JP2006274103A - Solid catalytic component for polymerizing olefins, catalyst for polymerizing olefins and method for producing olefin polymer or copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a solid catalytic component for polymerizing an olefin, which produces a polyolefin in which a fine powder polymer having ≤45 μm particle diameter hardly exists, in a high yield and to provide a polymerization method using a polymerization catalyst containing the catalytic component. <P>SOLUTION: The catalytic component for polymerizing an olefin is prepared by bringing a magnesium compound into contact with a small amount of a halogenating agent in the presence of an inert organic solvent containing a surfactant component to give a product and reacting the product with a tetravalent titanium halide compound. The catalyst for polymerizing an olefin is composed of the solid catalytic component and an organoaluminum compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and an olefin polymer or copolymer using the same, for obtaining a polyolefin having a particle size of 45 μm or less and almost no fine powder polymer in a high yield. It relates to a manufacturing method.

  Conventionally, in the polymerization of olefins, many solid catalyst components for olefin polymerization containing magnesium, titanium, an electron donating compound and halogen as essential components have been proposed.

  For example, in Patent Document 1 (JP-A-1-315406), titanium tetrachloride is brought into contact with a suspension formed of diethoxymagnesium and alkylbenzene, and then phthalic acid dichloride is added to react. A solid catalyst component prepared by catalytically reacting the solid product with titanium tetrachloride in the presence of alkylbenzene, a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound, and A process for the polymerization of olefins in the presence of a catalyst has been proposed.

  Each of the above prior arts has a high activity capable of omitting a so-called deashing step for removing catalyst residues such as chlorine and titanium remaining in the produced polymer, and also has a high degree of stereoregularity. These efforts are focused on improving the yield of coalescence and increasing the sustainability of the catalytic activity during polymerization, and each has achieved excellent results. This type of highly active catalyst component, organoaluminum compound and silicon Polymerization of olefins using a polymerization catalyst composed of an electron donating compound typified by a compound causes a fine polymer of the solid catalyst component itself and particle breakage due to heat of reaction when polymerized, resulting in a polymer produced There was a tendency to broaden the particle size distribution with a lot of fine powder contained therein. Increasing the amount of finely divided polymer prevents process continuation, causing blockage of piping during polymer transfer, etc., and widening the particle size distribution results in favorable polymer processing. As a result, the amount of fine powder polymer is as small as possible, and a polymer having a uniform particle size and a narrow particle size distribution has been sought.

  As a method for solving this problem, in Patent Document 2 (Japanese Patent Application Laid-Open No. 6-287225), a suspension of spherical dialkoxymagnesium, an aromatic hydrocarbon compound and a phthalic acid diester is used as an aromatic hydrocarbon compound. It is added to the mixed solution of titanium tetrachloride and allowed to react. The resulting reaction product is washed with an aromatic hydrocarbon compound, and the solid component obtained by reacting with titanium tetrachloride again is dried to remove fine powder. A solid catalyst component for olefin polymerization obtained through a process has been proposed.

  On the other hand, as a prior art, 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 3 (Japanese Patent Laid-Open No. 62-18405), a titanium alkoxy compound, dialkoxy magnesium, 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. Further, in Patent Document 4 (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 heated and reacted, 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.

  In the above proposal, although the catalyst component obtained by removing the fine powder of the solid catalyst component itself is used, the effect of reducing the fine powder amount in the region of 45 to 200 μm to some extent by the particle diameter in the produced polymer is recognized. In particular, the generation of an ultrafine polymer belonging to a region having a particle size of 45 μm or less, which is called microfine, has remained as an unsolved problem. Such ultrafine polymer causes problems such as clogging of the filter in the polymer recovery process and gas recycling system in the continuous operation of the polymerization process, accumulation in the vessel and piping in the system, and maintenance of plant equipment and temporary plant. It was recognized as a serious problem because it caused an increase in costs due to loss of production opportunities due to the suspension. From such an industrial point of view, a catalyst capable of obtaining a polymer in which the amount of ultrafine powder generated is greatly reduced is strongly desired.

  In Patent Document 5 (Japanese Patent Application Laid-Open No. 2004-269467), Patent Document 6 (Japanese Patent Application Laid-Open No. 2004-269808), and Patent Document 7 (Japanese Patent Application Laid-Open No. 2004-269809), the ultrafine powder polymer is referred to as a solid. There has been proposed a method of selectively removing solid catalyst fine particles, which cause generation of an ultrafine polymer, from mother particles by using a surfactant in the catalyst production process. These proposals are described as being effective to some extent for the removal of ultrafine powder electrostatically adhering to the base particles of the solid catalyst component. However, especially when the contact reaction with organoaluminum and the polymerization conditions are set within a range that can be applied industrially, the contact reaction between the solid catalyst component and the organoaluminum, and further the polymerization process with olefins, especially the polymerization The breakage of the solid catalyst component particles during the initial exothermic reaction became extremely significant, and the physical and chemical stability of the surface of the solid catalyst component particles was far from a sufficient level, and a drastic improvement was necessary.

Conventionally, the preparation of a solid catalyst component for polymerization using dialkoxymagnesium such as diethoxymagnesium as a raw material is a method of halogenating dialkoxymagnesium with titanium halides such as titanium tetrachloride. The titanium halide used in this step is added in excess so that dialkoxymagnesium is all converted to magnesium dichloride.
JP-A-1-315406 (Claims) JP-A-6-287225 (Claims) JP-A-62-18405 (Claims) Japanese Patent Laid-Open No. 3-72503 (Claims) JP 2004-269467 A (Claims) JP 2004-269808 A (Claims) JP 2004-269809 A (Claims)

  That is, an object of the present invention is to provide an olefin capable of obtaining a polymer in which an ultrafine polymer having a size of 45 μm or less is sufficiently reduced while maintaining a high yield of the polymer when subjected to polymerization of olefins. An object of the present invention is to provide a solid catalyst component and a catalyst for homopolymerization and a method for producing an olefin polymer or copolymer using the same.

  As a result of intensive studies by the present inventors in this situation, (1) In order to suppress the generation amount of the ultrafine polymer, it is generated when the solid catalyst component is formed from the raw material magnesium compound in the solid catalyst preparation step. It is important to suppress the fine particles as much as possible, and at the same time, to improve the surface strength and stability of the particles that are solid catalyst components. (2) The halogenation reaction of diethoxymagnesium is initially less than the reaction equivalent of titanium tetrachloride. Can be partially halogenated, and then completely halogenated, the reaction heat can be suppressed by partial halogenation, particle breakage can be suppressed, and the final solid catalyst component fine powder can be reduced. As a result, the present invention has been completed.

  That is, the present invention provides a magnesium compound (a) in an amount of 0.3 mol or less per 1 mol of the magnesium compound (a) in the presence of an inert organic solvent (c) containing the surfactant component (b). A solid catalyst component for polymerizing olefins is provided, which is prepared by contacting a halogenating agent (d) of the above to obtain a solid, and then contacting the solid with a titanium halogen compound (e). It is.

The present invention also provides (A) the solid catalyst component for olefin polymerization described above,
(B) The following general formula (3); R ² _p AlQ _3-p (3)
(Wherein R ² 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). The present invention provides a catalyst for olefin polymerization.

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

  The catalyst prepared by using the solid catalyst component for olefin polymerization of the present invention can obtain a polymer having very little fine powder of 45 μm or less, while maintaining a high polymer yield. Therefore, general-purpose polyolefin can be provided at low cost.

  The solid catalyst component (A) of the present invention (hereinafter sometimes simply referred to as “component (A)”) is first a magnesium compound (hereinafter also referred to as “first step”) as a magnesium compound ( a) (hereinafter sometimes simply referred to as “component (a)”) and a surface active component (b) (hereinafter sometimes simply referred to as “component (b)”) are liquids at room temperature. In the presence of the active organic solvent (c) (hereinafter sometimes simply referred to as “component (c)”), 0.3 mol or less of the halogenating agent (d) relative to 1 mol of the magnesium compound (a). (Hereinafter, simply referred to as “component (d)”) is contacted to obtain a solid.

Examples of the magnesium compound (a) used in the present invention include dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, and fatty acid magnesium. Among these magnesium compounds, the following general formula (1);
Mg X _n (OR ¹ ) _2-n (1)
A solid alkoxy-containing magnesium compound represented by the formula (wherein X represents a halogen atom, R ¹ represents an alkyl group, and n is 0 ≦ n <2) is preferably used. In the general formula (1), the alkyl group represented by R ¹ is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group , An isooctyl group and a 2,2-dimethylhexyl group. The halogen atom for X is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom. Specific examples of the component (a) include dimethoxy magnesium, methoxy chloro magnesium, diethoxy magnesium, ethoxy magnesium chloride, dipropoxy magnesium, propoxy magnesium chloride, dibutoxy magnesium, butoxy magnesium chloride, diphenoxy magnesium, phenoxy magnesium chloride. It is also possible to use a mixture of these. Of these, diethoxymagnesium and ethoxymagnesium chloride are particularly preferred.

The average particle size of the alkoxy-containing magnesium compound is 1 to 200 μm, preferably 3 to 150 μm, and more preferably 5 to 100 μm. As for the particle size, it is desirable to use one having a small particle size distribution and a small amount of fine powder and coarse powder. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. Moreover, a specific surface area is 5-100 m < ² > / g, Preferably it is 10-80 m < ² > / g, Most preferably, it is 10-50 m < ² > / g. The shape of the alkoxy-containing magnesium compound used is arbitrary, but it is desirable to use a spherical, elliptical or potato-shaped one.

  The surfactant component (b) is not particularly limited, but is a cationic surfactant, an anionic surfactant, an amphoteric surfactant, a nonionic surfactant, a fluorosurfactant, a reactive surfactant. 1 type (s) or 2 or more types chosen from an agent, silicone oil, and modified silicone oil can be used.

  Examples of the cationic surfactant include aliphatic primary to tertiary amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolium salts, and the like. Examples of the anionic surfactant include fatty acid soaps, N-acylamino acids or salts thereof, carboxylates such as polyoxyethylene alkyl ether carboxylates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, dialkylsulfosuccinates. Salts, sulfonates such as alkyl disulphates of sulfosuccinates, alkylsulfoacetates, sulfated oils, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, monoglyculates, etc. Examples thereof include phosphoric acid ester salts such as sulfate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene phenyl ether phosphates, and alkyl phosphates.

  Examples of the amphoteric surfactant include carboxybetaine type, aminated rubonate, inidazilinium betaine, lecithin, alkylamine oxide and the like. Examples of the nonionic surfactant include polyoxyethylene mono- or dialkyl ethers having 1 to 18 carbon atoms in the alkyl group, polyoxyethylene secondary alcohol ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene sterol ethers, Ether type such as polyoxyethylene lanolin derivative, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, and other ether esters, Polyethylene glycol fatty acid ester, ethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester , Propylene glycol fatty acid esters, ester type such as sucrose fatty acid esters, fatty acid alkanolamides, polyoxyethylene fatty acid amides, nitrogen-containing type such as polyoxyethylene alkyl amines, and the like.

  Examples of the fluorosurfactant include fluoroalkyl carboxylic acid, perfluoroalkyl carboxylic acid, and N-perfluorooctanesulfonyl glutamate disodium. Examples of the reactive surfactant include polyoxyethylene allyl glycidyl nonyl phenyl ether and polyoxyethylene propenyl phenyl ether.

  Silicone oils include dimethyl silicone oil, fatty acid modified silicone oil, alkyl modified silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, methylphenyl silicone oil, chain polydimethylsiloxane, cyclic polydimethylsiloxane, methylphenyl silicone oil. And polyether-modified silicone oil, amino-modified silicone oil, carbinol-modified silicone oil, epoxy-modified silicone oil, and fluorine-modified silicone oil.

  The surfactants exemplified above can be used alone or in combination of two or more. Among the above, the preferred surfactant used in the present invention is a nonionic surfactant, and in particular, a nonionic surfactant having an HLB (hydrophilic lipophilic balance) value of usually 3 to 20 is preferably used. Although it depends on the treatment method, it is desirable to select a nonionic surfactant that is sufficiently soluble in the solvent used. For example, when processing in polar organic solvents, such as alcohol, ethers, and acetone, the hydrophilic nonionic surfactant whose HLB value is 10-20 is used preferably. Moreover, when processing in organic solvents, such as hydrocarbon compounds, such as hexane and heptane, the slightly lipophilic nonionic surfactant whose HLB number is 3-15 is used preferably.

  Slightly lipophilic nonionic surfactants having an HLB value of 3 to 15 include polyoxyethylene alkylphenyl ethers such as nonylphenol ether, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyglycerin monostearate One or more selected from sorbitan fatty acid esters such as polyglycerin fatty acid esters such as rate, sorbitan monostearate and sorbitan distearate are particularly preferably used.

  The inert organic solvent (c) is a liquid at room temperature that does not dissolve the magnesium compound and forms a suspension with the magnesium compound, and is reactive to the component (d) and the component (e). What you do not have is selected. Specifically, saturated hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, and cyclohexane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene, methylene chloride, 1,2-dichlorobenzene, 2 Halogenated hydrocarbon compounds such as 1,4-dichlorotoluene. Of these, aromatic hydrocarbon compounds such as toluene and xylene are most preferably used.

Examples of the halogenating agent (d) in the present invention include halogen-containing compounds and acid halide compounds. The halogen-containing compound has the following general formula (2);
MX _n Y _pn (2)
(In the formula, M represents a metal atom, a metalloid atom, phosphorus or boron, X represents a halogen atom, Y represents a hydrogen atom, an oxygen atom, an alkyl group or an alkoxy group, and p represents the valence of M. And n is 0 <n ≦ p.). In the formula, the metal atom of M includes Mg, Al, Ti, V, Zr, Sn, W, and Mo, and the metalloid atom of M includes As, Sb, Bi, Si, and Ge.

  Specifically, halogen-containing magnesium compounds such as magnesium dichloride, ethyl magnesium chloride, ethyl magnesium bromide, butyl magnesium chloride, phenyl magnesium chloride, methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride and butoxy magnesium chloride, aluminum trichloride, Halogen-containing aluminum compounds such as ethoxyaluminum dichloride, isopropoxyaluminum dichloride, ethylaluminum dichloride and diethylaluminum chloride, tetrachlorosilane, tetrabromosilane, tetrafluorosilane, trichlorosilane, dichlorosilane, ethoxytrichlorosilane, diethoxydichloro Halogen-containing silicon compounds such as silane, triethoxychlorosilane and butoxytrichlorosilane, titanium trihalides such as titanium trichloride, titanium tribromide and titanium triiodide, and titanium such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide Halogen-containing titanium compounds such as tetrahalides, methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, dibutoxy titanium dichloride, trimethoxy Titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride and tributoxy titanium chloride Examples thereof include alkoxy titanium halides such as halide, halogen-containing vanadium compounds such as tetrachlorovanadium and oxytrichlorovanadium, and halogen-containing zirconium compounds such as tetrachlorozirconium and ethoxytrichlorozirconium, and germanium tetrachloride, tin tetrachloride, and antimony pentachloride. , Tungsten hexafluoride, molybdenum hexafluoride, tungsten hexachloride, molybdenum pentachloride, boron trifluoride, boron trichloride, boron tribromide, phosphorus trifluoride, phosphorus pentafluoride, phosphorus trichloride, phosphorus pentachloride , Phosphorus oxychloride, phosphorus oxytrichloride, arsenic trifluoride, arsenic pentafluoride, arsenic trichloride, arsenic pentachloride and the like.

  Preferred among the above compounds are compounds that are liquid at room temperature, or solid or gaseous compounds that can be used by being dissolved in an inert solvent. Specifically, ethyl magnesium chloride, butyl magnesium chloride, Tetrachlorosilane, trichlorosilane, trichloroaluminum, ethylaluminum dichloride, diethylaluminum chloride, titanium tetrachloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, oxytrichlorovanadium, etc. There is.

As the acid halide compound, a monocarboxylic acid halide, a polyvalent carboxylic acid halide, or the like is used. The monocarboxylic acid halide is an aliphatic monocarboxylic acid halide or an aromatic monocarboxylic acid halide, and specifically includes formic acid chloride, formic acid bromide, acetic acid chloride, acetic acid bromide, propionic acid chloride, propionic acid bromide, butyric acid chloride. , Acetic acid bromide, benzoic acid chloride, benzoic acid bromide, p-toluic acid chloride, p-toluic acid bromide, p-methoxybenzoate chloride, p-methoxybenzoate bromide, anisic acid chloride, anisic acid bromide, the following general formula (5 The monocarboxylic acid halide represented by this is mentioned.
(R ⁵ ) ₃ CCOX (5)
(In the formula, R ⁵ represents an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and X represents a chlorine atom or a bromine atom.)

In the above general formula (5), R ⁵ is a methyl group, an ethyl group, a propyl group or an isopropyl group, preferably a methyl group, and the compound in which R ⁵ is a methyl group is specifically a pivalic acid halide ( Or trimethylacetic acid halide). Specific compounds include trimethylacetic acid chloride (pivalic acid chloride), trimethylacetic acid bromide (pivalic acid bromide), triethylacetic acid chloride, triethylacetic acid bromide, tripropylacetic acid chloride, tripropylacetic acid bromide, triisopropylacetic acid chloride, triisopropyl. Examples include acetic acid bromide.

  The polyvalent carboxylic acid halide is an aliphatic polyvalent carboxylic acid halide or an aromatic polyvalent carboxylic acid halide. Specifically, succinic acid dichloride, maleic acid dichloride, maleic acid dibromide, malonic acid dichloride, malonic acid. Dibromide, diisopropylmalonic acid dichloride, diisopropylmalonic acid dibromide, diisobutylmalonic acid dichloride, diisobutylmalonic acid dibromide, adipic acid dichloride, adipic acid dibromide, phthalic acid dichloride, phthalic acid dibromide, terephthalic acid dichloride, terephthalic acid dichloride Bromide, 1,2-cyclohexanedicarboxylic acid dichloride, 1,2-cyclohexanedicarboxylic acid dibromide, sebacic acid dichloride, sebacic acid dibromide, etc. That. These compounds can be used alone or in combination of two or more.

  In the present invention, the solid component is obtained by reacting the component (a) and the component (d) with stirring in the presence of the component (c) containing the component (b). Under the present circumstances, the contact amount of a component (d) is 0.3 mol or less with respect to 1 mol of components (a), Preferably it is 0.01-0.3 mol, More preferably, it is 0.02-0.3 mol, Particularly preferred is 0.02 to 0.28 mol. When the amount of the component (d) used exceeds the above range, it is difficult to control the reaction with the component (a), resulting in breakage of formed particles, peeling of primary surface particles, and the like. Moreover, although it is beneficial in terms of stabilizing the surface state of the solid material in the first step, the solid particles are aggregated when the solid catalyst component is formed by contacting the component (e) with the solid material in the next step. Not only makes it difficult to form a stable particle surface state, but also some of these aggregates break down and become finer through the stirring operation, resulting in sufficiently suppressing the generation of fine particles. I can't.

  About the usage-amount of a component (c), although it can set arbitrarily in the range in which a solid component can form a suspension state, 1 ml-50 ml with respect to 1 g of component (a), Preferably it is 2 ml-20 ml. Used in a range. The component (b) can be used regardless of whether it is solid or liquid. In this case, the component (b) is generally used after being added to the component (c) in advance. It is also possible to add the component (b) after the contact between the component (a) and the component (c). After the component (b) is brought into contact with the component (d), it is suspended by the component (c). It is also possible to use for contact with the component (a). The addition ratio of component (b) is 0.001 to 2 g, preferably 0.005 to 0.5 g, with respect to 1 g of component (a), and 0.0001 with respect to 1 ml of component (c). -0.01 g, preferably 0.005-0.5 g.

  Here, the temperature at which the component (d) is added is also usually in the range of −20 ° C. to 140 ° C., preferably −15 ° C. to 90 ° C. About the reaction conditions after contact operation of each component, it is normally performed in -10 degreeC-150 degreeC for 1 minute-100 hours, Preferably it is 30 to 120 degreeC for 5 minutes-10 hours.

  At this time, when the reaction temperature and time are insufficient, the particle surface stability of the solid material remains insufficient, and when the reaction temperature and time are more than necessary, particle swelling occurs and the formed particles The physical stability of the is impaired. After completion of the reaction, the resulting solid is suspended in an inert organic solvent, and can be used as it is in the next step of preparing the solid catalyst component, but it can be washed with an inert organic solvent as necessary. It is also possible to use it as a powder by drying after removing the solvent.

  A solid material is prepared in the first step as described above. Particularly preferable preparation methods include dialkoxymagnesium as component (a) and aromatic carbonization having an boiling point of 50 to 150 ° C. as an inert organic solvent (c). A nonionic surfactant is dissolved as a surfactant component (b) in the hydrogen compound to form a suspension, and then component (d) is added to the suspension in the temperature range of -5 ° C to 50 ° C. Then, the preparation method by making it react for 10 minutes-5 hours at 50 to 100 degreeC can be mentioned.

  After the solid material is prepared in the first step as described above, the second step for obtaining the solid catalyst component (A) of the present invention is performed by contacting the solid material with the titanium halogen compound (e).

The titanium halogen compound (d) used in the second step (hereinafter sometimes simply referred to as “component (d)”) is a trivalent or tetravalent titanium halide, and has the general formula Ti (OR ⁶ ) _n. Z _pn (wherein R ⁶ represents an alkyl group having 1 to 4 carbon atoms, Z represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, and n is an integer of 0 or 1 to 3) P is a real number of 3 to 4 in terms of the valence of titanium.) And one or more compounds selected from the group consisting of titanium halides and alkoxytitanium halide groups.

  Specifically, titanium tetrachlorides such as titanium trichloride, titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide as titanium halides, and methoxytitanium dichloride, methoxytitanium trichloride, ethoxytitanium dichloride, ethoxytitanium trichloride as alkoxytitanium halides. Chloride, propoxy titanium 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 And tri-n-butoxytitanium chloride. 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 titanium halogen compound (e) (hereinafter sometimes simply referred to as “component (e)”) is the above-described trivalent or tetravalent titanium halide, preferably titanium tetrachloride.

  The contact between the solid substance and the component (e) is carried out 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 can be arbitrarily set within a range in which a rapid reaction is not caused between the components, but is usually performed in the range of −20 ° C. to 100 ° C. Moreover, about the reaction temperature after a contact, the temperature range of 40-130 degreeC is preferable. If the temperature during the reaction is less than 40 ° C., the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid component, and if it exceeds 130 ° C., the evaporation of the solvent used becomes remarkable. , It becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

  In the second step, it is also possible to use an inert organic solvent as a diluent during the contact reaction. As the inert organic solvent, aromatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. such as toluene, xylene and ethylbenzene are preferably used, and these may be used as a mixture of two or more. By using an aromatic hydrocarbon compound, the solubility of impurities in the solid substance or the solid catalyst component is improved during the reaction or washing, and as a result, the catalytic activity of the resulting solid catalyst component and the stereoregularity of the resulting polymer are improved. Can be improved.

  As a preferable preparation method in the second step, the solid material obtained in the first step is suspended in an aromatic hydrocarbon compound, and after the titanium halogen compound (e) is brought into contact with the solid material, a reaction treatment is performed. After washing the obtained solid reaction product with a liquid hydrocarbon compound at room temperature (intermediate washing), the titanium halogen compound (e) is again contacted at −20 to 100 ° C. in the presence of the aromatic hydrocarbon compound. The solid reaction product is washed with a hydrocarbon compound that is liquid at room temperature (final washing) to obtain the solid catalyst component (A). If necessary, the intermediate cleaning and reaction treatment may be repeated a plurality of times.

  The example of the specific preparation method in a 2nd process is shown below. A suspension is formed from the solid material obtained in the first step and the aromatic hydrocarbon compound (c) having a boiling point of 50 to 150 ° C. Component (e) is added to this suspension. Thereafter, the obtained suspension is heated and subjected to a reaction treatment (first reaction treatment). After completion of the reaction, the obtained solid product is washed with a liquid hydrocarbon compound at room temperature (intermediate washing), and then a component (e) and an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C are newly added to -20 to 20 ° C. Contact is performed at 100 ° C., the temperature is raised, and a reaction process (secondary reaction process) is performed. After completion of the reaction, the solid catalyst component (A) is obtained by washing (final washing) with a liquid hydrocarbon compound at room temperature.

Preferred conditions for the treatment or cleaning in the second step are as follows.
Reaction treatment: 0 to 130 ° C., preferably 40 to 120 ° C., particularly preferably 50 to 115 ° C., 0.5 to 6 hours, preferably 0.5 to 5 hours, particularly preferably 1 to 4 hours.
Washing: 0 to 110 ° C., preferably 30 to 100 ° C., particularly preferably 30 to 90 ° C., 1 to 20 times, preferably 1 to 15 times, particularly preferably 1 to 10 times.

  The hydrocarbon compound used for washing is preferably an aromatic hydrocarbon compound or a saturated hydrocarbon compound that is liquid at room temperature. Specifically, the aromatic hydrocarbon compound may be a saturated hydrocarbon such as toluene, xylene, or ethylbenzene. Examples of the compound include hexane, heptane, cyclohexane and the like. Preferably, an aromatic hydrocarbon compound is used in the intermediate cleaning, and a saturated hydrocarbon compound is used in the final cleaning.

  In the second step of the present invention, an electron donating compound can be used as necessary. These are organic compounds containing oxygen atoms or nitrogen atoms, such as alcohols, phenols, ethers, esters, ketones, aldehydes, amines, amides, nitriles, isocyanates, Si-O. -Organosilicon compounds containing a bond.

  Specifically, alcohols such as methanol, ethanol, propanol, butanol 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, Monocarboxylic acid esters such as ethyl varnish, diethyl maleate, dibutyl maleate, diethyl diisopropyl malonate, dipropyl diisopropyl malonate, diisopropyl diisopropyl malonate, dibutyl diisopropyl malonate, diisobutyl diisopropyl malonate, dimethyl adipate, adipic acid Diethyl, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, Di-iso-butyl phthalate, ethyl methyl phthalate, methyl phthalate (iso-propyl), ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate (i o-butyl), di-n-pentyl phthalate, di-iso-pentyl phthalate, di-neo-pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, phthalate Bis (2,2-dimethylhexyl) acid, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, di-iso-decyl phthalate, bis (2,2-dimethylheptyl) phthalate, phthalic acid n-butyl (iso-hexyl), n-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, n-pentyl phthalate (iso-hexyl), iso-pentyl phthalate (heptyl), n-phthalate -Pentyl (2-ethylhexyl), n-pentyl phthalate (iso-nonyl), iso-pentyl phthalate (n-decyl), phthalate N-pentyl undecyl acid, 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-heptyl phthalate (neo-decyl), phthalic acid Dicarboxylic acid esters such as 2-ethylhexyl (iso-nonyl), ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, methylamine, ethylamine, Tributyla Amines such as pyridine, piperidine, aniline and pyridine, 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 And organosilicon compounds containing Si—O— bonds such as alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, and polysiloxane.

  In the second step, the amount of component (e) used varies depending on the preparation method and cannot be defined unconditionally. For example, the tetravalent titanium halogen compound (e) is 0.5 to 100 moles per mole of magnesium compound. , Preferably it is 0.5-50 mol, More preferably, it is 1-10 mol.

  Further, the contents of titanium, magnesium and halogen atoms in the solid catalyst component (A) in the present invention are not particularly defined, but preferably titanium is 0.5 to 8.0% by weight, preferably 0.7 to 7. 0 wt%, more preferably 1.0 to 6.0 wt%, magnesium 8 to 50 wt%, more preferably 10 to 40 wt%, particularly preferably 15 to 30 wt%, still more preferably 15 to 25 wt% %, 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. Further, the total amount of electron donating compounds that can be used as needed is in the range of 0.5 to 40% by weight.

  The organoaluminum compound (B) (hereinafter sometimes simply referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention is represented by the general formula (3). Compounds can be used. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum, diethylaluminum bromide and diethylaluminum hydride, and one or more can be used. Triethylaluminum and tri-iso-butylaluminum are preferable.

  In forming the olefin polymerization catalyst of the present invention, the external electron donating compound (C) (hereinafter simply referred to as “component (C)” together with the organoaluminum compound (B) for the purpose of improving the stereoregularity of the polyolefin. ) ").) Can also be used. These may be the same electron donating compounds that can be used for the preparation of the above-described solid catalyst component, among which 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2- Ethers such as isopentyl-1,3-dimethoxypropane, esters such as methyl benzoate and ethyl benzoate, or organosilicon compounds.

  As the organosilicon compound in which the external electron donating property can be used as a compound, an organosilicon compound represented by the above general formula (4) can be used. Specifically, trimethylmethoxysilane, trimethylethoxysilane, Tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri-iso-butylmethoxysilane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexyl Methoxysilane, tricyclohexylethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane Di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-iso-propyldiethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxy Silane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldimethoxy Silane, dicyclohexyldiethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane Cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane 4-methylcyclohexylcyclohexyldimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, Lopentyl (iso-butyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, 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, phenyl Ethyldimethoxysilane, phenylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, 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, vinyltrimethoxysilane, vinyl Silane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, may be mentioned tetrabutoxy silane. Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldi Ethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxy Silane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylsilane Lopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used. It can be used in combination of more than one species.

  Next, the catalyst for olefin polymerization of the present invention is formed by the component (A), the component (B) and, if necessary, the component (C), and polymerization or copolymerization of olefins in the presence of the catalyst. Do. 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 use 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 component (B) is used per 1 mole of the titanium atom in the component (A). , 1 to 2000 mol, preferably 50 to 1000 mol. When an external electron donating compound is used, the amount thereof is used in the range of 0.002 to 10 mol, preferably 0.01 to 2 mol, per mol of component (B).

  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 formed from the component (A), the component (B), and, if necessary, the component (C) (also referred to as main polymerization), the catalytic activity and the polymer produced. In order to further improve the particle properties and the like, preliminary polymerization can be performed 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 prepolymerization is performed by combining an external electron donating compound, the component (B) is first charged into a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the external electron donating compound is contacted. Furthermore, after contacting the solid catalyst component (A) for olefin polymerization further, an olefin such as propylene and / or one or other two or more olefins is preferably contacted.

  When olefins are polymerized in the presence of the olefin polymerization catalyst formed according to the present invention, the resulting polymer has an ultrafine powder having a particle size of 45 μm or less as compared with the case where a conventional catalyst is used. Polyolefins that are hardly present can be obtained in a high yield, and when propylene is polymerized, a polymer with high stereoregularity can be obtained in a high yield. In fact, in continuous operation of the polymerization process on an industrial scale, problems such as clogging of the filter in the polymer recovery process and gas recycling system, accumulation in the vessel and piping, etc. are remarkably reduced, and the equipment maintenance load is expected to be reduced. be able to. In addition, improvement in polymer quality level can be expected by ensuring long-term stability of operation.

(Example)
EXAMPLES Next, the present invention will be described more specifically with reference to examples, but these are exemplifications and do not limit the present invention.

[Preparation of solid material: first step]
A 500-ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer was charged with 20 g of diethoxymagnesium, 0.4 g of sorbitan monolaurate, and 80 ml of toluene at room temperature, and stirred at 40 ° C. for 10 minutes. Next, the temperature in the system is cooled to −5 ° C., and 1.0 ml of silicon tetrachloride is added with stirring. Thereafter, the temperature is raised to 60 ° C. at 1 ° C./min, and the reaction is performed for 2 hours, thereby suspending the solid matter. A liquid was obtained.

[Preparation of solid catalyst component: second step]
The suspension obtained as described above was allowed to stand, and the supernatant was removed by decantation. Then, 160 ml of toluene was charged and cooled to −10 ° C. To this suspension, 40 ml of titanium tetrachloride was slowly added under stirring. When the temperature was raised to 80 ° C., 5.2 ml of di-n-butyl phthalate was added, and the mixture was further reacted at 105 ° C. for 2 hours. . After completion of the reaction, the obtained solid product was washed 4 times with 200 ml of toluene at 90 ° C., 60 ml of titanium tetrachloride and 140 ml of toluene were newly added, the temperature was raised to 110 ° C., and the mixture was reacted for 2 hours with stirring. After completion of the reaction, washing was performed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. In addition, it was 2.5 weight% when the titanium content rate in this solid catalyst component was measured.

[Formation of polymerization catalyst and propylene polymerization]
700 ml of n-heptane was charged into a stainless steel autoclave with a stirrer having an internal volume of 1800 ml that had been sufficiently dried with nitrogen gas and then replaced with propylene gas, and maintained in a propylene gas atmosphere. The polymerization catalyst was formed by charging 0.21 mmol of cyclohexylmethyldimethoxysilane and 0.0053 mmol of the solid catalyst component as Ti. Next, a preliminary polymerization was carried out at 20 ° C. for 30 minutes while applying a propylene pressure of 0.2 MPa and maintaining stirring. Thereafter, 150 ml of hydrogen was charged, and the polymerization was continued for 2 hours at 70 ° C. with a propylene pressure in the system of 0.7 MPa. In addition, the pressure which falls as superposition | polymerization advances was supplemented by supplying only propylene continuously, and was kept at the constant pressure during superposition | polymerization. According to the above polymerization method, propylene was polymerized, and the produced polymer was filtered and dried under reduced pressure to obtain a solid polymer. On the other hand, the filtrate is condensed to obtain a polymer dissolved in the polymerization solvent, the amount thereof is (M), and the amount of the solid polymer is (N). The polymerization activity per solid catalyst component (Y) and the polymerization yield (P) are represented by the following formulae.
(Y) = [(M) + (N)] (g) / solid catalyst component amount (g)
(P) = (N) / [(M) + (N)] x 100 (%)
Further, when the bulk specific gravity (BD), the average particle diameter of the produced solid polymer, and the amount of fine powder of 45 μm or less of the produced solid polymer were measured, the results shown in Table 1 were obtained. The average particle size of the produced solid polymer is determined by measuring the particle size distribution according to JISK0069 and obtaining the particle size corresponding to 50% of the accumulated weight. Ethanol was allowed to flow through the produced polymer placed above, and the ethanol suspension containing the fine particles that passed through the sieve was centrifuged to collect solids (fine particles), which were further dried under reduced pressure and measured for weight.

  A 500-ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer was charged with 20 g of diethoxymagnesium, 0.4 g of sorbitan distearate, and 80 ml of n-heptane at room temperature and stirred at 40 ° C. for 10 minutes. Next, the temperature in the system is cooled to −5 ° C., and 2.0 ml of diethylaluminum chloride is added with stirring, and then the temperature is raised to 70 ° C. at 1 ° C./min and reacted for 2 hours, and a suspension containing solid matter A liquid was obtained. The solid material thus obtained was treated in the same manner as in Example 1 to prepare a solid catalyst component, to form a polymerization catalyst, and to carry out propylene polymerization. The results shown in Table 1 were obtained.

Comparative Example 1
Table 1 shows the results of the preparation of the solid catalyst component and the polymerization of propylene in the same manner as in Example 1 except that silicon tetrachloride is not used during the preparation of the solid material in the first step.

Examples 3 to 5 and Comparative Example 2
Table 2 shows the results of the preparation of the solid catalyst component and the polymerization of propylene in the same manner as in Example 1 except that the silicon tetrachloride used in the preparation of the solid material in the first step is changed as shown in Table 2.

Examples 6-10
The preparation of the solid catalyst component and the polymerization of propylene were carried out in the same manner as in Example 1 except that the type and amount of the surface active component (component (b)) used in the preparation of the solid product in the first step were changed as shown in Table 3. The results are shown in Table 3.

Example 11
[Preparation of solid material; first step]
A 500-ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer was charged with 20 g of diethoxymagnesium, 0.3 g of sorbitan distearate, and 60 ml of xylene at room temperature, and then stirred at room temperature. Titanium (2.0 g) was added, and the mixture was reacted at 105 ° C. with stirring for 4 hours to obtain a suspension containing a solid material.

[Preparation of solid catalyst component; second step]
The suspension obtained as described above was allowed to stand and the supernatant was removed by decantation. Then, 100 ml of toluene was charged and cooled to −10 ° C. To this suspension, 100 ml of titanium tetrachloride was slowly added with stirring and reacted at 95 ° C. for 2 hours. After completion of the reaction, the obtained solid product was washed 4 times with 200 ml of toluene at 90 ° C., 60 ml of titanium tetrachloride and 140 ml of toluene were newly added, the temperature was raised to 100 ° C., and the reaction was carried out with stirring for 2 hours. After completion of the reaction, washing was performed 10 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. In addition, it was 4.5 weight% when the titanium content rate in this solid catalyst component was measured.

[Formation of polymerization catalyst and ethylene polymerization]
A stainless steel autoclave with a stirrer having a substituted internal volume of 1800 ml, which has been sufficiently dried with nitrogen gas, is charged with 700 ml of n-heptane, and 2.10 mmol of triethylaluminum with stirring at room temperature, and the solid catalyst component is added to Ti. 0.0053 mmol was charged to form a polymerization catalyst. Subsequently, 0.4 MPa of hydrogen pressure was applied, ethylene was further introduced so that the total pressure in the system was 9.0 MPa, and polymerization was continued at 70 ° C. for 2 hours. In addition, the pressure which falls as superposition | polymerization progressed was compensated by supplying ethylene only continuously, and was kept at the constant pressure during superposition | polymerization. When ethylene was polymerized according to the above polymerization method, the results shown in Table 4 were obtained.

Example 12
Table 4 shows the results of the preparation of solid materials and solid catalyst components and the polymerization of ethylene in the same manner as in Example 11 except that 3.0 g of aluminum chloride was used instead of 2.0 g of titanium trichloride.

Example 13
[Formation of polymerization catalyst]
7 mg of the solid catalyst component used in Example 1 was suspended in 0.20 ml of heptane, 4.0 mmol of triethylaluminum and 0.06 mmol of dicyclohexyldimethoxysilane were added thereto, and the mixture was stirred at room temperature for 5 minutes.

[Propylene polymerization]
An autoclave with a stirrer with an internal volume of 2.0 liters, which was completely replaced with nitrogen gas, was charged with 0.50 mmol of triethylaluminum, then with 1.5 liters of hydrogen gas and 1.2 liters of liquefied propylene, The temperature was raised to 70 ° C. The polymerization catalyst was charged into a catalyst charging vessel mounted on the top of the autoclave, and flushed with 0.2 liter of liquefied propylene to introduce into the autoclave, and polymerization was carried out at 70 ° C. for 1 hour. Table 5 shows the polymerization activity per gram of the solid catalyst component and the ratio (HI) of the boiling insoluble n-heptane in the produced polymer. In addition, the ratio (HI) of the boiling insoluble n-heptane insoluble content in the produced polymer is the percentage of the polymer insoluble in n-heptane when the produced polymer is extracted with boiling n-heptane for 6 hours. ).

Comparative Example 3
(Preparation of solid catalyst component)
A 500 ml round bottom flask equipped with a stirrer and fully substituted with nitrogen gas was charged with 10 g of diethoxymagnesium and 80 ml of toluene to form a suspension and cooled to 10 ° C. To this suspension, 12 ml of benzoic acid chloride was added, stirred at 10 ° C. for 6 hours, further washed with 100 ml of toluene at 40 ° C. twice and then with 100 ml of heptane at 40 ° C. for 5 times to obtain heptane containing solid matter. A suspension was obtained. The heptane suspension containing the solid substance obtained above was charged with 10 ml of toluene and 50 ml of titanium tetrachloride previously charged in a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas. Added in solution. Next, the suspension was reacted at −5 ° C. for 2 hours (low temperature aging treatment). Then, after heating up to 90 degreeC, the reaction process was performed for 2 hours, stirring. After completion of the reaction, the product was washed once with 100 ml of toluene at 70 ° C. and further washed 4 times with 100 ml of n-heptane at 70 ° C., 50 ml of titanium tetrachloride was newly added, and the mixture was stirred at 100 ° C. with stirring at 100 ° C. A reaction treatment for a time (second treatment) was performed. Further, 50 ml of titanium tetrachloride was added, and a reaction treatment was performed at 100 ° C. for 1 hour while stirring. The product was then washed 7 times with 100 ml of 40 ° C. heptane, filtered and dried to obtain a solid catalyst component. The titanium content in the solid catalyst component was measured and found to be 1.6% by weight.

[Formation of polymerization catalyst and propylene polymerization]
When the solid catalyst component obtained as described above was polymerized in the same manner as in Example 13, the results shown in Table 5 were obtained.

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

Claims (12)

  In the presence of an inert organic solvent (c) containing the surface active component (b) in the magnesium compound (a), 0.3 mol or less of the halogenating agent (d) per 1 mol of the magnesium compound (a) A solid catalyst component for polymerizing olefins, which is prepared by contacting a solid halogen compound (e) with the titanium halide compound (e). The magnesium compound (a) is represented by the following general formula (1);
Mg X _n (OR ¹ ) _2-n (1)
2. The olefin according to claim 1, wherein the olefin is an alkoxy group-containing magnesium compound represented by the formula: wherein X is a halogen atom, R ¹ is an alkyl group, and n is 0 ≦ n <2. Solid catalyst component for polymerization.   2. The solid catalyst component for olefin polymerization according to claim 1, wherein the surfactant component (b) is a nonionic surfactant.   The solid catalyst component for olefin polymerization according to claim 1, wherein the inert organic solvent (c) is an aromatic hydrocarbon compound. The halogenating agent (d) is represented by the following general formula (2);
MX _n Y _pn (2)
(In the formula, M represents a metal atom, a metalloid atom, phosphorus or boron, X represents a halogen atom, Y represents a hydrogen atom, an oxygen atom, an alkyl group or an alkoxy group, and p represents the valence of M. The solid catalyst component for olefin polymerization according to claim 1, wherein n is a halogen-containing compound represented by 0 <n ≦ p.   The solid catalyst component for olefin polymerization according to claim 1, wherein the titanium halogen compound (e) is a tetravalent titanium halogen compound.   The solid catalyst component for olefin polymerization according to claim 1, wherein the halogenating agent (d) is a tetravalent silicon halide compound, a titanium halogen compound or a carboxylic acid halide. (A) The solid catalyst component for olefin polymerization according to any one of claims 1 to 7,
(B) the following general formula (3);
R ² _p AlQ _3-p (3)
(Wherein R ² 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). A catalyst for olefin polymerization. (A) The solid catalyst component for olefin polymerization according to any one of claims 1 to 7,
(B) the following general formula (3);
R ² _p AlQ _3-p (3)
(Wherein R ² 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. The (C) external electron donating compound is represented by the following general formula (4):
R ³ _q Si (OR ⁴ ) _4-q (4)
(In the formula, R ³ 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 ⁴ has 1 carbon atom. Represents an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and q is an organic group represented by 0 ≦ q ≦ 3. The olefin polymerization catalyst according to claim 9, which is a silicon compound.   The manufacturing method of the olefin polymer or copolymer performed in presence of the catalyst for olefin polymerization of any one of Claims 8-10.   The olefin monomer used in the production of the olefin polymer or copolymer is propylene or a monomer of propylene and one or more other olefins. A process for producing an olefin polymer or copolymer.

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