimethoxysilane, cyclohexyl (cyclohexylamino) dimethoxysilane, 2-methylcyclohexyl (cyclohexylamino) dimethoxysilane, 2,6-dimethylcyclohexyl (cyclohexylamino) dimethoxysilane, methyl ( 2-methylcyclohexylamino) dimethoxysilane, ethyl (2-methylcyclohexyl) Ruamino) dimethoxysilane, n-propyl (2-methylcyclohexylamino) dimethoxysilane, isopropyl (2-methylcyclohexylamino) dimethoxysilane, sec-butyl (2-methylcyclohexylamino) dimethoxysilane, t-butyl (2-methylcyclohexyl) Amino) dimethoxysilane, cyclopentyl (2-methylcyclohexylamino) dimethoxysilane, 2-methylcyclopentyl (2-methylcyclohexylamino) dimethoxysilane, cyclohexyl (2-methylcyclohexylamino) dimethoxysilane, 2-methylcyclohexyl (2-methylcyclohexyl) Amino) dimethoxysilane, 2,6-dimethylcyclohexyl (2-methylcyclohexylamino) dimethoxysilane, methyl (isopropyl) Amino) diethoxysilane, ethyl (isopropylamino) diethoxysilane, n-propyl (isopropylamino) diethoxysilane, isopropyl (isopropylamino) diethoxysilane, sec-butyl (isopropylamino) diethoxysilane, t-butyl ( Isopropylamino) diethoxysilane, cyclopentyl (isopropylamino) diethoxysilane, cyclohexyl (isopropylamino) diethoxysilane, 2-methylcyclohexyl (isopropylamino) diethoxysilane, 2,6-dimethylcyclohexyl (isopropylamino) diethoxysilane Methyl (n-butylamino) diethoxysilane, ethyl (n-butylamino) ditooxysilane, n-propyl (n-butylamino) diethoxysilane, isopropyl (N-butylamino) diethoxysilane, sec-butyl (n-butylamino) diethoxysilane, t-butyl (n-butylamino) ditooxysilane, cyclopentyl (n-butylamino) diethoxysilane, cyclohexyl (n-butyl) Amino) diethoxysilane, 2-methylcyclohexyl (n-butylamino) diethoxysilane, 2,6-dimethylcyclohexyl (n-butylamino) diethoxysilane, methyl (n-butylamino) diethoxysilane, methyl (sec -Butylamino) diethoxysilane, ethyl (sec-butylamino) diethoxysilane, n-propyl (sec-butylamino) diethoxysilane, isopropyl (sec-butylamino) diethoxysilane, cyclopentyl (sec-butylamino) Diethoxysilane, cyclohexyl (Sec-butylamino) diethoxysilane, 2-methylcyclohexyl (sec-butylamino) diethoxysilane, 2,6-dimethylcyclohexyl (sec-butylamino) diethoxysilane, methyl (t-butylamino) diethoxysilane Ethyl (t-butylamino) diethoxysilane, n-propyl (t-butylamino) diethoxysilane, isopropyl (t-butylamino) diethoxysilane, n-butyl (t-butylamino) diethoxysilane, sec -Butyl (t-butylamino) diethoxysilane, t-butyl (t-butylamino) diethoxysilane, cyclopentyl (t-butylamino) diethoxysilane, cyclohexyl (t-butylamino) diethoxysilane, 2-methyl Cyclohexyl (t-butylamino) diethoxysilane, 2,6-dimethylcyclohexyl (t-butylamino) diethoxysilane, methyl (cyclopentylamino) diethoxysilane, ethyl (cyclopentylamino) diethoxysilane, n-propyl (cyclopentylamino) diethoxysilane, isopropyl (cyclopentylamino) Diethoxysilane, sec-butyl (cyclopentylamino) diethoxysilane, t-butyl (cyclopentylamino) diethoxysilane, cyclopentyl (cyclopentylamino) diethoxysilane, cyclohexyl (cyclopentylamino) diethoxysilane, 2-methylcyclohexyl (cyclopentyl) Amino) diethoxysilane, 2,6-dimethyl (cyclopentylamino) diethoxysilane, methyl (cyclohexylamino) diethoxysilane, ethyl Cyclohexylamino) diethoxysilane, n-propyl (cyclohexylamino) diethoxysilane, isopropyl (cyclohexylamino) diethoxysilane, sec-butyl (cyclohexylamino) diethoxysilane, t-butyl (cyclohexylamino) diethoxysilane, cyclopentyl (Cyclohexylamino) diethoxysilane, cyclohexyl (cyclohexylamino) diethoxysilane, 2-methylcyclohexyl (cyclohexylamino) diethoxysilane, 2,6-dimethyl (cyclohexylcyclohexylamino) diethoxysilane, methyl (2-methylcyclohexylamino) ) Diethoxysilane, ethyl (2-methylcyclohexylamino) diethoxysilane, n-propyl (2-methylcyclohexylamino) Ethoxysilane, isopropyl (2-methylcyclohexylamino) diethoxysilane, sec-butyl (2-methylcyclohexylamino) diethoxysilane, t-butyl (2-methylcyclohexylamino) diethoxysilane, cyclopentyl (2-methylcyclohexylamino) ) Diethoxysilane, cyclohexyl (2-methylcyclohexylamino) diethoxysilane, 2-methylcyclohexyl (2-methylcyclohexylamino) diethoxysilane, 2,6-dimethyl (2-methylcyclohexylcyclohexylamino) diethoxysilane, methyl (Isopropylamino) di-n-propoxysilane, ethyl (isopropylamino) di-n-propoxysilane, n-propyl (isopropylamino) di-n-propoxysilane, iso Propyl (isopropylamino) di-n-propoxysilane, sec-butyl (isopropylamino) di-n-propoxysilane, t-butyl (isopropylamino) di-n-propoxysilane, cyclopentyl (isopropylamino) di-n-propoxy Silane, cyclohexyl (isopropylamino) di-n-propoxysilane, 2-methylcyclohexyl (isopropylamino) di-n-propoxysilane, 2,6-dimethylcyclohexyl (isopropylamino) di-n-propoxysilane, methyl (n- Butylamino) di-n-propoxysilane, ethyl (n-butylamino) di-n-propoxysilane, n-propyl (n-butylamino) di-n-propoxysilane, isopropyl (n-butylamino) di-n -Propoxysilane, s ec-butyl (n-butylamino) di-n-propoxysilane, t-butyl (n-butylamino) di-n-propoxysilane, cyclopentyl (n-butylamino) di-n-propoxysilane, cyclohexyl (n- Butylamino) di-n-propoxysilane, 2-methylcyclohexyl (n-butylamino) di-n-propoxysilane, 2,6-dimethylcyclohexyl (n-butylamino) di-n-propoxysilane, methyl (sec- Butylamino) di-n-propoxysilane, ethyl (sec-butylamino) di-n-propoxysilane, n-propyl (sec-butylamino) di-n-propoxysilane, isopropyl (sec-butylamino) di-n -Propoxysilane, sec-butyl (sec-butylamino) di-n-propoxysilane, t-butyl (se c-butylamino) di-n-propoxysilane, cyclopentyl (sec-butylamino) di-n-propoxysilane, cyclohexyl (sec-butylamino) di-n-propoxysilane, 2-methylcyclohexyl (sec-butylamino) Di-n-propoxysilane, 2,6-dimethylcyclohexyl (sec-butylamino) di-n-propoxysilane, methyl (t-butylamino) di-n-propoxysilane, ethyl (t-butylamino) di-n -Propoxysilane, n-propyl (t-butylamino) di-n-propoxysilane, isopropyl (t-butylamino) di-n-propoxysilane, n-butyl (t-butylamino) di-n-propoxysilane, sec-butyl (t-butylamino) di-n-propoxysilane, t-butyl (t-butylamino) C) di-n-propoxysilane, cyclopentyl (t-butylamino) di-n-propoxysilane, cyclohexyl (t-butylamino) di-n-propoxysilane,

2-methylcyclohexyl (t-butylamino) di-n-propoxysilane, 2,6-dimethylcyclohexyl (t-butylamino) di-n-propoxysilane, methyl (cyclopentylamino) di-n-propoxysilane, ethyl ( Cyclopentylamino) di-n-propoxysilane, n-propyl (cyclopentylamino) di-n-propoxysilane, isopropyl (cyclopentylamino) di-n-propoxysilane, sec-butyl (cyclopentylamino) di-n-propoxysilane, t-butyl (cyclopentylamino) di-n-propoxysilane, cyclopentyl (cyclopentylamino) di-n-propoxysilane, cyclohexyl (cyclopentylamino) di-n-propoxysilane, 2-methylcyclohexyl (cyclopente) Ruamino) di-n-propoxysilane, 2,6-dimethyl (cyclopentylamino) di-n-propoxysilane, methyl (cyclohexylamino) di-n-propoxysilane, ethyl (cyclohexylamino) di-n-propoxysilane, n -Propyl (cyclohexylamino) di-n-propoxysilane, isopropyl (cyclohexylamino) di-n-propoxysilane, sec-butyl (cyclohexylamino) di-n-propoxysilane, t-butyl (cyclohexylamino) di-n- Propoxysilane, cyclopentyl (cyclohexylamino) di-n-propoxysilane, cyclohexyl (cyclohexylamino) di-n-propoxysilane, 2-methylcyclohexyl (cyclohexylamino) di-n-propoxysilane, 2, -Dimethyl (cyclohexylcyclohexylamino) di-n-propoxysilane, methyl (2-methylcyclohexylamino) di-n-propoxysilane, ethyl (2-methylcyclohexylamino) di-n-propoxysilane, n-propyl (2- Methylcyclohexylamino) di-n-propoxysilane, isopropyl (2-methylcyclohexylamino) di-n-propoxysilane, sec-butyl (2-methylcyclohexylamino) di-n-propoxysilane, t-butyl (2-methyl) Cyclohexylamino) di-n-propoxysilane, cyclopentyl (2-methylcyclohexylamino) di-n-propoxysilane, 2-methylcyclopentyl (2-methylcyclohexylamino) di-n-propoxysilane, cyclohexyl (2 -Methylcyclohexylamino) di-n-propoxysilane, 2-methylcyclohexyl (2-methylcyclohexylamino) di-n-propoxysilane, 2,6-dimethyl (2-methylcyclohexylcyclohexylamino) di-n-propoxysilane, Decahydronaphthyl (2-methylcyclohexylamino) di-n-propoxysilane, 1,2,3,4-tetrahydronaphthyl (2-methylcyclohexylamino) diethoxysilane.

  Next, the catalyst for olefin polymerization of the present invention contains the above-described solid catalyst component (A), component (B), and component (C) for olefin polymerization, and polymerization of olefins in the presence of the catalyst. Copolymerization is performed. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene. In the case of polymerization of propylene, copolymerization with other olefins can also be performed. Examples of olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene and 1-butene are preferably used.

  The amount of each component used is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the organoaluminum compound (B) is titanium in the solid catalyst component (A). It is used in the range of 1 to 2000 mol, preferably 50 to 1000 mol, per mol of atoms. The organosilicon compound (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per 1 mol of the component (B).

  The order of contacting the components is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the external electron-donating compound (C) is contacted, and then the solid catalyst component (A ) Is desirable.

  The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Further, in the present invention, when polymerizing an olefin using a catalyst containing the solid catalyst component (A), the component (B), and the component (C) for olefin polymerization (also referred to as main polymerization), the catalytic activity and the steric properties are determined. In order to further improve the regularity and the particle properties of the polymer to be produced, it is desirable to perform prepolymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

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

  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)>
In a 500 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer, 10 g of diethoxymagnesium and a mixed solvent of toluene and n-heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt. %) 80 ml was charged and suspended. Next, 20 ml of titanium tetrachloride was added to the suspension solution, and the temperature was raised. When the temperature reached 90 ° C., 2.7 ml of di-n-butyl phthalate was added, and the temperature was further raised to 115 ° C. Thereafter, the reaction was carried out with stirring for 2 hours while maintaining a temperature of 115 ° C. After completion of the reaction, the mixture was washed 3 times with 100 ml of a mixed solvent of toluene and n-heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt%) at 90 ° C., and newly added with 20 ml of titanium tetrachloride and toluene. 80 ml of a mixed solvent of n-heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt%) was added, the temperature was raised to 115 ° C., and the mixture was allowed to react for 1 hour with stirring. After completion of the reaction, the solid catalyst component was obtained by washing 7 times with 100 ml of n-heptane at 40 ° C. In addition, when solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 2.6 weight%.

<Formation and polymerization of polymerization catalyst>
Into an autoclave with a stirrer having an internal volume of 2.0 liters completely substituted with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of phenyltriethoxysilane and 0.0066 mmol of the solid catalyst component as titanium atoms were charged, A polymerization catalyst was formed. Thereafter, 1.8 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 30 minutes. Polymerization activity per gram of the solid catalyst component at this time, ratio of boiling n-heptane insoluble matter in the produced polymer (HI), melt index value (MI) of the produced polymer (a), and 105 μm or less in the polymer Table 1 shows the fine powder amount (%).

The polymerization activity per solid catalyst component used here was calculated by the following equation.
Polymerization activity = produced polymer (g) / solid catalyst component (g)
Further, the ratio (HI) of boiling n-heptane insoluble matter in the produced polymer is the ratio (% by weight) of the polymer insoluble in n-heptane when this produced polymer is extracted with boiling n-heptane for 6 hours. ). Further, the melt index value (MI) of the produced polymer (a) was measured according to ASTM D 1238 and JIS K 7210. Moreover, the fine powder amount (%) of 105 μm or less in the polymer was measured by a screening test according to JIS K0069.

Comparative Example 1
A solid catalyst component was prepared in the same manner as in Example 1 except that a solvent of 100% toluene was used instead of a mixed solvent of toluene and n-heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt%). Prepared, formed polymerization catalyst and polymerized. The polymerization results are shown in Table 1.

<Preparation of solid catalyst component>
A round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 10 g of diethoxymagnesium [measured in accordance with JIS K6721 (hereinafter the same), bulk specific gravity of 0.29 g / ml, specific surface area (N2SA) of 19.8 m ^2. / G, sphericity (l / w) 1.10, average particle size 32 μm, pore volume 0.03 ml / g, pore distribution [ln (R90 / R10)] 2.30, fine powder content 5 or less 5 μm %, Particle size distribution [(D90-D10) / D50] 1.05], 50 ml of a mixed solvent of toluene and n-heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt%), diphthalate −3.6 ml of n-butyl was charged into a suspended state. Then, the suspension was mixed with toluene and n-heptane (toluene / n-heptane = 83.) Previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas. 5 wt% / 16.5 wt%) and a solution of 30 ml of titanium tetrachloride were added while maintaining the liquid temperature at 10 ° C. Thereafter, the liquid temperature was raised from 10 ° C. to 90 ° C., and the reaction treatment was carried out for 2 hours while stirring. After completion of the reaction, the product was washed 4 times with 100 ml of a mixed solvent of toluene and n-heptane at 90 ° C. (toluene / n-heptane = 83.5 wt% / 16.5 wt%). 70 ml of a mixed solvent of heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt%) and 30 ml of titanium tetrachloride were added, and the reaction treatment was performed at 112 ° C. for 2 hours with stirring. The product was then washed 10 times with 100 ml of 40 ° C. heptane to obtain a solid catalyst component. The titanium content in the solid component was measured and found to be 3.7% by weight.

<Formation and polymerization of polymerization catalyst>
Into an autoclave with a stirrer having an internal volume of 2.0 liters completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane and 0.0033 mmol of the solid catalyst component as titanium atoms were charged, and polymerization was performed. A catalyst was formed. Thereafter, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 1 hour. The obtained polymer was measured for catalytic activity, boiling heptane insoluble matter (HI, wt%), melt flow rate (MI, g-PP / 10 min) and the amount of fine powder (%) of 105 μm or less in the polymer. did. The results are shown in Table 1.

  Instead of a mixed solvent of toluene and n-heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt%), a mixed solvent of toluene and n-heptane (toluene / n-heptane = 98.4 wt%) The solid catalyst component was prepared in the same manner as in Example 2 except that /1.6 wt% was used, and the polymerization catalyst was formed and polymerized. The polymerization results are shown in Table 1.

  Instead of a mixed solvent of toluene and n-heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt%), a mixed solvent of toluene and n-heptane (toluene / n-heptane = 55.9 wt%) /44.1 wt%) was used in the same manner as in Example 2 except that a solid catalyst component was formed, and a polymerization catalyst was formed and polymerized. The polymerization results are shown in Table 1.

  Instead of a mixed solvent of toluene and n-heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt%), a mixed solvent of toluene, ethyl toluene, n-heptane (toluene / ethyl toluene / n-heptane) = 81.4 wt% / 2.1 wt% / 16.5 wt%) was used, and a solid catalyst component was prepared in the same manner as in Example 2, and a polymerization catalyst was formed and polymerized. The polymerization results are shown in Table 1.

Comparative Example 2
A solid catalyst component was prepared and polymerized in the same manner as in Example 2 except that toluene was used instead of a mixed solvent of toluene and n-heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt%). Catalyst formation and polymerization were performed. The polymerization results are shown in Table 1.

Comparative Example 3
[Preparation of solid catalyst component (A)]
A 200 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer was charged with 5 g of diethoxymagnesium, 2.0 g of di-n-butyl phthalate and 50 ml of methylene chloride to form a suspension. Stir for 1 hour under reflux. The suspension was then pumped into 200 ml of room temperature titanium tetrachloride in a 500 ml round bottom flask equipped with a stirrer, heated to 90 ° C. and maintained at 90 ° C. for 2 hours. The reaction was carried out with stirring. After completion of the reaction, the solid catalyst component was obtained by washing with n-heptane until no chlorine was detected in the washing solution. In addition, when the solid content in this solid catalyst component was isolate | separated and the titanium content rate in solid content was measured, it was 3.7 weight%.

[Formation and polymerization of polymerization catalyst]
In the same manner as in Example 1, the polymerization catalyst was formed and polymerized. The polymerization results are shown in Table 1.

Comparative Example 4
In the same manner as in Example 2 except that n-heptane was used as a solvent instead of a mixed solvent of toluene and n-heptane (toluene / n-heptane = 83.5 wt% / 16.5 wt%). Preparation was attempted. However, during the preparation, the particles aggregated and adhered, and a solid catalyst component could not be obtained.

  The present invention shows high activity when used as a component of a catalyst for polymerization of olefins, and is capable of obtaining a stereoregular polymer in a high yield and further capable of obtaining a polymer with less fine powder. Since it relates to a performance solid catalyst component and a catalyst for olefin polymerization using the same, high productivity can be increased, and general-purpose polyolefin can be provided at low cost.

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

Claims (18)

  It can be obtained by contacting the magnesium compound (a), the tetravalent titanium halogen compound (b) and the electron donating compound (c) in the presence of a mixed solvent of an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound. A solid catalyst component for olefin polymerization.   The solid catalyst component for olefin polymerization according to claim 1, wherein the aromatic hydrocarbon compound is benzene or alkylbenzene.   The solid catalyst component for olefin polymerization according to claim 1, wherein the aliphatic hydrocarbon compound is a saturated aliphatic hydrocarbon compound that is liquid at 25 ° C.   The solid catalyst component for olefin polymerization according to claim 1, wherein the aliphatic hydrocarbon compound is a linear saturated aliphatic hydrocarbon compound having 6 to 10 carbon atoms.   The solid catalyst component for olefin polymerization according to claim 1, wherein the component (a) magnesium compound is dialkoxymagnesium.   The solid catalyst component for olefin polymerization according to claim 1, wherein the tetravalent titanium halogen compound is titanium tetrachloride.   The magnesium compound (a) is suspended in a mixed solvent of an aromatic hydrocarbon compound and an aliphatic hydrocarbon compound, and then contacted with the titanium compound (b). At any point of this time, the electron donating compound (c) is added. The solid catalyst component for olefin polymerization according to claim 1, which is obtained by contacting.   2. The solid catalyst component for olefin polymerization according to claim 1, wherein a solvent in which the weight of the aliphatic hydrocarbon compound is mixed in the mixed solvent at a ratio not exceeding the weight of the aromatic hydrocarbon compound is used.   The solid catalyst component for olefin polymerization according to claim 1 or 7, wherein the electron donating compound is a compound selected from a carboxylic acid ester or an ether compound.   The solid catalyst component for olefin polymerization according to claim 1 or 7, wherein the electron donating compound is a dicarboxylic acid diester.   2. The solid catalyst component for olefin polymerization according to claim 1, wherein the mixing ratio of the aliphatic hydrocarbon and the aromatic hydrocarbon in the mixed solvent is 1 to 99 to 48 to 52 by weight ratio.   The solid catalyst component for olefin polymerization according to claim 10, wherein the dicarboxylic acid diester is an aromatic dicarboxylic acid diester.   The solid catalyst component for olefin polymerization according to claim 1, wherein the aromatic hydrocarbon compound is a mixture of an alkylbenzene having one alkyl group and an alkylbenzene having two or more alkyl groups.   The solid catalyst component for olefin polymerization according to claim 13, wherein the alkylbenzene having two or more alkyl groups is an alkylbenzene having two or more alkyl groups having different carbon numbers. (A) The solid catalyst component according to any one of claims 1 to 14, and (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 r is a real number of 0 <p ≦ 3). A catalyst for olefin polymerization. (A) The solid catalyst component according to any one of claims 1 to 14,
(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 from an external electron donating compound.   A method for producing an olefin polymer, which is carried out in the presence of the olefin polymerization catalyst according to claim 15 or 16.   The method for producing an olefin polymer according to claim 17, wherein the olefin polymer is a propylene polymer.

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