JP5816481B2 - SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION, PROCESS FOR PRODUCING THE SAME, OLEFIN POLYMERIZATION CATALYST, AND METHOD FOR PRODUCING OLEFIN POLYMER - Google Patents

Description

  The present invention provides a solid catalyst component for olefin polymerization that can obtain a polyolefin having a high flowability at the time of melting and a wide molecular weight distribution without using a large amount of hydrogen at the time of polymerization, its production method, catalyst, and The present invention relates to a method for producing an olefin polymer.

  Conventionally, it is known that a solid catalyst component containing magnesium, titanium, an electron donor and a halogen as essential components is subjected to polymerization of olefins such as propylene. From the above solid catalyst component, organoaluminum compound and organosilicon compound Many methods for polymerizing or copolymerizing olefins in the presence of the olefin polymerization catalyst are proposed.

  Among these olefin polymerization catalysts, in particular, a solid titanium catalyst component on which an electron donor, typically phthalic acid diester, is supported, an organoaluminum compound as a promoter component, and at least one Si- Japanese Patent Application Laid-Open No. 58-83006 (Patent Document 1) exhibits excellent polymerization activity and stereospecificity when a silicon compound having an OR bond (wherein R is a hydrocarbon group) is used. JP-A-56-811 (Patent Document 2) or JP-A-63-3010 (Patent Document 3). In many reports including the above-mentioned patent documents, phthalic acid diester is preferably used as an electron donor. The polymer obtained by using the olefin polymerization catalyst as described above is melted and pelletized, and then stretched by a uniaxial or biaxial stretching machine to form a film, or molded by various molding machines. It is often used as products such as home appliances and automobile parts.

  However, a polymer obtained using such an olefin polymerization catalyst is suitable for use as a film after being drawn by a uniaxial or biaxial drawing machine, but is used for high-speed drawing or high-speed injection molding. However, the melt flowability, melt tension, and molecular weight distribution are not wide enough, and improvement has been demanded.

  As a method for obtaining such an olefin polymer having a wide molecular weight distribution, a solid catalyst component obtained by using a magnesium compound, a titanium compound and a specific phthalic acid diester is subjected to multistage polymerization of olefins. (Japanese Patent Application Laid-Open No. H10-228707). However, the above method has a limit in the length of time during which the activity of the olefin polymerization catalyst can be maintained at a high level, that is, the so-called sustainability of the polymerization activity, and in order to improve the melt fluidity of the olefin polymer, Of hydrogen had to be added.

  Further, as a method for obtaining an olefin polymer having a wide molecular weight distribution, a solid catalyst component using a magnesium compound, a titanium compound, and a monosubstituted succinic diester having a specific structure as an electron donor component is disclosed in JP-T-2003-522231. (Patent Document 5). However, the catalyst system composed of the solid catalyst component using the above succinic acid diesters, when subjected to olefin polymerization, has a broad molecular weight distribution compared to the case of using phthalic acid diesters. The olefin polymer obtained has a low melt fluidity for use in molding. Further, when a large amount of hydrogen is added at the time of polymerization in order to improve the melt fluidity, the molecular weight distribution is narrowed, and further, the performance such as stereoregularity is deteriorated.

JP 58-83006 A JP-A-56-811 JP-A 63-3010 JP 2009-57473 A Special table 2003-522231 gazette

  Accordingly, an object of the present invention is to provide a solid catalyst component for olefin polymerization, which can obtain a polyolefin having a high flowability at the time of melting and a wide molecular weight distribution in a high yield without using a large amount of hydrogen during the polymerization. The present invention provides a method, a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same.

  Under such circumstances, the present inventor has intensively studied, and as a result, a solid catalyst component for olefin polymerization using the ester compound represented by the general formula (1) as an internal electron donor solves the above technical problem. As a result, the present invention has been completed.

（式中、ｎとｍは、シクロアルキル基の環状骨格の炭素数を表し、５〜８の整数で、互いに同じであっても異なってもよい。Ｒは水素原子、ハロゲン原子、炭素数１〜８のアルキル基、ビニル基またはアリル基であり、互いに同じであっても異なってもよい。Ｒ^１およびＲ^２は、炭素数２〜４のアルキル基であり、互いに同じであっても異なってもよい。）で表わされるエステル化合物を含有することを特徴とするオレフィン類重合用固体触媒成分を提供するものである。 That is, the present invention relates to titanium, magnesium, a halogen atom and the general formula (1);

(In the formula, n and m represent the carbon number of the cyclic skeleton of the cycloalkyl group, and are integers of 5 to 8 , which may be the same or different. R is a hydrogen atom, a halogen atom, or a carbon number of 1; Are an alkyl group of ˜8, a vinyl group or an allyl group, and may be the same or different, and R ¹ and R ² are an alkyl group having 2 to 4 carbon atoms, and may be the same or different from each other; It is also possible to provide a solid catalyst component for olefin polymerization, characterized in that it contains an ester compound represented by

  The present invention also includes a step of bringing a magnesium compound, a titanium compound, and, if necessary, a halogen compound other than the titanium compound and an ester compound represented by the general formula (1) into contact with each other. A method for producing a solid catalyst component for polymerization is provided.

The present invention also provides: (I) the solid catalyst component for olefin polymerization, (II) general formula (2);
R ³ _p AlQ _3-p (2)
(Wherein, ^{R 3} represents an alkyl group having 1 to 4 carbon atoms, Q is a hydrogen atom or a halogen atom, p is a real number of 0 <p ≦ 3, when ^{R 3} is more, each ^{R 3} May be the same or different, and when Q is plural, each Q may be the same or different.) And (III) formed from an external electron donor The present invention provides a catalyst for olefin polymerization.

  The present invention also provides a method for producing an olefin polymer, characterized in that olefins are polymerized in the presence of the olefin polymerization catalyst.

  According to the present invention, during the polymerization of olefins, the problems of conventional solid catalyst components containing phthalic diesters and succinic diesters are overcome, and without using a large amount of hydrogen during polymerization, An olefin polymer having a high flowability in time and a wide molecular weight distribution characteristic can be obtained with a high yield.

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

(Description of solid catalyst component for olefin polymerization)
Examples of the halogen atom contained in the solid catalyst component for olefin polymerization of the present invention (hereinafter also simply referred to as “solid catalyst component (I)”) include fluorine, chlorine, bromine or iodine atoms, Among them, preferred is chlorine, bromine or iodine, and particularly preferred is chlorine or iodine.

  In the general formula (1), examples of the halogen atom for R include fluorine, chlorine, bromine, and iodine atoms. Among them, chlorine, bromine, and iodine are preferable, and chlorine or bromine is particularly preferable. It is. Moreover, as a C1-C8 alkyl group, it is a linear alkyl group, a C3-C8 branched alkyl group, or a C3-C8 cycloalkyl group, Specifically, a methyl group , Ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc. Is mentioned.

In the general formula (1), the alkyl group having 1 to 12 carbon atoms of ^{R 1} and ^{R 2,} include straight-chain alkyl group or branched alkyl group having 3 to 12 carbon atoms having 1 to 12 carbon atoms . Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group , An isopropyl group, an isobutyl group, a t-butyl group, an isopentyl group, a texyl group, an isononyl group, a neopentyl group, and the like, and an ethyl group, an n-propyl group, and an n-butyl group are particularly preferable.

  In the general formula (1), the cyclic skeleton of the cycloalkyl group is a cycloalkyl group having 3 to 14 carbon atoms, specifically, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, Examples include decahydronaphthalene, tetradecahydroanthracene, and tetradecahydrophenanthrene. Among these, cyclopentane, cyclohexane, and cyclooctane are particularly preferable. The cyclic skeleton of the cycloalkyl group may contain a heteroatom such as nitrogen, sulfur or oxygen.

Specific examples of the ester compound (A) represented by the general formula (1) include dimethyl 2,2′-bicyclopentanedicarboxylate, diethyl 2,2′-bicyclopentanedicarboxylate, and 2,2′-bicyclopentane. Methyl ethyl dicarboxylate, di-n-propyl 2,2′-bicyclopentanedicarboxylate, diisopropyl 2,2′-bicyclopentanedicarboxylate, ethyl n-propyl 2,2′-bicyclopentanedicarboxylate,
2,2′-bicyclopentanedicarboxylic acid ethyl isopropyl, 2,2′-bicyclopentane dicarboxylic acid di-n-butyl, 2,2′-bicyclopentane dicarboxylic acid ethyl-n-butyl, 2,2′-bicyclopentane dicarboxylic acid 2,2′-bicyclopentanedicarboxylic acid diesters such as diisobutyl acid, di-n-ethylhexyl 2,2′-bicyclopentanedicarboxylic acid, diisononyl 2,2′-bicyclopentanedicarboxylic acid; 2,2′-bicyclohexanedicarboxylic acid Dimethyl, diethyl 2,2′-bicyclohexanedicarboxylate, methyl ethyl 2,2′-bicyclohexanedicarboxylate, di-n-propyl 2,2′-bicyclohexanedicarboxylate, diisopropyl 2,2′-bicyclohexanedicarboxylate 2,2'-bicyclohexanedicarboxylic acid Tert-n-propyl, ethyl isopropyl 2,2′-bicyclohexanedicarboxylate, di-n-butyl 2,2′-bicyclohexanedicarboxylate, ethyl n-butyl 2,2′-bicyclohexanedicarboxylate, 2, 2,2′-bicyclohexanedicarboxylic acid diester such as diisobutyl 2′-bicyclohexanedicarboxylate, di-n-ethylhexyl 2,2′-bicyclohexanedicarboxylic acid, diisononyl 2,2′-bicyclohexanedicarboxylic acid; 2-cyclo Dimethyl pentane-2'-cyclohexanedicarboxylate, diethyl 2-cyclopentane-2'-cyclohexanedicarboxylate, methyl ethyl 2-cyclopentane-2'-cyclohexanedicarboxylate, di-cyclopentane-2'-cyclohexanedicarboxylate n-propyl, 2-cyclopent Diisopropyl tan-2′-cyclohexanedicarboxylate, ethyl-n-propyl 2-cyclopentane-2′-cyclohexanedicarboxylate, ethylisopropyl 2-cyclopentane-2′-cyclohexanedicarboxylate, 2-cyclopentane-2′-cyclohexane Di-n-butyl dicarboxylate, 2-cyclopentane-2′-cyclohexanedicarboxylate ethyl-n-butyl, 2-cyclopentane-2′-cyclohexanedicarboxylate diisobutyl, 2-cyclopentane-2′-cyclohexanedicarboxylate dicarboxylate 2-cyclopentane-2'-cyclohexanedicarboxylic acid diester such as 2-ethylhexyl, 2-cyclopentane-2'-cyclohexanedicarboxylic acid diisononyl, 2-cyclohexane-2'-cyclooctanedicarboxylic acid dimethyl, 2- Cyclohexane-2′-cyclooctanedicarboxylate diethyl, 2-cyclohexane-2′-cyclooctanedicarboxylate methyl ethyl, 2-cyclohexane-2′-cyclooctanedicarboxylate di-n-propyl, 2-cyclohexane-2′-cyclo Diisopropyl octanedicarboxylate, ethyl-2-n-propyl-2-cyclohexane-2′-cyclooctanedicarboxylate, ethylisopropyl 2-cyclohexane-2′-cyclooctanedicarboxylate, di-n-2-cyclohexane-2′-cyclooctanedicarboxylate -Butyl, ethyl 2-cyclohexane-2'-cyclooctanedicarboxylate-n-butyl, diisobutyl 2-cyclohexane-2'-cyclooctanedicarboxylate, di-2-ethyl 2-cyclohexane-2'-cyclooctanedicarboxylate Hexyl, 2-cyclohexane-2'-cyclooctane dicarboxylic acid diester such as 2-cyclohexane-2'-cyclooctane dicarboxylic acid diisononyl, 2-cyclopentane-2'-cyclooctane dicarboxylic acid dimethyl, 2-cyclopentane-2 ' -Diethyl cyclooctane dicarboxylate, methyl ethyl 2-cyclopentane-2'-cyclooctane dicarboxylate, di-n-propyl 2-cyclopentane-2'-cyclooctane dicarboxylate, 2-cyclopentane-2'-cyclooctane Diisopropyl dicarboxylate, 2-cyclopentane-2′-cyclooctanedicarboxylate ethyl-n-propyl, 2-cyclopentane-2′-cyclooctanedicarboxylate ethyl isopropyl, 2-cyclopentane-2′-cyclooctane dicarboxylate -N-Buchi 2-cyclopentane-2′-cyclooctanedicarboxylate ethyl-n-butyl, 2-cyclopentane-2′-cyclooctanedicarboxylate diisobutyl, 2-cyclopentane-2′-cyclooctanedicarboxylate di-2- And 2-cyclopentane-2′-cyclooctanedicarboxylic acid diesters such as ethylhexyl and 2-cyclopentane-2′-cyclooctanedicarboxylic acid diisononyl.

  Among these, 2,2′-bicyclopentane dicarboxylic acid diester and 2,2′-bicyclohexane dicarboxylic acid diester having the same number of carbon atoms n and m in the general formula (1) are preferable, and particularly preferable. Is a 2,2′-bicyclohexanedicarboxylic acid diester, specifically, 2,2′-bicyclohexanedicarboxylic acid diethyl, 2,2′-bicyclohexanedicarboxylic acid di-n-propyl, 2,2′- These are di-n-butyl bicyclohexanedicarboxylate, ethyl-n-butyl 2,2′-bicyclohexanedicarboxylate, and diisobutyl 2,2′-bicyclohexanedicarboxylate. These compounds can be used alone or in combination of two or more.

  The solid catalyst component (I) in the present invention may be referred to as an electron donating compound other than the ester compound (A) represented by the general formula (1) (hereinafter referred to as “electron donating compound (D)”). ) May be included. Examples of such electron donating compounds (D) include acid halides, acid amides, nitriles, acid anhydrides, diether compounds and phthalic acid esters, succinic acid esters, maleic acid esters, and malonic acid esters. Organic acid esters other than ester compounds (A) such as carboxylic acid esters, glutaric acid esters, cyclohexane dicarboxylic acid esters, and cyclohexene dicarboxylic acid esters. Two or more of these electron donating compounds (D) can be used in combination.

The solid catalyst component (I) in the present invention may contain polysiloxane (hereinafter sometimes simply referred to as “polysiloxane (E)”). By using polysiloxane, the stereoregularity or crystallinity of the produced polymer can be improved, and further the fine powder of the produced polymer can be reduced. Polysiloxane is a polymer having a siloxane bond (—Si—O—Si— 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), more preferably 0.03 to ⁵ cm ² / s (3 to 500 centistokes), which is a liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature.

  As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used. As the partially hydrogenated polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylcyclotrimethyl is used. Examples thereof include siloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane.

  Further, the content of titanium, magnesium, halogen atom and ester compound (A) in the solid catalyst component (I) in the present invention is not particularly specified, but preferably 0.1 to 10% by weight of titanium, preferably 0 0.5 to 8.0 wt%, more preferably 1.0 to 8.0 wt%, magnesium is 10 to 70 wt%, more preferably 10 to 50 wt%, particularly preferably 15 to 40 wt%, More preferably, it is 15 to 25% by weight, the halogen atom is 20 to 88% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, still more preferably 45 to 75% by weight, The total amount of the ester compound (A) is 0.5 to 40% by weight, more preferably 1 to 30% by weight, and particularly preferably 2 to 25% by weight.

  The solid catalyst component (I) of the present invention has, for example, a titanium content of 3 to 8% by weight, a magnesium content of 15 to 25% by weight, a halogen atom content of 45 to 75% by weight, an ester compound ( When the content of A) is 2 to 20% by weight, the performance as a solid catalyst component can be exerted in a well-balanced manner, the hydrogen activity and the polymerization activity are high, and the high melt flowability is achieved with a smaller amount of hydrogen. In addition, a polymer having a wide molecular weight distribution can be obtained with good yield.

(Description of production method of solid catalyst component for olefin polymerization)
The production method of the solid catalyst component (I) for olefin polymerization of the present invention includes the following magnesium compound, titanium compound, and if necessary, a halogen compound other than the titanium compound and the ester compound of the general formula (1) ( Prepared by bringing A) into contact with each other.

  Examples of the magnesium compound used in the method for producing a solid catalyst component of the present invention (hereinafter sometimes simply referred to as “magnesium compound (B)”) include magnesium dihalide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium. , One or more selected from diaryloxymagnesium, halogenated alkoxymagnesium, fatty acid magnesium and the like. 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 dialkoxymagnesiums may be prepared by reacting metal magnesium with alcohol in the presence of halogen or a halogen-containing metal compound. One or more of the above dialkoxymagnesium can be used in combination.

  Furthermore, in the preparation of the solid catalyst component of the present invention, when dialkoxymagnesium is used, it is preferably in the form of granules or powder, and the shape can be indefinite or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrower particle size distribution is obtained during the polymerization, and the handling operability of the produced polymer powder during the polymerization operation is improved and the product weight is increased. Problems such as blockage caused by fine powder contained in the coalesced powder are solved.

  The spherical dialkoxymagnesium does not necessarily have a true spherical shape, and an elliptical shape or a potato shape 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 diameter of the dialkoxymagnesium is 1 to 1 in terms of an average particle diameter D50 (50% in the cumulative particle size distribution) when measured using a laser light scattering diffraction particle size analyzer. The thing of 200 micrometers is preferable and the thing of 5-150 micrometers is more preferable. In the case of spherical dialkoxymagnesium, the average particle size is preferably 1 to 100 μm, more preferably 5 to 50 μm, and even more preferably 10 to 40 μm. Further, as for the particle size, those having a small particle size distribution with less fine powder and coarse powder are desirable. Specifically, the particle size of 5 μm or less is preferably 20% or less, more preferably 10% or less when measured using a laser light scattering diffraction particle size measuring instrument. On the other hand, particles having a particle size of 100 μm or more are preferably 10% or less, more preferably 5% or less.

  Furthermore, the particle size distribution is ln (D90 / D10) (where D90 is the cumulative particle size in the volume cumulative particle size distribution and 90% of the particle size, and D10 is the cumulative particle size in the volume cumulative particle size distribution of 10%). Is preferably 3 or less, more preferably 2 or less.

  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, as the magnesium compound (B), either a solution-like magnesium compound or a magnesium compound suspension can be used. When the magnesium compound (B) is a solid, it is dissolved in a solvent having a solubilizing ability for the magnesium compound (B) to form a solution-like magnesium compound, or has a solubilizing ability for the magnesium compound (B). Suspend in a non-solvent and use as a magnesium compound suspension. When the magnesium compound (B) is a liquid, it can be used as it is as a solution-like magnesium compound, or it can be dissolved in a solvent capable of solubilizing the magnesium compound and used as a solution-like magnesium compound. .

  Examples of the compound that can solubilize the solid magnesium compound (B) include at least one compound selected from the group consisting of alcohols, ethers, and esters. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropyl benzyl alcohol Alcohols having 1 to 18 carbon atoms such as ethylene glycol; halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether , Tetrahydrofuran, ethyl benzyl ether, dibutyl ether, anisole, diphenyl ether, etc. Ethers having 2 to 20 elementary atoms; metal alkoxides such as tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium, tetrahexoxy titanium, tetrabutoxy zirconium and tetraethoxy zirconium Of these, alcohols such as ethanol, propanol, butanol and 2-ethylhexanol are preferable, and 2-ethylhexanol is particularly preferable.

  On the other hand, as a medium that does not have the solubilizing ability of the magnesium compound (B), a saturated hydrocarbon solvent or an unsaturated hydrocarbon solvent that does not dissolve the magnesium compound is used. Saturated hydrocarbon solvents or unsaturated hydrocarbon solvents have high safety and industrial versatility, and are specifically linear or branched having a boiling point of 50 to 200 ° C. such as hexane, heptane, decane, and methylheptane. Examples include aliphatic hydrocarbon compounds, cycloaliphatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as cyclohexane, ethylcyclohexane, decahydronaphthalene, and aromatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as toluene, xylene, and ethylbenzene. Of these, linear aliphatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as hexane, heptane, and decane, and aromatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as toluene, xylene, and ethylbenzene are preferably used. Moreover, these may be used independently or may be used in mixture of 2 or more types.

Examples of the titanium compound (hereinafter sometimes referred to as “titanium compound (C)”) used for the preparation of the component (I) in the present invention include, for example, the general formula (5);
Ti (OR ⁹ ) _j X _4-j (5)
(R ⁹ is a hydrocarbon group having 1 to 10 carbon atoms, and when a plurality of OR ⁹ groups are present, the plurality of R ⁹ may be the same or different, X is a halogen atom, In the case where a plurality of are present, each X may be the same or different, and j is 0 or an integer of 1 to 4.).

  The tetravalent titanium compound represented by the general formula (5) is one or more compounds selected from the group consisting of an alkoxy titanium, a titanium halide, and an alkoxy titanium halide group. Specifically, titanium tetrahalide, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and other titanium tetrahalides, alkoxy titanium halides such as methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxy Alkoxy titanium trihalides such as titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, dialkoxy titanium dihalide, trimethoxy titanium chloride, triethoxy titanium chloride, Trialkoxy titanium halides such as tripropoxy titanium chloride and tri-n-butoxy titanium chloride are exemplified. Among these, halogen-containing titanium compounds are preferably used, and titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide are preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Furthermore, the tetravalent titanium compound represented by the general formula (5) may be used after diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

  In the preparation of the solid catalyst component (I) of the present invention, a halogen compound other than the titanium compound (C) may be used as necessary. Examples of such a halogen compound include a tetravalent halogen-containing silicon compound. More specifically, tetrachlorosilane (silicon tetrachloride), silane tetrahalides such as tetrabromosilane, methoxytrichlorosilane, ethoxytrichlorosilane, propoxytrichlorosilane, n-butoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, Examples include alkoxy group-containing halogenated silanes such as dipropoxydichlorosilane, di-n-butoxydichlorosilane, trimethoxychlorosilane, triethoxychlorosilane, tripropoxychlorosilane, and tri-n-butoxychlorosilane.

  The ester compound (A) used in the method for producing the solid catalyst component (I) of the present invention and the electron donating compound (D) used as necessary are the ester compound of the solid catalyst component (I) of the present invention. This is the same as (A) and the electron donating compound (D), and the description thereof is omitted. Further, the polysiloxane (E) used as necessary in the production method of the solid catalyst component (I) of the present invention is the same as the polysiloxane (E) of the solid catalyst component (I) of the present invention. Description is omitted.

  In the present invention, suitable methods for producing the solid catalyst component (I) include, for example, a method of co-grinding a solid magnesium compound having no reducing property, an ester compound (A) and a titanium halide, or an adduct such as alcohol. A halogenated magnesium compound, ester compound (A) and titanium halide in the presence of an inert hydrocarbon solvent, dialkoxymagnesium, ester compound (A) and titanium halide in an inert hydrocarbon solvent Examples thereof include a method in which the solid catalyst is brought into contact, a method in which a reducing magnesium compound, an ester compound (A) and a titanium halide are brought into contact with each other to precipitate a solid catalyst. Below, the specific preparation method of the solid catalyst component (I) for olefin polymerization is illustrated. In the following methods (1) to (16), in addition to the ester compound (A), an electron donating compound (D) other than the ester compound (A) may be used in combination. Furthermore, you may perform the said contact in coexistence of other reaction reagents, such as silicon, phosphorus, aluminum, and surfactant, for example.

(1) After dissolving magnesium halide in an alkoxytitanium compound, an organosilicon compound is contacted to obtain a solid product, the solid product and titanium halide are reacted, and then the ester compound (A) is contacted. To prepare a solid catalyst component (I) for olefin polymerization. At this time, the component (I) can be further subjected to preliminary polymerization treatment with an organoaluminum compound, an organosilicon compound and olefins.
(2) After reacting magnesium halide and alcohol to make a uniform solution, the solid solution is contacted with titanium halide to obtain a solid, and the solid is further contacted with titanium halide to polymerize olefins. A solid catalyst component (I) for olefin polymerization is prepared by contacting an ester compound (A) at any stage where the titanium halide is contacted. Method.
(3) An organomagnesium compound is synthesized by reacting magnesium metal, butyl chloride and dialkyl ether, and the organomagnesium compound is contacted with alkoxytitanium to obtain a solid product, and the solid product is converted to an ester compound (A ) And a titanium halide are contact-reacted to prepare a solid catalyst component (I) for olefin polymerization. At this time, the solid catalyst component (I) can be prepared by subjecting the solid catalyst component (I) to preliminary polymerization with an organoaluminum compound, an organosilicon compound and an olefin.
(4) An organomagnesium compound such as dialkylmagnesium and an organoaluminum compound are brought into contact with alcohol in the presence of a hydrocarbon solvent to form a homogeneous solution, and a silicon compound such as silicon tetrachloride is brought into contact with this solution to form a solid. Then, the solid product is contacted with titanium halide and the ester compound (A) in the presence of an aromatic hydrocarbon solvent, and then further contacted with titanium tetrachloride to obtain a solid catalyst for olefin polymerization. Method for obtaining component (I).
(5) Magnesium chloride, tetraalkoxytitanium and aliphatic alcohol are contact-reacted in the presence of a hydrocarbon solvent to obtain a homogeneous solution, and after contacting the solution and titanium halide, the temperature is raised to precipitate a solid, A method in which an ester compound (A) is brought into contact with the solid and further reacted with titanium halide to obtain a solid catalyst component (I) for olefin polymerization.
(6) Metal magnesium powder, alkyl monohalogen compound and iodine are contact-reacted, and then tetraalkoxytitanium, acid halide and aliphatic alcohol are contact-reacted in the presence of a hydrocarbon solvent to form a homogeneous solution, and the solution After adding titanium tetrachloride to the mixture, the temperature was raised to precipitate a solid product. The solid product was brought into contact with the ester compound (A), and further reacted with titanium tetrachloride to react with the solid catalyst component (I ).
(7) After suspending dialkoxymagnesium in a hydrocarbon solvent, the temperature is raised after contact with titanium tetrachloride, and contact with the ester compound (A) to obtain a solid product, and the solid product is carbonized. A method of preparing the solid catalyst component (I) for olefin polymerization by washing with a hydrogen solvent and then again contacting with titanium tetrachloride in the presence of a hydrocarbon solvent. In this case, the solid catalyst component (I) can be heat-treated in the presence or absence of a hydrocarbon solvent.
(8) After suspending dialkoxymagnesium in a hydrocarbon solvent, contact reaction with titanium halide and ester compound (A) to obtain a solid product, and washing the solid product with an inert organic solvent And a method of obtaining a solid catalyst component (I) for olefin polymerization by contacting and reacting with titanium halide again in the presence of a hydrocarbon solvent. In this case, the solid catalyst component (I) and the titanium halide can be contacted twice or more.
(9) Dialkoxymagnesium, calcium chloride, and alkoxy group-containing silicon compound are co-ground, and the obtained pulverized solid is suspended in a hydrocarbon solvent, and then contacted with titanium halide and ester compound (A). Then, a method for preparing a solid catalyst component (I) for olefin polymerization by further contacting with a titanium halide.
(10) The dialkoxymagnesium and the ester compound (A) are suspended in a hydrocarbon solvent, and the suspension is contacted and reacted with a titanium halide to obtain a solid product. The solid product is reacted with a hydrocarbon solvent. A method of obtaining a solid catalyst component (I) for olefin polymerization by contacting titanium halide in the presence of a hydrocarbon solvent after washing.
(11) A solid catalyst component (I) for olefin polymerization is prepared by contacting a fatty acid magnesium such as magnesium stearate with a titanium halide and an ester compound (A) and then further contacting with a titanium halide. Method.
(12) The dialkoxymagnesium is suspended in a hydrocarbon solvent, brought into contact with titanium halide, heated, and contacted with the ester compound (A) to obtain a solid product, which is then converted into a hydrocarbon. A method of preparing a solid catalyst component (I) for olefin polymerization by contacting with titanium halide again in the presence of a hydrocarbon solvent after washing with a solvent, and contacting aluminum chloride at any stage. To prepare a solid catalyst component (I) for olefin polymerization.
(13) Dialkoxymagnesium, 2-ethylhexyl alcohol and carbon dioxide are contact-reacted in the presence of a hydrocarbon solvent to obtain a homogeneous solution, and this solution is contacted with titanium halide and the ester compound (A) to form a solid product. Further, this solid product is dissolved in tetrahydrofuran, and then a solid product is further precipitated. The solid product is contacted with titanium halide, and if necessary, contact reaction with titanium halide is repeated to obtain an olefin. A method for preparing a solid catalyst component (I) for polymerization. At this time, for example, a silicon compound such as tetrabutoxysilane can be used at any stage of the contact reaction and dissolution.
(14) After suspending magnesium chloride, an organic epoxy compound and a phosphoric acid compound in a hydrocarbon solvent, the mixture is heated to obtain a homogeneous solution, and this solution is contacted with a carboxylic acid anhydride and a titanium halide to form a solid. A product is obtained, the solid compound is brought into contact with the ester compound (A) and reacted, and the resulting reaction product is washed with a hydrocarbon solvent and then contacted again with a titanium halide in the presence of the hydrocarbon solvent. To obtain a solid catalyst component (I) for olefin polymerization.
(15) A dialkoxymagnesium, a titanium compound and an ester compound (A) are contact-reacted in the presence of a hydrocarbon solvent, and the resulting reaction product is contacted with a silicon compound such as polysiloxane, and titanium halide is further reacted. A method for obtaining a solid catalyst component (I) for olefin polymerization by contacting a metal salt of an organic acid and then contacting a titanium halide again.
(16) The dialkoxymagnesium and the ester compound (A) are suspended in a hydrocarbon solvent, and then heated to be brought into contact with the silicon halide, and then brought into contact with the titanium halide to obtain a solid product. A method for preparing the solid catalyst component (I) for olefin polymerization by washing the product with a hydrocarbon solvent and then bringing the product into contact with a titanium halide again in the presence of the hydrocarbon solvent. At this time, the solid catalyst component (I) may be heat-treated in the presence or absence of a hydrocarbon solvent.

  In addition, in order to further improve the polymerization activity at the time of olefin polymerization and the stereoregularity of the produced polymer, a titanium halide is newly added to the solid catalyst component (I) after washing in the methods (1) to (16). And a hydrocarbon solvent are contacted at 20 to 100 ° C., the temperature is raised, a reaction treatment (secondary reaction treatment) is performed, and then an operation of washing with a liquid inert organic solvent at room temperature is repeated 1 to 10 times. May be.

  As the method for preparing component (I) in the present invention, any of the above methods can be suitably used, and among these, (1), (2), (3), (4), (5), The method (7), (8) or (10) is preferable, and the method (2), (3), (4), (7), (8), (10) is an olefin having high stereoregularity. It is particularly preferable in that a solid catalyst component for homopolymerization is obtained. The most preferred preparation method is to suspend dialkoxymagnesium and the ester compound (A) in a hydrocarbon solvent selected from linear hydrocarbons or branched aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons. The suspension is added to titanium halide and reacted to obtain a solid product. The solid product is washed with a hydrocarbon solvent, and further contacted with titanium halide in the presence of a hydrocarbon solvent. This is a method for obtaining a solid catalyst component (I) for olefin polymerization.

  The obtained solid catalyst component (I) for olefin polymerization is a powdered solid component by removing the remaining solvent until the weight ratio to the solid component is 1/3 or less, preferably 1/20 to 1/6. In addition, it is preferable to remove fine powder having a particle size of 11 μm or less mixed in the powder solid component by means such as sieving or air classification.

  The amount of each component used in preparing the solid catalyst component (I) varies depending on the preparation method and cannot be defined unconditionally. For example, a tetravalent titanium halogen compound (C) per mole of the magnesium compound (B) can be used. ) Is 0.5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the ester compound (A) or the sum of the ester compound (A) and the electron donating compound (D) The amount is 0.01 to 10 mol, preferably 0.01 to 1 mol, more preferably 0.02 to 0.6 mol, and the solvent is 0.001 to 500 mol, preferably 0.001 to 100 mol, More preferably, it is 0.005-10 mol, and polysiloxane (E) is 0.01-100 g, Preferably it is 0.05-80 g, More preferably, it is 1-50 g.

In the preparation of the solid catalyst component (I) for olefin polymerization according to the present invention, when the dialkoxymagnesium, titanium compound, halogen compound other than the titanium compound and the ester compound (A) are contacted and reacted, the ester compound (A) There may be a transesterification reaction in which an alkoxy group contained in an ester residue is exchanged with an alkoxy group contained in a halogen compound other than a dialkoxymagnesium component or a titanium compound. For example, when diethoxymagnesium is used as dialkoxymagnesium and R ¹ and R ^{2 of} the ester compound (A) are butyl groups, the solid catalyst component (I) contains an ester compound (A), an ester compound (A 3): an asymmetric ester compound in which either the butyl group of R ¹ or R ² is substituted with an ethyl group and an ester compound in which R ¹ and R ² of the ester compound (A) are both substituted with an ethyl group There will be an electron donor.

(Description of olefin polymerization catalyst)
The catalyst for olefin polymerization of the present invention comprises (I) a solid catalyst component, (II) an organoaluminum compound (hereinafter sometimes referred to as “organoaluminum compound (F)”) and (III) an external electron donating compound ( Hereinafter, the catalyst for olefin polymerization can be formed simply by contacting with "external electron donating compound (G)", and polymerization or copolymerization of olefins can be carried out in the presence of the catalyst. .

(II) As organoaluminum compound (F), following general formula (2);
R ³ _p AlQ _3-p (2)
(R ³ represents an alkyl group having 1 to 6 carbon atoms, Q represents a hydrogen atom or a halogen atom, p is a real number of 0 <p ≦ 3, and when a plurality of R ³ are present, each R ³ is the same. or different even if the Q there is a plurality, if each Q is a compound represented by a may be different even) the same is not particularly limited, as R ³ is ethyl Group is preferably an isobutyl group, and Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, and q is preferably 2 or 3, and particularly preferably 3.

  Specific examples of such organoaluminum compound (F) include trialkylaluminum such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, triisobutylaluminum, diethylaluminum chloride, diethyl Examples include aluminum halides such as aluminum bromide, diethylaluminum hydride, etc. Among them, alkylaluminum halides such as diethylaluminum chloride, or trialkylaluminums such as triethylaluminum, tri-n-butylaluminum and triisobutylaluminum are preferably used. Particularly preferred are triethylaluminum and triisobutylaluminum. These aluminum compounds can be used alone or in combination of two or more.

  Specific examples of such organoaluminum compound (F) include trialkylaluminum such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, triisobutylaluminum, diethylaluminum chloride, diethyl Examples include aluminum halides such as aluminum bromide, diethylaluminum hydride, etc. Among them, alkylaluminum halides such as diethylaluminum chloride, or trialkylaluminums such as triethylaluminum, tri-n-butylaluminum and triisobutylaluminum are preferably used. Particularly preferred are triethylaluminum and triisobutylaluminum. These aluminum compounds can be used alone or in combination of two or more.

  Examples of the (III) external electron donating compound used in forming the olefin polymerization catalyst of the present invention include organic compounds containing oxygen atoms or nitrogen atoms, such as alcohols, phenols, ethers, Examples thereof include esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, and organosilicon compounds. Among these, ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, the above ester compound (A), etc. Preferred are esters, 1,3-diethers, organosilicon compounds containing Si—O—C bonds, and aminosilane compounds containing Si—N—C bonds, particularly organosilicon compounds having Si—O—C bonds, Si An aminosilane compound having a —N—C bond and 2,2′-biphenyldicarboxylic acid ester are preferred.

Among the external electron donating compounds of the above (III), as the organosilicon compound having a Si—O—C bond, the following general formula (3);
R ⁴ _q Si (OR ⁵ ) _4-q (3)
(In the formula, R ⁴ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, an alkylamino group having 1 to 12 carbon atoms, or a carbon number. Any one of 1 to 12 dialkylamino groups, which may be the same or different, R ⁵ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a vinyl group, or an allyl group; And an aralkyl group, which may be the same or different, and q is an integer of 0 ≦ q ≦ 3).

Among the external electron donating compounds of the above (III), as the aminosilane compound having a Si—N—C bond, the following general formula (4);
(R ⁶ R ⁷ N) _s SiR ⁸ _4-s (4)
(Wherein R ⁶ and R ⁷ are a hydrogen atom, a straight chain having 1 to 20 carbon atoms, or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, or a cycloalkyl having 3 to 20 carbon atoms. R ⁶ and R ⁷ may be the same or different, and R ⁶ and R ⁷ may be bonded to each other to form a ring, and R ⁸ is a straight chain having 1 to 20 carbon atoms. Or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a linear or branched alkoxy group having 1 to 20 carbon atoms, a vinyloxy group, an allyloxy group, and a cycloalkyl group having 3 to 20 carbon atoms. , aryl group, aryloxy group, and shows their derivatives, if R ⁸ is plural, R ⁸ is an integer of good .s be the same or different 1 to 3.) aminosilane compound represented by the Is mentioned.

  Examples of such organosilicon compounds include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, alkyl (cycloalkyl) alkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, Cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane, trialkyl (alkylamino) silane, etc. Specifically, phenyltrimethoxysilane, t-butyltrimethoxysilane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane Diisopentyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxy Silane, tetrabutoxysilane, bis (ethylamino) methylethylsilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methyl Cyclopentylamino) methylsilane, diethylaminotriethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (par Hydroisoquinolino) dimethoxysilane, bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, and the like. Among them, phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopropyl Dimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis (ethylamino) silane, bis (ethyl Amino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (perhydroisoquinolino) dimethoxysilane, Diethylaminotriethoxysilane or the like is preferably used.

  Of the external electron donating compounds of (III) above, as the ester compound (A), the same compounds as the ester compound (A) of the solid catalyst component (I) of the present invention can be used. '-Bicyclohexanedicarboxylic acid diester is preferred. Examples of such 2,2′-bicyclohexanedicarboxylic acid ester include diethyl 2,2′-bicyclohexanedicarboxylate, di-n-propyl 2,2′-bicyclohexanedicarboxylate, and 2,2′-bicyclohexanedicarboxylic acid. Di-n-butyl acid, ethyl 2,2′-bicyclohexanedicarboxylate-n-butyl, diisobutyl 2,2′-bicyclohexanedicarboxylate and the like are preferably used.

  In addition, the external electron donating compound (III) may be used in combination of two or more. For example, two or more types can be selected from the organosilicon compound represented by the general formula (3) and the organosilicon compound represented by the general formula (4) and used in combination. The external electron donating compound (III) is an organosilicon compound represented by the general formula (3), an organosilicon compound represented by the general formula (4), or a 2, Two or more kinds selected from 1,3-diethers such as 2′-biphenyldicarboxylic acid diester, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, and 9,9-bis (methoxymethyl) fluorene It can also be used in combination.

  In the present invention, olefins are polymerized or copolymerized in the presence of the olefin polymerization 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. Ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene.

  When propylene is polymerized, it can be copolymerized with other olefins. 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 ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the organoaluminum compound (F) is contained in the solid catalyst component (I). It is used in the range of 1 to 2000 mol, preferably 50 to 1000 mol, per 1 mol of titanium atom. The external electron donating compound (G) 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 (F). Used.

  The order of contact of each component is arbitrary, but the organoaluminum compound (F) is first charged into the polymerization system, and then the external electron donating compound (G) is contacted and then the solid catalyst component (I) is contacted. It is desirable. The polymerization of olefin in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Furthermore, in the present invention, when polymerizing an olefin using a catalyst containing a solid catalyst component for olefin polymerization, an organoaluminum compound, and an external electron donating compound (also referred to as main polymerization), catalytic activity, stereoregularity and In order to further improve the particle properties and the like of the polymer produced, it is desirable to carry out 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 components and monomers is arbitrary, but preferably, the organoaluminum compound (F) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, Next, after contacting the solid catalyst component (I), an olefin such as propylene, or a mixture of propylene and one or more other olefins is contacted.

  When prepolymerization is performed by combining the external electron donating compound (G), the organoaluminum compound (F) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then externally. A method in which the electron donating compound (G) is contacted and the solid catalyst component (I) is further contacted, and then an olefin such as propylene, or a mixture of propylene and one or more other olefins is contacted. 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 proportion of the polypropylene part is 20 to 80% by weight in the first stage, and then in the second stage, ethylene and propylene or other α -Olefin is introduced and polymerized so that the proportion of rubber part such as ethylene-propylene rubber (EPR) is 20 to 80% by weight. The polymerization temperatures in the first and second stages are both 200 ° C. or less, preferably 100 ° C. or less, and the polymerization pressure is 10 MPa or less, preferably 5 MPa or less. In the case of polymerization time in each polymerization stage or continuous polymerization, the residence time is usually 1 minute to 5 hours.

  Examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane and heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas phase polymerization method using substantially no solvent. It is done. Preferred polymerization methods are bulk polymerization and gas phase polymerization.

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

<Preparation of solid catalyst component (I-1)>
20 g of diethoxymagnesium, 140 ml of toluene, 40 ml of titanium tetrachloride, di-n-butyl 2,2-bicyclohexanedicarboxylate previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas A 2 ml (14 mmol) suspension was heated to 100 ° C. and then reacted for 2 hours with stirring. Then, after standing, the supernatant was removed, and the operation of washing the obtained solid product with 200 ml of toluene at 90 ° C. was repeated 4 times, and then 80 ml of toluene and 20 ml of titanium tetrachloride were newly added and stirred. The reaction was then performed at 100 ° C. for 30 minutes (second reaction treatment). This second reaction process was repeated two more times. Next, the product was washed 7 times with 150 ml of 60 ° C. heptane, filtered and dried to obtain a powdered solid catalyst component (I-1).

  The titanium content in the solid catalyst component was measured and found to be 3.1% by weight. Further, in the solid catalyst component, di-n-butyl 2,2-bicyclohexanedicarboxylate was 13.6 wt%, ethylbutyl 2,2-bicyclohexanedicarboxylate was 1.0 wt%, 2,2-bicyclohexanedicarboxylic acid Each contained 0.5 wt% of diethyl acid.

<Formation of polymerization catalyst and polymerization of olefin>
In an autoclave with a stirrer with an internal volume of 2.0 liters completely substituted with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of dicyclopentyldimethoxysilane, and the solid catalyst component obtained above in terms of titanium atoms A polymerization catalyst was prepared by charging 0.0026 mmol. Next, 2.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged into the autoclave, preliminarily polymerized with stirring at 20 ° C. for 5 minutes, and then heated to 70 ° C. for 1 hour. By performing, a polymer (polypropylene) was obtained.

<Evaluation of polymer>
The polymerization activity per gram of the solid catalyst component, the xylene soluble content (XS) of the obtained polymer, the bulk density of the polymer, the melt flowability (MFR) of the polymer and the molecular weight distribution of the polymer were measured by the following methods. . The results are shown in Table 1.

(Polymerization activity per gram of solid catalyst component)
The polymerization activity per gram of the solid catalyst component was determined by the following formula.
Polymerization activity (g-pp / g-catalyst) = mass of polymer (g) / mass of solid catalyst component (g)

(Measurement of xylene solubles (XS) of polymer)
A flask equipped with a stirrer was charged with 4.0 g of a polymer (polypropylene) and 200 ml of p-xylene, and the external temperature was set to be equal to or 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 polymer was dissolved over 2 hours. Thereafter, the liquid temperature was cooled to 23 ° C. over 1 hour, and insoluble components and dissolved components were separated by filtration. A solution of the dissolved component was collected, p-xylene was distilled off by heating under reduced pressure, and the resulting residue was defined as xylene solubles (XS), and the weight was relative to the polymer (polypropylene) (wt% ).

(Polymer melt flowability (MFR))
The melt flow rate (MFR) indicating the melt flowability of the polymer was measured according to ASTM D 1238 and JIS K 7210.

(Measurement of molecular weight distribution of polymer)
The molecular weight distribution of the polymer is determined by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn determined by gel permeation chromatography (GPC) (Alliance GPC / V2000, manufactured by Waters) under the following conditions. evaluated.
Solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Column: Showa Denko UT-806 × 3, HT-803 × 1 Sample concentration: 1 mg / mL-ODCB (10 mg / 10 ml-ODCB)
Injection volume: 0.5ml
Flow rate: 1.0ml / min

(Measurement of bulk density (BD))
The bulk density of the polymer was measured according to JIS K 6721.

(Measurement of 2,2′-bicyclohexanedicarboxylic acid diester compound)
The content of the 2,2-bicyclohexanedicarboxylic acid diester compound contained in the solid catalyst component is determined by measuring under the following conditions using gas chromatography (manufactured by Shimadzu Corporation, GC-14B). It was. In addition, the number of moles of each component was obtained from a measurement result of gas chromatography using a calibration curve measured in advance at a known concentration.
Column: packed column (φ2.6 × 2.1 m, Silicone SE-30 10%, Chromosorb WAW DMCS 80/100, manufactured by GL Sciences Inc.)
・ Detector: FID (Frame Ionization Detector)
Carrier gas: helium, flow rate 40 ml / min Measurement temperature: vaporization chamber 280 ° C, column 225 ° C, detector 280 ° C

  Preparation of a solid catalyst component in the same manner as in Example 1, except that the same mole of diethyl 2,2′-bicyclohexanedicarboxylate was used instead of di-n-butyl 2,2′-bicyclohexanedicarboxylate, Formation of a polymerization catalyst, olefin polymerization, and evaluation of the polymer were performed. The titanium content in the obtained solid catalyst component was 2.8% by weight. The results are shown in Table 1.

  A solid catalyst was prepared in the same manner as in Example 1 except that the same mole of di-n-propyl 2,2'-bicyclohexanedicarboxylate was used instead of di-n-butyl 2,2'-bicyclohexanedicarboxylate. Component preparation, polymerization catalyst formation, olefin polymerization and polymer evaluation were performed. The titanium content in the obtained solid catalyst component was 3.0% by weight. The results are shown in Table 1.

Comparative Example 1
In the same manner as in Example 1 except that the same mole of diethyl n-hexyl succinate was used in place of di-n-butyl 2,2′-bicyclohexanedicarboxylate, the preparation of the solid catalyst component, the polymerization catalyst Formation, olefin polymerization and polymer evaluation were performed. In addition, titanium content in the obtained solid catalyst component was 3.5 weight%. The results are shown in Table 1.

Comparative Example 2
Preparation of a solid catalyst component, polymerization catalyst in the same manner as in Example 1 except that the same mole of di-n-butyl adipate was used instead of di-n-butyl 2,2′-bicyclohexanedicarboxylate Formation, olefin polymerization, and evaluation of the resulting polymer. The titanium content in the obtained solid catalyst component was 3.4% by weight. The results are shown in Table 1.

Comparative Example 3
Preparation of solid catalyst component and polymerization catalyst in the same manner as in Example 1 except that the same mole of di-n-butyl phthalate was used instead of di-n-butyl 2,2'-bicyclohexanedicarboxylate , Polymerization of olefins and evaluation of the resulting polymers. The titanium content in the obtained solid catalyst component was 3.4% by weight. The results are shown in Table 1.

  Instead of 5.2 ml (14 mmol) of di-n-butyl 2,2′-bicyclohexanedicarboxylate, 7.6 ml (20 ml) of di-n-butyl 2,2′-bicyclohexanedicarboxylate was added. The solid catalyst component was prepared, the polymerization catalyst was formed, the olefin was polymerized, and the obtained polymer was evaluated in the same manner as in Example 1 except that the amount was changed to (mmol). The titanium content in the obtained solid catalyst component was 2.5% by weight. The content of the electron donor in the solid catalyst component was 14.2 wt% for 2,2′-bicyclohexanedicarboxylate di-n-butyl, and 1.3 wt% for ethyl butyl 2,2′-bicyclohexanedicarboxylate. , Diethyl 2,2′-bicyclohexanedicarboxylate was 0.7 wt%. The results are shown in Table 1.

  The solid catalyst component was prepared, the olefin was polymerized, and the resulting polymer was evaluated in the same manner as in Example 1, except that n-heptane was used instead of toluene, and the reaction temperature was 90 ° C. instead of 100 ° C. went. The titanium content in the obtained solid catalyst component was 3.6% by weight. The results are shown in Table 1.

<Preparation of solid catalyst component (I-2)>
20 g of diethoxymagnesium, 160 ml of toluene, 40 ml of titanium tetrachloride, di-n 2,2′-bicyclohexanedicarboxylic acid previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas A suspension of 5.2 ml (14 mmol) of butyl was reacted with stirring for 2 hours while maintaining a temperature of 100 ° C. Then, after standing, the supernatant was removed, and the operation of washing the obtained solid product with 200 ml of toluene at 90 ° C. was repeated 4 times, and then 40 ml of titanium tetrachloride and 160 ml of toluene were newly added, and then 110 ° C. The reaction was continued for 2 hours with stirring while maintaining the temperature at 110 ° C. Then, after standing, the supernatant was removed, and the operation of washing the resulting solid product with 200 ml of 70 ° C. n-heptane was repeated three times. The operation of washing with 200 ml of heptane was repeated four times, and the resulting solid product was dried under reduced pressure to obtain a powdery solid catalyst component (I-2). The titanium content in the obtained solid catalyst component was 2.7% by weight.

<Formation of polymerization catalyst, polymerization of olefin and evaluation of polymer>
In the same manner as in Example 1, except that the solid catalyst component (I-2) was used instead of the solid catalyst component (I-1), the formation of a polymerization catalyst, the polymerization of the olefin, and the obtained polymer Evaluation was performed. The results are shown in Table 1.

<Preparation of solid catalyst component (I-3)>
4. In a 500 ml round bottom flask equipped with a stirrer and fully substituted with nitrogen gas, 20 g of diethoxymagnesium, 160 ml of toluene, 40 ml of titanium tetrachloride, di-n-butyl 2,2′-bicyclohexanedicarboxylate 2 ml (14 mmol) of the suspension was heated, and when the liquid temperature of the suspension reached 60 ° C. and 80 ° C., 1.2 ml (3.2 mmol) of 2, After the addition of di-n-butyl 2′-bicyclohexanedicarboxylate, the temperature was further raised to 100 ° C., and the reaction was continued for 2 hours while stirring at 100 ° C. Then, after standing, the supernatant was removed, and the operation of washing the obtained solid product with 200 ml of toluene at 90 ° C. was repeated 4 times, and then 40 ml of titanium tetrachloride and 160 ml of toluene were newly added, and then 110 ° C. The reaction was continued for 2 hours with stirring while maintaining the temperature at 110 ° C. After the reaction was completed, the supernatant was removed by removing the supernatant, and the operation of washing the resulting solid product with 200 ml of toluene at 90 ° C. was repeated 4 times. Then, 40 ml of titanium tetrachloride and 160 ml of toluene were newly added. The temperature was raised to 110 ° C., and the reaction was carried out with stirring for 2 hours while maintaining the temperature at 110 ° C. Then, after standing, the supernatant was removed, and the operation of washing the resulting solid product with 200 ml of 70 ° C. n-heptane was repeated three times. The operation of washing with 200 ml of heptane was repeated four times, and the obtained solid product was dried under reduced pressure to obtain a powdery solid catalyst component (I-3).

  The titanium content in the obtained solid catalyst component was 2.5% by weight. In the solid catalyst component, di-n-butyl 2,2-bicyclohexanedicarboxylate was 14.2 wt%, ethylbutyl 2,2-bicyclohexanedicarboxylate was 1.3 wt%, 2,2-bicyclohexanedicarboxylic acid Diethyl acid was contained in an amount of 0.7 wt%.

<Formation of polymerization catalyst, polymerization of olefin and evaluation of polymer>
In the same manner as in Example 1 except that the solid catalyst component (I-3) was used instead of the solid catalyst component (I-1), the formation of a polymerization catalyst, the polymerization of the olefin, and the obtained polymer Evaluation was performed. The results are shown in Table 1.

<Preparation of solid catalyst component (I-4)>
A 200 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen was charged with 9.5 g of anhydrous magnesium chloride, 48.5 ml of decane and 39.1 g of 2-ethylhexyl alcohol, and the mixture was stirred under 140 ml. A uniform solution was obtained by heating at 0 ° C. for 2 hours. Next, 5.2 ml (14 mmol) of 2,2′-bicyclohexanedicarboxylic acid di-n-butyl was added to this solution, and then the temperature was raised to 130 ° C., followed by stirring and mixing at 130 ° C. for 1 hour. . After cooling the homogeneous solution thus obtained to room temperature, 30 ml of this homogeneous solution was dropped into 80 ml of titanium tetrachloride kept at −20 ° C. over 20 minutes. After completion of the charging, 7.5 ml of methyl hydrogen polysiloxane was further added, and the temperature of the mixed solution was raised to 110 ° C. over 4 hours, and the temperature was maintained at 110 ° C. for 2 hours with stirring. Reacted. After completion of the reaction, the solid part was collected by hot filtration, and this solid part was resuspended in 110 ml of titanium tetrachloride, and then heated to 110 ° C. with stirring, while maintaining the temperature at 110 ° C. The reaction was allowed to proceed for 2 hours with stirring. After completion of the reaction, the solid part was again collected by hot filtration, washed with decane at 110 ° C., and further thoroughly washed with hexane at room temperature until no free titanium compound was detected in the washing solution. The product was dried under reduced pressure to obtain a powdered solid catalyst component (I-4). The titanium content in the obtained solid catalyst component was 2.2% by weight.

<Formation of polymerization catalyst, polymerization of olefin and evaluation of polymer>
In the same manner as in Example 1, except that the solid catalyst component (I-4) was used in place of the solid catalyst component (I-1), the formation of a polymerization catalyst, the polymerization of olefins, and the obtained polymer Evaluation was performed. The results are shown in Table 1.

<Formation of polymerization catalyst, polymerization of olefin and evaluation of polymer>
The same as Example 1 except that 0.065 mmol of dicyclopentyl dimethoxysilane and 0.065 mmol of 2,2′-bicyclohexanedicarboxylic acid di-n-butyl were used instead of 0.13 mmol of dicyclopentyldimethoxysilane. In this manner, formation of a polymerization catalyst, polymerization of olefin, and evaluation of the obtained polymer were performed. The results are shown in Table 1.

<Formation of polymerization catalyst, polymerization of olefin and evaluation of polymer>
In the same manner as in Example 1 except that 0.13 mmol of dicyclopentyldimethoxysilane was used instead of the same mole of diethylaminotriethoxysilane, formation of a polymerization catalyst, polymerization of olefin, and evaluation of the obtained polymer Was done. The results are shown in Table 1.

<Formation of polymerization catalyst, polymerization of olefin and evaluation of polymer>
In the same manner as in Example 1, except that the same mole of dicyclopentylbis (ethylamino) silane was used instead of 0.13 mmol of dicyclopentyldimethoxysilane, formation of a polymerization catalyst, polymerization of an olefin, and obtained The polymer was evaluated. The results are shown in Table 1.

ＤＣＰＤＭＳ：シ゛シクロヘ゜ンチルシ゛メトキシシラン
ＤＥＡＴＥＳ：シ゛エチルアミノトリエトキシシラン
ＢＥＡＤＣＰＳ：シ゛シクロヘ゜ンチルヒ゛ス(エチルアミノ)シラン

DCPDMS: Dicyclopentylmethoxymethoxysilane DEATES: Diethylaminotriethoxysilane BEADCPS: Dicyclopentylbis (ethylamino) silane

  The solid catalyst for olefin polymerization of the present invention can obtain a polyolefin having a wide molecular weight distribution and a high flowability at the time of melting without using a large amount of hydrogen at the time of polymerization. For this reason, the obtained polymer is suitably molded by high-speed stretching or high-speed injection molding, and can be used for various containers, home appliances, automobile members, and the like.

Claims (6)

Titanium, magnesium, halogen atom and general formula (1);

(In the formula, n and m represent the carbon number of the cyclic skeleton of the cycloalkyl group, and are integers of 5 to 8, which may be the same or different. R is a hydrogen atom, a halogen atom, or a carbon number of 1; Are an alkyl group of ˜8, a vinyl group or an allyl group, and may be the same or different, and R ¹ and R ² are an alkyl group having 2 to 4 carbon atoms, and may be the same or different from each other; A solid catalyst component for olefin polymerization, which comprises an ester compound represented by:   The solid catalyst component for olefin polymerization according to claim 1, wherein n and m are the same integer. A magnesium compound, a titanium compound, a halogen compound other than the titanium compound as necessary, and the following general formula (1);

(In the formula, n and m represent the carbon number of the cyclic skeleton of the cycloalkyl group, and are integers of 5 to 8, which may be the same or different. R is a hydrogen atom, a halogen atom, or a carbon number of 1; Are an alkyl group of ˜8, a vinyl group or an allyl group, and may be the same or different, and R ¹ and R ² are an alkyl group having 2 to 4 carbon atoms, and may be the same or different from each other; A method for producing a solid catalyst component for olefin polymerization, which comprises a step of bringing the ester compounds represented by formula (1) into contact with each other. (I) The solid catalyst component for olefin polymerization according to claim 1 or 2,
(II) the general formula _{^{(2); R 3 p AlQ}} 3-p (2)
(Wherein, ^{R 3} represents an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 <a real number of p ≦ 3, ^{if R 3} there are a plurality each of ^{R 3} May be the same or different, and when a plurality of Q are present, each Q may be the same or different.)
(III) A catalyst for olefin polymerization, which is formed from an external electron donor. The external electron donating compound (III) is represented by the following general formula (3):
R ⁴ _q Si (OR ⁵ ) _4-q (3)
(In the formula, R ⁴ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, an alkylamino group having 1 to 12 carbon atoms, or a carbon number. C1-12 dialkylamino groups, q is an integer of 0 ≦ q ≦ 3, when q is 2 or more, plural R ⁴ is optionally be the same or different .R ⁵ is C 1 -C Represents an alkyl group of ˜4, a cycloalkyl group of 3 to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group or an aralkyl group, and a plurality of R ⁵ may be the same or different. An organosilicon compound and the following general formula (4):
(R ⁶ R ⁷ N) _s SiR ⁸ _4-s (4)
(Wherein R ⁶ and R ⁷ are a hydrogen atom, a straight chain having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, and a cycloalkyl having 3 to 20 carbon atoms. group, an aryl group, R ⁶ and R ⁷ may be the same or different and also may be attached R ⁶ and R ⁷ together form a ring .R ⁸ is 1 to carbon atoms 20 straight chain or branched alkyl group having 3 to 20 carbon atoms, vinyl group, allyl group, aralkyl group, straight chain or branched alkoxy group having 1 to 20 carbon atoms, vinyloxy group, allyloxy group, 3 to 20 carbon atoms cycloalkyl group, an aryl group, an aryloxy group, if R ⁸ is plural, R ⁸ is optionally independently identical or different .s is an integer from 1 to 3.) Table Selected from aminosilane compounds At least one or two or more in claim 4, wherein the catalyst for polymerization of olefins, characterized in that that.   6. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 4 or 5.

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