Method for producing solid catalyst component for olefin polymerization and method for producing propylene-based polymer

Abstract

To provide a method for producing a solid catalyst component for olefin polymerization capable of obtaining a propylene-based polymer with reduced amorphous content and improved stereoregularity for enhancing performance such as improvement in rigidity and suppression of stickiness and to provide a method for producing a propylene-based polymer.SOLUTION: There is provided a method for producing a solid catalyst component for olefin polymerization which comprises: a step 1 of contacting components (a1), (a2), (a3) and (a4) to obtain a contact product (1); and a step 2 of contacting a component containing the contact product (1), components (a2) and (a5) to obtain a contact product (2). Component (a1): a solid component containing titanium, magnesium, a halogen and an electron donor as essential components. Component (a2): a silane compound having an alkenyl group. Component (a3): an alkoxysilane compound [However, this is different from a silane compound having an alkenyl group.]. Component (a4): an organic aluminum compound represented by the general formula, R3-aAlXa. Component (a5): a specific organic aluminum compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a solid catalyst component for olefin polymerization, and a method for producing a propylene polymer using the method for producing a solid catalyst component for olefin polymerization. [Background technology]

[0002] Olefin polymers, typified by polypropylene, are the most important plastic materials as industrial materials, and are widely used in a variety of applications, including as films or sheets for packaging materials and electrical materials, as molded articles for industrial materials such as automobile components and home appliances, and as textile materials and building materials. Because of the wide and diverse range of uses, olefin polymers such as polypropylene have been continuously required to be improved and enhanced in various properties in view of their applications, and in order to meet these demands, technological developments have been carried out mainly through improvements in polymerization catalysts.

[0003] Ziegler catalysts using transition metal compounds and organometallic compounds have significantly increased the polymerization activity of propylene, making industrial production possible. Since then, various improvements have been made to its performance, including improvements in the polymer's physical properties due to molecular weight distribution, reduction of amorphous components (polymers with low stereoregularity and low molecular weight) in propylene polymers, and improvement of stereoregularity. Specifically, catalysts using magnesium compounds as catalyst supports and solid catalyst components containing titanium and halogen as essential components have been developed. Furthermore, catalysts using electron donors to enhance catalytic activity and stereoregularity have been proposed (see, for example, Patent Documents 1 to 3). Subsequently, proposals have been made to further improve catalytic activity and stereoregularity by adding specific organosilicon compounds to the catalyst components (see, for example, Patent Document 4). Furthermore, proposals have been made to further improve catalytic activity and stereoregularity by using silicon compounds with special structures containing alkenyl groups, such as vinyl groups or allyl groups, in addition to specific organosilicon compounds, thereby improving performance, such as by improving the response to hydrogen used as a molecular weight regulator (see, for example, Patent Documents 5 to 8). Furthermore, proposals have been made to reduce amorphous components by using specific amide compounds, sulfite esters, unsaturated cyclic ether compounds, etc., in combination with organosilicon compounds as external donors (see, for example, Patent Documents 9 to 11). Furthermore, many improved techniques have been disclosed, such as the use of cross-linked alkylaluminum during polymerization, which improves polymerization activity and increases stereoregularity at low molecular weights (see Patent Document 12). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 58-138706 [Patent Document 2] Japanese Patent Application Publication No. 57-59909 [Patent Document 3] Japanese Patent Application Publication No. 58-147409 [Patent Document 4] Japanese Patent Application Publication No. 187707 / 1983 [Patent Document 5] Japanese Patent Application Publication No. 03-234707 [Patent Document 6] Japanese Patent Application Publication No. 07-2923 [Patent Document 7] Japanese Patent Application Laid-Open No. 2006-169283 [Patent Document 8] Japanese Patent Application Laid-Open No. 2008-163151 [Patent Document 9] Japanese Patent Application Laid-Open No. 2004-124090 [Patent Document 10] Japanese Patent Application Laid-Open No. 2006-225449 [Patent Document 11] Japanese Patent Publication No. 2020-164852 [Patent Document 12] Japanese Patent Application Publication No. 6-306115 Summary of the Invention [Problem to be solved by the invention]

[0005] However, to the best of our knowledge, none of these catalyst systems has yet achieved sufficient improvements in the properties of the resulting propylene polymer, such as reducing the amount of amorphous components and increasing the stereoregularity, and improvements in these properties are needed in various fields. For example, in the field of automotive parts and materials, high rigidity is required for molded products, and further improvements are particularly desired in terms of high crystallinity, i.e., stereoregularity, and reducing the amount of amorphous components. In addition, in the field of packaging materials, further improvements in stickiness, etc. are strongly desired.

[0006] An object of the present application is to provide a method for producing a solid catalyst component for olefin polymerization, which further reduces amorphous components and gives a propylene polymer having improved stereoregularity, in order to meet the demand for further performance improvements, such as improved rigidity and suppressed stickiness, in the field of polypropylene materials and olefin polymerization catalysts, as described above in the prior art, and to provide a method for producing a propylene polymer using the same. [Means for solving the problem]

[0007] As a result of intensive research to achieve the above object, the present researchers have found a method for producing a solid catalyst component for olefin polymerization, which can further reduce amorphous components and give propylene polymers with improved stereoregularity, and a method for producing propylene polymers using the same. That is, the present invention includes the following aspects.

[0008] <1> Step 1: contacting the following components (a1), (a2), (a3), and (a4) to obtain a contact product (1); a step 2 of contacting a component containing the contact product (1) with the following components (a2) and (a5) to obtain a contact product (2): Component (a1): A solid component containing titanium, magnesium, a halogen, and an electron donor as essential components. Component (a2): Silane compound having an alkenyl group Component (a3): Alkoxysilane compound (however, different from a silane compound having an alkenyl group). Component (a4): an organoaluminum compound represented by the following general formula (1): General formula (1) R 3-a AlX a (wherein, each R independently represents a hydrocarbon group having 1 to 20 carbon atoms, each X independently represents a hydrogen atom or a halogen atom, and a represents a number satisfying 0≦a≦2.) Component (a5): an organoaluminum compound represented by the following general formula (2):

[0009] [ka] (where R 1 ~R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and R 5 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. <2> The component (a2) is a vinylsilane compound and / or the component (a3) ​​is a compound represented by the following general formula (3): <1> 1. A method for producing the solid catalyst component for olefin polymerization according to claim 1. General formula (3) R 6 R 7 m Si(OR 8 ) n (where R 6 represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. 7 R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 8 each independently represents a hydrocarbon group, m is 0, 1 or 2, n is 1, 2 or 3, and m+n=3 is satisfied. <3> The aforementioned <1> or <2> A method for producing a propylene polymer, comprising homopolymerizing or copolymerizing propylene in the presence of a solid catalyst component (A) for olefin polymerization obtained by the method described in 1. above and an organoaluminum compound (B) represented by the following general formula (1): General formula (1) R 3-a AlX a (wherein, each R independently represents a hydrocarbon group having 1 to 20 carbon atoms, each X independently represents a hydrogen atom or a halogen atom, and a represents a number satisfying 0≦a≦2.) [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a method for producing a solid catalyst component for olefin polymerization, which can reduce amorphous components and give a propylene-based polymer having improved stereoregularity, and a method for producing a propylene-based polymer having few amorphous components and high stereoregularity. DETAILED DESCRIPTION OF THE INVENTION

[0011] The method for producing a solid catalyst component for olefin polymerization and the method for producing a propylene-based polymer of the present invention will be described in detail below. In this specification, the symbol "to" indicating a range of values ​​is used to mean that the values ​​before and after it are included as the lower and upper limits.

[0012] I. Method for producing a solid catalyst component for olefin polymerization The method for producing a solid catalyst component for olefin polymerization of the present invention comprises: Step 1, which comprises contacting the following components (a1), (a2), (a3), and (a4) to obtain a contact product (1); and Step 2 of contacting the components containing the contact product (1) with the following components (a2) and (a5) to obtain a contact product (2). Component (a1): A solid component containing titanium, magnesium, a halogen, and an electron donor as essential components. Component (a2): Silane compound having an alkenyl group Component (a3): Alkoxysilane compound (however, different from a silane compound having an alkenyl group). Component (a4): an organoaluminum compound represented by the following general formula (1): General formula (1) R 3-a AlX a (wherein, each R independently represents a hydrocarbon group having 1 to 20 carbon atoms, each X independently represents a hydrogen atom or a halogen atom, and a represents a number satisfying 0≦a≦2.) Component (a5): an organoaluminum compound represented by the following general formula (2):

[0013] [ka] (where R 1 ~R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and R 5 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.

[0014] In the present invention, a solid catalyst component for olefin polymerization is produced by including Step 1 of contacting the components (a1), (a2), (a3), and (a4) to obtain a contact product (1), and Step 2 of contacting a component containing the contact product (1), the components (a2), and (a5) to obtain a contact product (2). This further reduces the amount of amorphous components, and makes it possible to produce a solid catalyst component for olefin polymerization that can give a propylene polymer with improved stereoregularity. In the present invention, the components (a1), (a2), (a3), and (a4) are first contacted to obtain the contact product (1). This allows the alkoxysilane compound (a3) ​​to be supported by substituting an appropriate amount of the electron donor in the component (a1) while the alkenyl-containing silane compound (a2) protects the titanium at the active site. The alkoxysilane compound (a3) ​​coordinates near the titanium atom, which can serve as the active site, to form an active species. When the contact product (1) is then contacted with the bridged organoaluminum compound (a5) in the presence of the alkenyl-containing silane compound (a2), the alkenyl-containing silane compound (a2) protects the active species, and the bridged organoaluminum compound (a5) is supported on the solid catalyst component for olefin polymerization without the bridged organoaluminum compound (a5) directly over-reducing (deactivating) the active species. It is presumed that the bridged organoaluminum compound (a5) suppresses the formation of active sites that generate amorphous components and controls the insertion reaction (polymerization reaction) of propylene by donating electrons to the active species and sterically controlling the space around the active species. In the present invention, it is possible to support appropriate amounts of the alkoxysilane compound (a3) ​​and the bridged organoaluminum compound (a5) in the solid catalyst component for olefin polymerization in this stepwise manner, which is believed to suppress the formation of active sites that produce amorphous components during polymerization. Furthermore, as described above, it is believed that the high activity can be maintained due to the protective effect of the active sites by the silane compound (a2) having an alkenyl group. In contrast, as shown in the comparative examples described below, when propylene polymerization was carried out by adding an organoaluminum compound corresponding to component (a4) and a bridged organoaluminum compound corresponding to component (a5) during polymerization, the reduction in amorphous components was insufficient. This is thought to be due to insufficient support of the bridged organoaluminum compound (a5) in the early stages of polymerization. Furthermore, when propylene polymerization was carried out using a solid catalyst component for olefin polymerization produced by contacting solid component (a1) with components (a2), (a3), (a4), and (a5) without obtaining contact product (1), the amorphous components actually increased. This is thought to be due to insufficient coordination of the alkoxysilane compound (a3) ​​near titanium atoms, which can serve as active sites.

[0015] 1.Process 1 Step 1 is a step of contacting the following components (a1), (a2), (a3), and (a4) to obtain a contact product (1).

[0016] 1-1. Component (a1) The component (a1) is a solid component containing titanium, magnesium, a halogen, and an electron donor as essential components.

[0017] 1-1-1.Titanium Any titanium compound can be used as the titanium source for the solid component, and representative examples include the compounds disclosed in JP-A-3-234707. With regard to the valence of titanium, titanium compounds having any valence of tetravalent, trivalent, divalent, or zero valence can be used, and preferably tetravalent or trivalent titanium compounds, more preferably tetravalent titanium compounds.

[0018] Examples of the tetravalent titanium compound include titanium halides such as titanium tetrachloride and titanium tetrabromide, alkoxytitaniums such as tetraethoxytitanium and tetrabutoxytitanium, condensed compounds of alkoxytitanium having a Ti-O-Ti bond such as tetrabutoxytitanium dimer (BuO)3Ti-O-Ti(OBu)3, and organotitaniums such as dicyclopentadienyltitanium dichloride. Further, a compound having an average composition formula which is a mixed formula of the above titanium compounds (for example, Ti(OBu) m Cl 4-m ; 0 < m < 4), or a complex of the above titanium compound and a phthalic acid ester or other compound (for example, Ph(CO2Bu)2·TiCl4) may also be used. Examples of the trivalent titanium compound include titanium halides such as titanium trichloride. As the titanium trichloride, those produced by any known method such as a hydrogen reduction type, a metal aluminum reduction type, a metal titanium reduction type, and an organoaluminum reduction type can be used. Among the above titanium compounds, titanium tetrachloride and tetrabutoxytitanium are preferred. The above titanium compounds may be used alone or in combination of two or more.

[0019] 1-1-2. Magnesium As the magnesium source of magnesium contained in the solid component, metallic magnesium or any magnesium compound can be used. Representative examples include the compounds disclosed in JP-A-3-234707. Examples of magnesium compounds include magnesium halides such as magnesium chloride and magnesium bromide, inorganic magnesium compounds such as magnesium oxide and magnesium hydroxide, Grignard compounds such as ethyl magnesium chloride, butyl magnesium chloride, butyl magnesium bromide and phenyl magnesium bromide, alkoxy magnesium compounds such as diethoxy magnesium and dibutoxy magnesium, organic magnesium compounds such as butyloctyl magnesium, inorganic and organic magnesium salts such as magnesium carbonate and magnesium stearate, etc. Also, compounds whose average composition formula is a mixture of the above magnesium compounds (for example, Mg(OEt) m Cl 2-m ;0 <m<2)であってもよい。 Among the above magnesium compounds, magnesium chloride, diethoxy magnesium, metallic magnesium, and butylmagnesium chloride are preferred. The above magnesium compounds may be used alone or in combination of two or more.

[0020] 1-1-3.Halogen The halogen contained in the solid component may be fluorine, chlorine, bromine, or iodine. Among the above halogens, chlorine is preferred. The above halogens may be used alone or in combination of two or more. The halogen contained in the solid component is generally a halogen-containing compound selected from the titanium compounds and / or magnesium compounds described above. Other halogen-containing compounds may also be used as the halogen source. Examples of other halogen-containing compounds include silicon halide compounds such as silicon tetrachloride, aluminum halide compounds such as aluminum chloride, halogen-containing organic compounds such as 1,2-dichloroethane and benzyl chloride, borane halides such as trichloroborane, phosphorus halides such as phosphorus pentachloride, tungsten halides such as tungsten hexachloride, and molybdenum halides such as molybdenum pentachloride. Among the other halogen-containing compounds described above, silicon tetrachloride is preferred. The halogen-containing compounds may be used alone or in combination of two or more. Among the titanium compounds and / or magnesium compounds, a halogen-containing compound may be used in combination with another halogen-containing compound.

[0021] 1-1-4. Electron donor The electron donor contained in the solid component can be any electron donor, and representative examples include the compounds disclosed in JP-A-2004-124090. Examples of the electron donor include organic acids, inorganic acids, and derivatives thereof (esters, acid halides, amides, acid anhydrides), ether compounds, ketone compounds, aldehyde compounds, alcohol compounds, amine compounds, etc. The above electron donors may be used alone or in combination of two or more.

[0022] Examples of organic acids include aromatic carboxylic acids such as benzoic acid and phthalic acid; aliphatic carboxylic acids such as propionic acid, maleic acid, malonic acid, and malonic acids having one or two substituents at the 2-position such as 2-n-butyl-malonic acid; succinic acid and succinic acids having one or two substituents at the 2-position or one or more substituents at each of the 2- and 3-positions such as 2-n-butyl-succinic acid; aromatic sulfonic acids such as benzenesulfonic acid; and aliphatic sulfonic acids such as methanesulfonic acid.

[0023] Examples of the derivatives of organic acids include organic acid esters, acid anhydrides, acid halides, and amides.

[0024] Examples of the organic acid ester include esters of the above organic acids. The alcohol, which is a component of the organic acid ester, can be an aliphatic alcohol, an aromatic alcohol, or an alicyclic alcohol. Examples of the alcohol include alcohols having an aliphatic free radical of 1 to 20 carbon atoms, such as an ethyl group, butyl group, isobutyl group, heptyl group, octyl group, or dodecyl group, and alcohols having an alicyclic free radical, such as a cyclopentyl group, cyclohexyl group, or cycloheptyl group. Among these alcohols, alcohols having an aliphatic free radical of 1 to 20 carbon atoms, such as an ethyl group, butyl group, isobutyl group, heptyl group, octyl group, or dodecyl group, are preferred. More preferred are alcohols having an aliphatic free radical of 2 to 12 carbon atoms. Examples of organic acid esters include phthalate diesters such as diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, and diheptyl phthalate; malonate esters having one or two substituents at the 2-position such as 2-n-butyl-diethyl malonate; and succinate esters having one or two substituents at the 2-position or one or more substituents at each of the 2- and 3-positions such as 2-n-butyl-diethyl succinate.

[0025] Examples of the acid anhydride include the acid anhydrides of the above organic acids. Examples of the organic acid halide include acid halides of the above organic acids. Examples of halogens that are components of acid halides include fluorine, chlorine, bromine, and iodine. Among these halogens, chlorine is preferred. When the organic acid halide is a polyhalide of a polyvalent organic acid, the multiple halogens may be the same or different. Examples of organic acid halides include phthalic acid dihalides such as phthaloyl dichloride. Examples of organic acid amides include amides of the above organic acids. Examples of amines that are components of amides include ammonia, aliphatic amines such as ethylamine and dibutylamine, and aromatic amines such as aniline and benzylamine. Among these amines, ethylamine and dibutylamine are preferred. Examples of organic acid amides include acetamide, benzamide, toluic acid amide, etc. Among these organic acid amides, benzamide and toluic acid amide are preferred.

[0026] Examples of inorganic acids include carbonic acid, phosphoric acid, silicic acid, sulfuric acid, and nitric acid. Preferred inorganic acid derivatives are inorganic acid esters such as tetraethoxysilane (ethyl silicate), tetrabutoxysilane (butyl silicate), and tributyl phosphate.

[0027] Examples of the ether compound include aliphatic ethers such as dibutyl ether, aromatic ethers such as diphenyl ether, aliphatic polyvalent ethers such as 1,3-dimethoxypropane having one or two substituents at the 2-position, such as 2-isopropyl-2-isobutyl-1,3-dimethoxypropane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, aromatic polyvalent ethers such as 9,9-bis(methoxymethyl)fluorene, and cyclic ethers such as furan, 2-methylfuran, 2-ethylfuran, 2,5-dimethylfuran, 2,5-diethylfuran, benzofuran, dibenzofuran, and tetrahydrofuran.

[0028] Examples of the ketone compound include aliphatic ketones such as methyl ethyl ketone, aromatic ketones such as acetophenone, and polyhydric ketones such as 2,2,4,6,6-pentamethyl-3,5-heptanedione. Examples of the aldehyde compound include aliphatic aldehydes such as propionaldehyde, and aromatic aldehyde compounds such as benzaldehyde. Examples of alcohol compounds include aliphatic alcohols such as butanol and 2-ethylhexanol, aromatic alcohols such as phenol and cresol, aliphatic polyhydric alcohols such as glycerin, and aromatic polyhydric alcohols such as 1,1'-bi-2-naphthol.

[0029] Examples of the amine compound include aliphatic amines such as diethylamine, heterocyclic amines such as 2,2,6,6-tetramethyl-piperidine, pyridine, and 2,6-lutidine, aromatic amines such as aniline, and polyamines such as 1,3-bis(dimethylamino)-2,2-dimethylpropane.

[0030] Furthermore, compounds that can be used as electron donors include compounds containing multiple electron-donating functional groups in the same molecule. Examples of compounds containing multiple electron-donating functional groups in the same molecule include carboxylic acid esters having alkoxy groups in the molecule, such as 2-ethoxyethyl acetate and ethyl 3-ethoxy-2-t-butylpropionate, keto esters such as ethyl 2-benzoylbenzoate, keto ethers such as (1-t-butyl-2-methoxyethyl)methyl ketone, and amino ethers such as N,N-dimethyl-2,2-dimethyl-3-methoxypropylamine.

[0031] The electron donor is more preferably at least one of an organic acid ester compound, an acid halide compound, and an ether compound. Among the above electron donors, preferred are phthalate diesters such as diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, and diheptyl phthalate; malonate diesters having one or two substituents at the 2-position such as 2-n-butyl-diethyl malonate; succinate esters having one or two substituents at the 2-position or one or more substituents at each of the 2- and 3-positions such as 2-n-butyl-ethyl succinate; phthalate dihalides such as phthaloyl dichloride; aliphatic polyvalent ethers such as 1,3-dimethoxypropane having one or two substituents at the 2-position such as 2-isopropyl-2-isobutyl-1,3-dimethoxypropane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane; and polyvalent ethers having an aromatic free radical in the molecule such as 9,9-bis(methoxymethyl)fluorene. Phthalate diesters and phthalate dihalides are more preferred. The above electron donors may be used alone or in combination of two or more.

[0032] 1-1-5. Preparation of solid component (a1) The solid component can be obtained by contacting the titanium compound, magnesium compound and electron donor components, or by contacting the titanium compound, magnesium compound, other halogen-containing compound and electron donor components. The ratio of the amounts of the components used may be any within a range that does not significantly impair the effects of the present invention, but the following ranges are generally preferred. The amount of the titanium compound used relative to the amount of the magnesium compound used is preferably 0.0001 to 1,000, more preferably 0.001 to 100, and even more preferably 0.01 to 50, in terms of molar ratio (number of moles of titanium compound / number of moles of magnesium compound).

[0033] When other halogen-containing compounds are used in addition to the magnesium compound and the titanium compound, the amount of the compounds used is preferably 0.01 to 1,000, more preferably 0.1 to 100, in terms of molar ratio (number of moles of other halogen-containing compounds / number of moles of magnesium compound) relative to the amount of the magnesium compound, regardless of whether the magnesium compound and the titanium compound each contain a halogen.

[0034] The amount of electron donor used is preferably 0.001 to 10, more preferably 0.01 to 5, in terms of molar ratio (number of moles of electron donor / number of moles of magnesium compound) relative to the amount of magnesium compound used, regardless of whether other halogen-containing compounds are used.

[0035] The contact conditions for the components may be any as long as they do not significantly impair the effects of the present invention, but the following conditions are generally preferred. The contact temperature is preferably from -50°C to 200°C, more preferably from 0°C to 150°C. Examples of the contacting method include a dry contacting method using a rotary ball mill or a vibration mill, and a wet contacting method using stirring in the presence of an inert diluent.

[0036] In the preparation of the solid component (a1), intermediate and / or final washing with an inert solvent may be carried out. Preferred solvents include aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as toluene and xylene, and halogen-containing hydrocarbons such as 1,2-dichloroethylene and chlorobenzene.

[0037] Any method can be used to prepare the solid component (a1) according to the present invention, and specific examples include the methods described below as (i) to (vii). However, the present invention is not limited to the following examples.

[0038] (i) Co-grinding method This method involves co-grinding a halogen-containing magnesium compound, typically magnesium chloride, with a titanium compound to support the titanium compound on the magnesium compound. An electron donor may be co-grinded at the same time or in a separate step. As a mechanical pulverization method, any pulverizer such as a rotary ball mill or a vibration mill can be used. Not only a dry pulverization method that does not use a solvent, but also a wet pulverization method in which pulverization is performed in the presence of an inert solvent can be used.

[0039] (ii) Heat treatment method This method involves stirring a halogen-containing magnesium compound, such as magnesium chloride, with a titanium compound in an inert solvent to carry out a contact treatment, thereby supporting the titanium compound on the magnesium compound. An electron donor may be contacted simultaneously or in a separate step. When a liquid compound such as titanium tetrachloride is used as the titanium compound, the contact treatment can be carried out without using an inert solvent. If necessary, an optional component such as a silicon halide compound may be contacted simultaneously or in a separate step. There is no particular limitation on the contact temperature, but it is often preferable to carry out the contact treatment at a relatively high temperature of about 90°C to 130°C.

[0040] (iii) Elution method The dissolution-precipitation method is a method in which a halogen-containing magnesium compound, such as magnesium chloride, is dissolved by contacting it with an electron donor, and the resulting solution is brought into contact with a precipitating agent to cause a precipitation reaction, thereby forming particles. Examples of electron donors used for dissolution include alcohol compounds, epoxy compounds, phosphate ester compounds, silicon compounds having an alkoxy group, titanium compounds having an alkoxy group, and ether compounds. Examples of the precipitating agent include titanium halide compounds, silicon halide compounds, hydrogen chloride, halogen-containing hydrocarbon compounds, siloxane compounds (including polysiloxane compounds) having a Si-H bond, and aluminum compounds. The method for contacting the solution with the precipitating agent may be to add the precipitating agent to the solution, or to add the solution to the precipitating agent. In either the dissolution or precipitation step, when no titanium compound is used, the particles formed by the precipitation reaction are further brought into contact with a titanium compound, thereby supporting the titanium compound on the magnesium compound. If necessary, the grains formed by the above method may be contacted with an optional component such as a titanium halide compound or a silicon halide compound, or may be contacted with an electron donor, which may be different from or the same as the electron donor used for dissolution. The order of contacting these optional components is not particularly limited, and they may be contacted in independent steps or may be contacted together during dissolution, precipitation and contact with the titanium compound. An inert solvent may be present in any of the steps of dissolution, precipitation, and contact with an optional component.

[0041] (iv) Granulation method The granulation method, like the dissolution-precipitation method, involves dissolving a halogen-containing magnesium compound, such as magnesium chloride, by contacting it with an electron donor, and granulating the resulting solution primarily by physical means. Examples of electron donors used for dissolution are the same as those used in the dissolution-precipitation method. Examples of granulation techniques include a method in which a high-temperature solution is dropped into a low-temperature inert solvent, a method in which the solution is sprayed from a nozzle toward a high-temperature gas phase to dry it, and a method in which the solution is sprayed from a nozzle toward a low-temperature gas phase to cool it. The particles formed by granulation are brought into contact with a titanium compound, thereby supporting the titanium compound on the magnesium compound. If necessary, the mixture may be contacted with an optional component such as a silicon halide compound or an electron donor. In this case, the electron donor may be the same as or different from that used in the dissolution. The order of contacting these optional components is not particularly limited, and they may be contacted in independent steps or together when dissolving or contacting with the titanium compound. An inert solvent may be present in any of the steps of dissolution, contact with the titanium compound, and contact with the optional components.

[0042] (v) Halogenation of magnesium (Mg) compounds The halogenation method for magnesium (Mg) compounds is a method in which a halogen-free magnesium compound is contacted with a halogenating agent to halogenate it, and an electron donor may be contacted with the compound simultaneously or in a separate step. Examples of halogen-free magnesium compounds include dialkoxy magnesium compounds, magnesium oxide, magnesium carbonate, and magnesium salts of fatty acids. When a dialkoxymagnesium compound is used, it can be prepared in situ by reacting metallic magnesium with an alcohol. When this preparation method is used, particles are generally formed by granulation or the like at the stage of the starting material, a halogen-free magnesium compound. Examples of the halogenating agent include titanium halide compounds, silicon halide compounds, and phosphorus halide compounds. When a titanium halide compound is not used as the halogenating agent, the halogen-containing magnesium compound formed by halogenation is further contacted with a titanium compound to support the titanium compound on the magnesium compound. If necessary, the grains formed by the above method may be contacted with an optional component such as a titanium halide compound or a silicon halide compound, or may be contacted with an electron donor. The order of contacting these optional components is not particularly limited, and they may be contacted as independent steps, or they may be contacted together with the halogenation of a halogen-free magnesium compound or the contact with a titanium compound. An inert solvent may be present in either the step of contacting with the titanium halide compound or the step of contacting with the optional component.

[0043] (vi) Precipitation from organomagnesium compounds This method involves contacting a precipitating agent with a solution of an organomagnesium compound such as a Grignard reagent, typically butylmagnesium chloride, or a dialkylmagnesium compound. An electron donor may be contacted simultaneously or in a separate step. Examples of the precipitating agent include titanium compounds, silicon compounds, and hydrogen chloride. When a titanium compound is not used as the precipitating agent, the particles formed by the precipitation reaction are further brought into contact with a titanium compound, thereby supporting the titanium compound on the magnesium compound. If necessary, the grains formed by the above method may be contacted with an optional component such as a titanium halide compound or a silicon halide compound, or may be contacted with an electron donor. There is no particular limitation on the order of contacting these optional components, and they may be contacted as independent steps or together with the precipitation or contact with the titanium compound. An inert solvent may be present in any of the steps of precipitation, contact with the titanium compound, and contact with the optional component.

[0044] (vii) Impregnation method This method involves impregnating an inorganic compound support or an organic compound support with a solution of an organic magnesium compound or a solution in which a magnesium compound is dissolved with an electron donor. Examples of the organomagnesium compound are the same as those in the example of the precipitation method from an organomagnesium compound. The magnesium compound used to dissolve the magnesium compound may or may not contain a halogen, and examples of the electron donor are the same as those in the example of the dissolution-precipitation method. Examples of inorganic carriers include silica, alumina, magnesia, and the like. Examples of organic carriers include polyethylene, polypropylene, and polystyrene. After the impregnation treatment, the carrier particles are subjected to a chemical reaction with a precipitating agent or physical treatment such as drying to precipitate and immobilize the magnesium compound. Examples of the precipitating agent are the same as those in the dissolution-precipitation method. When a titanium compound is not used as a precipitating agent, the particles thus formed are further contacted with a titanium compound to support the titanium compound on the magnesium compound. If necessary, the particles thus formed may be further contacted with an optional component such as a titanium halide compound or a silicon halide compound, or may be contacted with an electron donor. The order of contacting these optional components is not particularly limited, and they may be contacted as independent steps, or they may be contacted together during impregnation, precipitation, drying, and contact with a titanium compound. In addition, an inert solvent may be present in any of the steps of impregnation, precipitation, contact with a titanium compound, and contact with an optional component.

[0045] (viii) Combined method The methods (i) to (vii) above can also be used in combination. Examples of such combinations include "a method in which magnesium chloride is co-ground with an electron donor, followed by heat treatment with a titanium halide compound," "a method in which a magnesium chloride compound is co-ground with an electron donor, then dissolved using another electron donor, and then precipitated using a precipitating agent," "a method in which a dialkoxymagnesium compound is dissolved using an electron donor, and then contacted with a titanium halide compound to precipitate and simultaneously halogenate the magnesium compound," and "a method in which a dialkoxymagnesium compound is contacted with carbon dioxide to produce and simultaneously dissolve a magnesium carbonate ester compound, the resulting solution is impregnated into silica, and then contacted with hydrogen chloride to simultaneously halogenate and precipitate and fix the magnesium compound, and then contacted with a titanium halide compound to support the titanium compound."

[0046] 1-1-6. Prepolymerization of solid component (a1) In the present invention, the solid component (a1) may be prepolymerized using a polymerization monomer in the presence of an organoaluminum compound as a co-catalyst. The compounds disclosed in JP-A-2004-124090 can be used as the prepolymerization monomer in the prepolymerization. Specific examples of the prepolymerization monomer include ethylene, propylene, 1-butene, 3-methylbutene-1, 1-pentene, 1-hexene, 4-methylpentene-1, 1-octene, 1-decene, 1-undecene, 1-eicosene, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,4-pentadiene, 2,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, cis-2,trans-4-hexadiene, trans-2,trans-4-hexadiene, 1,3-heptadiene, 1,4-hept ... ,5-heptadiene, 1,6-heptadiene, 2,4-heptadiene, 2,6-octadiene, cyclopentadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,3-cycloheptadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,9-decadiene, 1,13-tetradecadiene, p-divinylbenzene, m-divinylbenzene, o-divinylbenzene, styrene, α-methylstyrene, allylbenzene, chlorostyrene, and the like.

[0047] The reaction conditions for the prepolymerization may be any as long as they do not significantly impair the effects of the present invention. Generally, the following ranges are preferred. The amount of prepolymerization is preferably 0.001 g to 100 g, more preferably 0.1 g to 50 g, and even more preferably 0.5 g to 10 g per gram of the solid component (a1). The reaction temperature during prepolymerization is preferably −150° C. to 150° C., and more preferably 0° C. to 100° C. The reaction temperature during prepolymerization is preferably lower than the polymerization temperature during main polymerization. The reaction is generally preferably carried out under stirring, and an inert solvent such as hexane or heptane may be present. The prepolymerization may be carried out multiple times, and the polymerizable monomers used in these steps may be the same or different. Furthermore, the solid component after the prepolymerization may be washed with an inert solvent such as hexane or heptane. The type and amount of the organoaluminum compound used may be the same as those described below for component (a4).

[0048] 1-2. Silane compounds having alkenyl groups (a2) Component (a2) is a silane compound having an alkenyl group. Representative examples include the compounds disclosed in JP-A-2-34707, JP-A-2003-292522, JP-A-2006-169283, and JP-A-2011-74360.

[0049] The silane compound having an alkenyl group is preferably a compound represented by the following general formula (4). General formula (4) SiR 9 n R 10 4-n (where R 9 each independently represents an alkenyl group, and R 10 each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, and n is 1, 2, 3, or 4. When n is 1 or 2, R 10 They may be linked to each other to form a ring structure.)

[0050] In general formula (4), R 9 Each of R independently represents an alkenyl group. Specific examples of the alkenyl group include a vinyl group, an allyl group, and a 3-butenyl group. As the alkenyl group, a vinyl group and an allyl group are preferred, and a vinyl group is more preferred. When the value of n is 2 or more, multiple R 9 may be the same or different. n may be 1, 2, or 3, and may also be 1 or 2.

[0051] In general formula (4), R 10 each independently represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. R 10Examples of the halogen atom that can be used as the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 10 The alkyl group as R may be a linear alkyl group, a branched alkyl group, or a cycloalkyl group. 10 is an alkyl group, R 10 is generally an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, a thexyl group, a cyclopentyl group, and a cyclohexyl group. R 10 When R is an alkoxy group, 10 is generally an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, an i-butoxy group, an s-butoxy group, and a t-butoxy group. If the value of n is 1 or 2, there are multiple R 10 may be the same or different. When n is 1 or 2, R 10 They may be linked together to form a ring structure. 10 An example of a cyclic structure in which rings are linked together is a silacyclopentane structure. R 10 is preferably a halogen atom or an alkyl group, more preferably an alkyl group, still more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

[0052] Specific examples of the silane compound (a2) having an alkenyl group include vinylsilane, methylvinylsilane, dimethylvinylsilane, trimethylvinylsilane, trichlorovinylsilane, dichloromethylvinylsilane, chlorodimethylvinylsilane, chloromethylvinylsilane, triethylvinylsilane, chlorodiethylvinylsilane, dichloroethylvinylsilane, dimethylethylvinylsilane, diethylmethylvinylsilane, tripentylvinylsilane, triphenylvinylsilane, and diphenylmethylvinylsilane. divinylsilane, dimethylphenylvinylsilane, CH2=CH-Si(CH3)2(C6H4CH3), (CH2=CH)(CH3)2Si-O-Si(CH3)2(CH=CH2), divinylsilane, dichlorodivinylsilane, dimethyldivinylsilane, diphenyldivinylsilane, allyltrimethylsilane, allyltriethylsilane, allyltrivinylsilane, allylmethyldivinylsilane, allyldimethylvinylsilane, allylmethyldichlorosilane, allyltrichlorosilane, allyltrimethyl Bromosilane, diallyldimethylsilane, diallyldiethylsilane, diallyldivinylsilane, diallylmethylvinylsilane, diallylmethylchlorosilane, diallyldichlorosilane, diallyldibromosilane, triallylmethylsilane, triallylethylsilane, triallylvinylsilane, triallylchlorosilane, triallylbromosilane, tetraallylsilane, di-3-butenyldimethylsilane, di-3-butenyldiethylsilane, di-3-butenyldivinylsilane, di-3-butenyl Silane, methyl vinyl silane, di-3-butenyl silane, methyl chloro silane, di-3-butenyl silane, dichloro silane, tri-3-butenyl silane, ethyl silane, tri-3-butenyl silane, vinyl silane, chloro silane, bromo silane, tetra-3-butenyl silane, 1-methyl-1-vinyl silacyclobutane, 1-methyl-1-vinyl silacyclopentane, 1-methyl-1-vinyl silacyclohexane, 1,1-divinyl silacyclopentane, 1,Examples include 1-divinylsilacyclohexane, 1-chloro-1-vinylsilacyclopentane, 1-chloro-1-vinylsilacyclohexane, 1-allyl-1-methylsilacyclopentane, and 1-allyl-1-methylsilacyclohexane.

[0053] Among the above silane compounds having an alkenyl group, vinylsilane compounds are preferred, with trimethylvinylsilane, trichlorovinylsilane, dimethyldivinylsilane, and 1-methyl-1-vinylsilacyclopentane being more preferred. The above silane compounds having an alkenyl group may be used alone or in combination of two or more.

[0054] The amount of the silane compound (a2) having an alkenyl group used may be any amount within the range that does not significantly impair the effects of the present invention, but the following ranges are generally preferred. The amount of the silane compound (a2) having an alkenyl group used is preferably 0.001 to 1,000, more preferably 0.01 to 100, in terms of the molar ratio to the titanium constituting the solid component (a1) (number of moles of the silane compound (a2) having an alkenyl group / number of moles of titanium atoms in the solid component (a1)).

[0055] The silane compound (a2) having an alkenyl group used in the present invention has a greater steric hindrance than the α-olefin monomer usually used in polymerization, and is not polymerized with a Ziegler-Natta catalyst. However, due to the presence of an organic silyl group with very strong electron-donating properties, the charge density of the carbon-carbon double bond is very high, and it is thought that the silane compound (a2) having an alkenyl group coordinates or inserts into the titanium atom, which is the active site. Therefore, it is expected to be effective in preventing over-reduction of the titanium atom by the organic aluminum compound of component (a4) used in preparing the contact product (1) and deactivation of the active site by impurities.

[0056] 1-3. Alkoxysilane compound (a3) The component (a3) ​​is an alkoxysilane compound. The alkoxysilane compound (a3) ​​is different from the silane compound (a2) having an alkenyl group. The alkoxysilane compound may be a compound represented by the following general formula (3). General formula (3) R 6 R 7 m Si(OR 8 ) n (where R 6 represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. 7 R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. 8 each independently represents a hydrocarbon group, m is 0, 1 or 2, n is 1, 2 or 3, and m+n=3 is satisfied.

[0057] In general formula (3), R 6 represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. R 6 When R is a hydrocarbon group, it is a hydrocarbon group excluding an alkenyl group. 6 is generally a hydrocarbon group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the hydrocarbon group include linear aliphatic hydrocarbon groups such as n-propyl groups, branched aliphatic hydrocarbon groups such as i-propyl groups and t-butyl groups, alicyclic hydrocarbon groups such as cyclopentyl groups and cyclohexyl groups, and aromatic hydrocarbon groups such as phenyl groups. 6 is preferably a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group, more preferably a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group having 3 to 6 carbon atoms, such as an i-propyl group, an i-butyl group, a t-butyl group, a thexyl group, a cyclopentyl group, or a cyclohexyl group. R 6 When is a heteroatom-containing hydrocarbon group, the heteroatom is preferably selected from a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, or a silicon atom, and more preferably a nitrogen atom or an oxygen atom. R6 The skeleton structure of the heteroatom-containing hydrocarbon group is 6 is a hydrocarbon group, more preferably an N,N-diethylamino group, a quinolino group, or an isoquinolino group.

[0058] In general formula (3), R 7 each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 7 When R is a hydrocarbon group, it is a hydrocarbon group excluding an alkenyl group. 7 is generally a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group include linear aliphatic hydrocarbon groups such as methyl and ethyl groups, branched aliphatic hydrocarbon groups such as i-propyl and t-butyl groups, alicyclic hydrocarbon groups such as cyclopentyl and cyclohexyl groups, and aromatic hydrocarbon groups such as phenyl groups. 7 is more preferably a linear or branched aliphatic hydrocarbon group or alicyclic hydrocarbon group having 1 to 6 carbon atoms, and a methyl group, an ethyl group, a propyl group, an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, a thexyl group, a cyclopentyl group, a cyclohexyl group, etc. are preferred. R 7 is a heteroatom-containing hydrocarbon group, R 6 is preferably selected from the examples of a heteroatom-containing hydrocarbon group, more preferably an N,N-diethylamino group, a quinolino group, or an isoquinolino group. Moreover, regardless of the value of m, R 7 is R 6 may be the same as or different from. m is 0, 1 or 2, but may be 0 or 1, or may be 1.

[0059] In general formula (3), R 8 R each independently represents a hydrocarbon group. 8is generally a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specific examples of the hydrocarbon group include linear aliphatic hydrocarbon groups such as a methyl group and an ethyl group, and branched aliphatic hydrocarbon groups such as an i-propyl group and a t-butyl group. 8 As the alkyl group, a methyl group and an ethyl group are preferred. If the value of n is 2 or more, there are multiple R 8 may be the same or different. n is 1, 2 or 3, and m+n=3 is satisfied, but n may be 2 or 3, or may be 2.

[0060] Specific examples of the alkoxysilane compound (a3) ​​include t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-butylethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isobutylisopropyldimethoxysilane, n-propylmethyldimethoxysilane, t-butyltriethoxysilane, bis(diethylamino)dimethoxysilane, diethylaminotriethoxysilanemethoxysilane, and bisperhydroisoquinolinodimethoxysilane. The above alkoxysilane compounds may be used alone or in combination of two or more.

[0061] The amount of the alkoxysilane compound (a3) ​​used may be any amount within the range that does not significantly impair the effects of the present invention, but the following ranges are generally preferred. The amount of the alkoxysilane compound (a3) ​​used is preferably 0.01 to 1,000, more preferably 0.1 to 100, in terms of the molar ratio to titanium constituting the solid component (a1) (number of moles of alkoxysilane compound (a3) / number of moles of titanium atoms in the solid component (a1)).

[0062] The alkoxysilane compound (a3) ​​used in the present invention is thought to be coordinated in the vicinity of titanium atoms that can serve as active sites, and to control catalytic performance such as the catalytic activity of the active sites and the regularity of the polymer.

[0063] 1-4. Organoaluminum compound (a4) represented by general formula (1) The component (a4) is an organoaluminum compound represented by the following general formula (1). General formula (1) R 3-a AlX a (wherein, each R independently represents a hydrocarbon group having 1 to 20 carbon atoms, each X independently represents a hydrogen atom or a halogen atom, and a represents a number satisfying 0≦a≦2.)

[0064] In general formula (1), each R independently represents a hydrocarbon group having 1 to 20 carbon atoms. R is generally a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. A methyl group, an ethyl group, and an isobutyl group are preferred. In general formula (1), X represents a hydrogen atom or a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Chlorine is preferred as the halogen atom.

[0065] Specific examples of the organoaluminum compound (a4) include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, and ethylaluminum chloride. Among the above organoaluminum compounds, triethylaluminum and triisobutylaluminum are preferred. The organoaluminum compounds (a4) may be used singly or in combination of two or more.

[0066] The amount of the organoaluminum compound (a4) used may be any amount within the range that does not significantly impair the effects of the present invention, but the following ranges are generally preferred. The amount of the organoaluminum compound (a4) used is preferably 0.1 to 100, more preferably 1 to 50, in terms of the molar ratio to titanium constituting the solid component (a1) (number of moles of aluminum atoms / number of moles of titanium atoms in the solid component (a1)).

[0067] The organoaluminum compound (a4) used in the present invention is used mainly for the purpose of efficiently supporting the alkoxysilane compound (a3) ​​in the contact product (1). Therefore, the organoaluminum compound (a4) used in step 1 is distinguished from the organoaluminum compounds used as a co-catalyst for the polymerization reaction during prepolymerization or main polymerization, as their main purpose is different.

[0068] 1-5. Contact products (1) In the production method of the present invention, the contact product (1) can be obtained by contacting a solid component (a1), an alkenyl group-containing silane compound (a2), an alkoxysilane compound (a3), and an organoaluminum compound (a4). In the production method of the present invention, the contact treatment may be carried out multiple times when preparing the contact product (1). When the contact treatment is carried out multiple times, the compounds used in the multiple contact treatments, including the silane compound (a2) having an alkenyl group, the alkoxysilane compound (a3), and the organoaluminum compound (a4), may be the same or different from one another. The contact product (1) is obtained by contacting the above-mentioned constituent components in the above-mentioned ratios. Furthermore, the range of the amount of each component used was indicated above, but this is the amount used per contact, and from the second time onwards, the components may be contacted any number of times as long as the amount used per contact is within the range of the amount used above.

[0069] The contact conditions for the components may be any as long as they do not significantly impair the effects of the present invention, but the following conditions are generally preferred.

[0070] The contact temperature may be from 0°C to 110°C, and is preferably from 20°C to 100°C. Examples of the contacting method include a dry contacting method using a rotary ball mill or a vibration mill, a wet contacting method by stirring in the presence of an inert diluent, etc. A wet contacting method by stirring in the presence of an inert diluent is preferred.

[0071] In the contact treatment, the solid component (a1), the silane compound (a2) having an alkenyl group, the alkoxysilane compound (a3), and the organoaluminum compound (a4) may be contacted in any procedure. Specific examples include the following procedures (i) to (iv), with the procedure (i) or (ii) being preferred. Step (i): A method in which the solid component (a1) is contacted with a silane compound (a2) having an alkenyl group, then with an alkoxysilane compound (a3), and then with an organoaluminum compound (a4). Step (ii): A method in which the solid component (a1) is contacted with a mixture which has been previously prepared by contacting a silane compound (a2) having an alkenyl group with an alkoxysilane compound (a3), and then the mixture is contacted with an organoaluminum compound (a4). Step (iii): A method in which the solid component (a1) is contacted with an alkoxysilane compound (a3), then with a silane compound (a2) having an alkenyl group, and then with an organoaluminum compound (a4). Step (iv): A method of contacting the solid component (a1) with a mixture of an alkenyl-containing silane compound (a2), an alkoxysilane compound (a3), and an organoaluminum compound (a4) that have already been contacted.

[0072] When preparing the contact product (1), optional components may be contained within the range that does not significantly impair the effects of the present invention. In the step of obtaining the contact product (1), it is preferable not to contact the component (a5) (organoaluminum compound represented by general formula (2)) used in the step 2 described below, in order to improve the effects of the present invention.

[0073] In preparing the contact product (1), intermediate and / or final washing with an inert solvent may be performed. Preferred solvents include aliphatic hydrocarbon compounds such as heptane, aromatic hydrocarbon compounds such as toluene and xylene, and halogen-containing hydrocarbon compounds such as 1,2-dichloroethylene and chlorobenzene.

[0074] 1-6. Prepolymerization of Contact Product (1) In the present invention, the contact product (1) may be prepolymerized using a polymerization monomer in the presence of an organoaluminum compound as a co-catalyst. Examples of the prepolymerized monomer in the prepolymerization include the same as the prepolymerized monomer described above.

[0075] The reaction conditions for the prepolymerization may be any as long as they do not significantly impair the effects of the present invention. Generally, the following ranges are preferred. The amount of prepolymerization is preferably 0.001 g to 100 g, more preferably 0.1 g to 50 g, and even more preferably 0.5 g to 10 g per gram of the contact product (1). The reaction temperature during prepolymerization is preferably −150° C. to 150° C., and more preferably 0° C. to 100° C. The reaction temperature during prepolymerization is preferably lower than the polymerization temperature during main polymerization. The reaction is generally preferably carried out under stirring, and an inert solvent such as hexane or heptane may be present. The prepolymerization may be carried out multiple times, and the polymerization monomers used in these steps may be the same or different. After the prepolymerization, the contact product (1) may be washed with an inert solvent such as hexane or heptane. The type and amount of the organoaluminum compound used may be the same as those described above for component (a4).

[0076] 2.Process 2 Step 2 is a step of contacting components including the contact product (1) with the following components (a2) and (a5) to obtain a contact product (2).

[0077] 2-1. Components containing contact product (1) The component containing the contact product (1) may be the contact product (1) itself obtained in step 1, or may contain the contact product (1) and further include optional components within the range that does not significantly impair the effects of the present invention.

[0078] 2-2. Silane compounds having alkenyl groups (a2) Component (a2) is a silane compound having an alkenyl group. Examples of the silane compound having an alkenyl group include the same silane compound having an alkenyl group as component (a2) in step 1.

[0079] Among the above silane compounds having an alkenyl group, vinylsilane compounds are preferred, with trimethylvinylsilane, trichlorovinylsilane, dimethyldivinylsilane, and 1-methyl-1-vinylsilacyclopentane being more preferred. The above silane compounds having an alkenyl group may be used alone or in combination of two or more. The silane compound having an alkenyl group used in step 2 may be the same as or different from the silane compound having an alkenyl group, which is component (a2) used in step 1.

[0080] The amount of the silane compound (a2) having an alkenyl group used may be any amount within the range that does not significantly impair the effects of the present invention, but the following ranges are generally preferred. The amount of the silane compound (a2) having an alkenyl group used is preferably 0.001 to 1,000, more preferably 0.01 to 100, in terms of the molar ratio to the titanium constituting the solid component (a1) (number of moles of the silane compound (a2) having an alkenyl group / number of moles of titanium atoms in the solid component (a1)).

[0081] When a solid catalyst component for olefin polymerization is produced without contacting it with a silane compound (a2) having an alkenyl group in step 2, the effect of reducing the 40°C soluble component (amorphous component) is small, as shown in the comparative example described below. It is presumed that by allowing the silane compound (a2) having an alkenyl group to coexist with the component (a5) used in step 2, the silane compound (a2) having an alkenyl group protects and stabilizes the active species (Ti), and the bridged organoaluminum compound of component (a5) directly controls the coordination field without over-reducing (deactivating) the active species (Ti).

[0082] 2-3. Organoaluminum compound (a5) represented by general formula (2) The component (a5) is an organoaluminum compound represented by the following general formula (2).

[0083] [ka] (where R 1 ~R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and R 5 represents a divalent hydrocarbon group having 1 to 20 carbon atoms.

[0084] In general formula (2), R 1 ~R 4 R each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different. 1 ~R 4 are each independently a hydrocarbon group having a length of preferably 1 to 10. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group. 1 ~R 4 are each independently more preferably a hydrocarbon group having 1 to 4 carbon atoms, and a methyl group, an ethyl group, or an isobutyl group is even more preferred.

[0085] In general formula (2), R 5 represents a divalent hydrocarbon group having 1 to 20 carbon atoms. 5is preferably a divalent hydrocarbon group having an integer of 1 to 10. Specific examples of the divalent hydrocarbon group include a methylene group, an ethylene group, a methylethylene group, a dimethylethylene group, a tetramethylethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, a vinylidene group, a propenylene group, a 1,4-cyclohexylene group, and a 1,2-cyclohexylene group.

[0086] Specific examples of the organoaluminum compound represented by general formula (2) include compounds represented by the following chemical formula: In this specification, Et represents an ethyl group, iBu represents an i-butyl group, nPr represents an n-propyl group, and nHex represents an n-hexyl group.

[0087] [ka]

[0088] [ka]

[0089] The amount of the organoaluminum compound (a5) used may be any amount within the range that does not significantly impair the effects of the present invention, but the following ranges are generally preferred. The amount of the organoaluminum compound (a5) used is preferably 0.1 to 100, more preferably 1 to 50, in terms of the molar ratio to the titanium constituting the solid component (a1) (number of moles of aluminum atoms / number of moles of titanium atoms in the solid component (a1)).

[0090] The organoaluminum compound (a5), which is a bridged aluminum compound used in the present invention, is supported in the vicinity of the active species in order to reduce the 40°C soluble component (amorphous component), thereby sterically controlling the space around the active species and mainly used for the purpose of controlling the insertion reaction (polymerization reaction) of propylene. Therefore, the organoaluminum compound (a5), which is a bridged aluminum compound, is distinguished from the organoaluminum compound (a4), which is used for the purpose of efficiently supporting the alkoxysilane compound (a3), because the main purpose of the organoaluminum compound (a5) is different. In the present invention, the organoaluminum compound (a5), which is a crosslinked aluminum compound, is not used during polymerization, but rather, the organoaluminum compound (a5) is used during catalyst preparation, which is believed to enable the organoaluminum compound (a5) to be supported in the vicinity of the active site more efficiently than when used during polymerization. Therefore, the method for producing a propylene polymer of the present invention is believed to enable a further reduction in amorphous components and an improvement in stereoregularity.

[0091] 2-4. Contact products (2) In the production method of the present invention, the contact product (2) can be obtained by contacting a component containing the contact product (1), a silane compound (a2) having an alkenyl group, and an organoaluminum compound (a5). When preparing the contact product (2), optional components may be contained within the range that does not significantly impair the effects of the present invention. In step 2, when the components containing the contact product (1), the component (a2), and the component (a5) are contacted, an alkoxysilane compound different from the component (a2), an organoaluminum compound different from the component (a5), or the like may be further contacted to obtain the contact product (2).

[0092] Examples of the alkoxysilane compound different from component (a2) used in step 2 include the same alkoxysilane compound as component (a3) ​​in step 1 above. The alkoxysilane compound different from component (a2) used in step 2 may be the same as or different from the alkoxysilane compound that is component (a3) ​​used in step 1.

[0093] The amount of the alkoxysilane compound different from component (a2) used in step 2 is optional, but the molar ratio to the titanium constituting solid component (a1) (number of moles of alkoxysilane compound / number of moles of titanium atoms in solid component (a1)) is preferably 0.01 to 1,000, more preferably 0.1 to 100.

[0094] Examples of organoaluminum compounds different from component (a5) used in step 2 include the same organoaluminum compounds as component (a4) in step 1, which are represented by general formula (1). The organoaluminum compound different from component (a5) used in step 2 may be the same as or different from the organoaluminum compound of component (a4) used in step 1.

[0095] The amount of the organoaluminum compound different from component (a5) used in step 2 is optional, but the molar ratio to the titanium constituting solid component (a1) (number of moles of aluminum atoms / number of moles of titanium atoms in solid component (a1)) is preferably 0.1 to 100, more preferably 1 to 50.

[0096] In the production method of the present invention, the contact product (2) can also be obtained by contacting a component containing the contact product (1), a silane compound (a2) having an alkenyl group, and an organoaluminum compound (a5), as well as the alkoxysilane compound (a3) ​​and the organoaluminum compound (a4).

[0097] In the production method of the present invention, the contact treatment may be carried out multiple times when preparing the contact product (2). When the contact treatment is carried out multiple times, the compounds used in the multiple contact treatments may be the same or different from each other, for example, the silane compound (a2) having an alkenyl group, the alkoxysilane compound (a3), the organoaluminum compound (a4), and the organoaluminum compound (a5).

[0098] The solid catalyst component for olefin polymerization used in the present invention can be obtained by contacting the above-mentioned constituent components in the above-mentioned ratios. Furthermore, the range of the amount of each component used was indicated above, but this is the amount used per contact, and from the second time onwards, the components may be contacted any number of times as long as the amount used per contact is within the range of the amount used above.

[0099] The contact conditions for the components may be any as long as they do not significantly impair the effects of the present invention, but the following conditions are generally preferred.

[0100] The contact temperature is preferably 0°C to 110°C, more preferably 20°C to 100°C. Examples of the contacting method include a dry contacting method using a rotary ball mill or a vibration mill, a wet contacting method by stirring in the presence of an inert diluent, etc. A wet contacting method by stirring in the presence of an inert diluent is preferred.

[0101] In the contact treatment, the solid component (a1), the silane compound (a2) having an alkenyl group, and the organoaluminum compound (a5) may be contacted in any procedure. Specific examples include the following procedures (v) and (vi), with procedure (v) being preferred. Step (v): A method in which the solid component (a1) is contacted with the silane compound (a2) having an alkenyl group, and then with the organoaluminum compound (a5). Step (vi): A method of contacting the solid component (a1) with a compound which has been previously contacted with a silane compound (a2) having an alkenyl group and an organoaluminum compound (a5).

[0102] In the contact treatment, when the solid component (a1), the silane compound (a2) having an alkenyl group, the alkoxysilane compound (a3), the organoaluminum compound (a4), and the organoaluminum compound (a5) are used, any contact procedure may be used. Specific examples include the following procedures (vii) to (x), with the procedures (vii) and (viii) being preferred. Step (vii): A method in which the solid component (a1) is contacted with a silane compound (a2) having an alkenyl group, then with an alkoxysilane compound (a3), and then with an organoaluminum compound (a4) and an organoaluminum compound (a5). Step (viii): A method in which the solid component (a1) is contacted with a mixture which has been previously prepared by contacting a silane compound (a2) having an alkenyl group with an alkoxysilane compound (a3), and then the solid component is contacted with an organoaluminum compound (a4) and an organoaluminum compound (a5). Step (ix): A method in which the solid component (a1) is contacted with an alkoxysilane compound (a3), then with a silane compound (a2) having an alkenyl group, and then with an organoaluminum compound (a4) and an organoaluminum compound (a5). Step (x): A method of contacting a solid component (a1) with a mixture of an alkenyl-containing silane compound (a2), an alkoxysilane compound (a3), an organoaluminum compound (a4), and an organoaluminum compound (a5) that have already been contacted.

[0103] In preparing the contact product (2), intermediate and / or final washing with an inert solvent may be performed. Preferred solvents include aliphatic hydrocarbon compounds such as heptane, aromatic hydrocarbon compounds such as toluene and xylene, and halogen-containing hydrocarbon compounds such as 1,2-dichloroethylene and chlorobenzene.

[0104] 2-5. Prepolymerization of Contact Product (2) In the present invention, the contact product (2) may be prepolymerized using a polymerization monomer in the presence of an organoaluminum compound as a co-catalyst. Examples of the prepolymerized monomer in the prepolymerization include the same as the prepolymerized monomer described above.

[0105] The reaction conditions for the prepolymerization may be any as long as they do not significantly impair the effects of the present invention. Generally, the following ranges are preferred. The amount of prepolymerization is preferably 0.001 g to 100 g, more preferably 0.1 g to 50 g, and even more preferably 0.5 g to 10 g per gram of the contact product (2). The reaction temperature during prepolymerization is preferably −150° C. to 150° C., and more preferably 0° C. to 100° C. The reaction temperature during prepolymerization is preferably lower than the polymerization temperature during main polymerization. The reaction is generally preferably carried out under stirring, and an inert solvent such as hexane or heptane may be present. The prepolymerization may be carried out multiple times, and the polymerization monomers used in these steps may be the same or different. The contact product (2) after the prepolymerization may be washed with an inert solvent such as hexane or heptane. The type and amount of the organoaluminum compound used may be the same as those described above for component (a4).

[0106] 3. Solid catalyst components for olefin polymerization The solid catalyst component for olefin polymerization produced by the present invention includes a contact product (2). The solid catalyst component for olefin polymerization of the present invention may be the contact product (2) itself, or may be a product obtained by subjecting the contact product (2) to a prepolymerization treatment, or may be a product of these products that have been subjected to an appropriate further treatment. Examples of the appropriate further treatment include physical treatments such as classification, washing, and drying, and chemical treatments such as oxidation and reduction reactions.

[0107] II. Method for producing propylene polymer The method for producing a propylene polymer of the present invention is characterized by homopolymerizing or copolymerizing propylene in the presence of the solid catalyst component (A) for olefin polymerization obtained by the production method of the present invention and an organoaluminum compound (B) represented by the following general formula (1): General formula (1) R 3-a AlX a (wherein, each R independently represents a hydrocarbon group having 1 to 20 carbon atoms, each X independently represents a hydrogen atom or a halogen atom, and a represents a number satisfying 0≦a≦2.)

[0108] 1. Olefin polymerization catalysts The olefin polymerization catalyst used in the method for producing a propylene polymer of the present invention contains the solid catalyst component (A) for olefin polymerization produced by the present invention and the organoaluminum compound (B) represented by the general formula (1). The olefin polymerization catalyst used in the present invention may further contain an external electron donor.

[0109] The solid catalyst component (A) for olefin polymerization is a solid catalyst component for olefin polymerization that can be obtained by the above-mentioned method for producing a solid catalyst component for olefin polymerization of the present invention.

[0110] The organoaluminum compound (B) represented by the general formula (1) may be the same as the organoaluminum compound (a4) represented by the general formula (1) used in preparing the contact product (1). The organoaluminum compound (B) represented by the general formula (1) used in the polymerization can be selected from the same group as the examples of the organoaluminum compound (a4) used in preparing the contact product (1).

[0111] The organoaluminum compound (B) represented by the general formula (1) may be the same as or different from the organoaluminum compound (a4) used in preparing the contact product (1). The organoaluminum compound (B) represented by the general formula (1) can be used not only as a single compound, but also as a combination of two or more compounds.

[0112] The amount of the organoaluminum compound (B) represented by the general formula (1) used may be any amount within the range that does not significantly impair the effects of the present invention, but the following ranges are generally preferred. The amount of the organoaluminum compound (B) represented by general formula (1) used is preferably 1 to 5,000, more preferably 10 to 500, in terms of the molar ratio to the titanium component contained in the solid component (a1) (number of moles of organoaluminum compound (B) / number of moles of titanium atoms in the solid component (a1)).

[0113] Examples of external electron donors that may be further contained in the olefin polymerization catalyst used in the method for producing a propylene-based polymer of the present invention include alkoxysilane compound (a3), unsaturated cyclic ether compounds disclosed in JP-A-2020-164852, compounds having a C(=O)N bond in the molecule disclosed in JP-A-2004-124090, and sulfite ester compounds disclosed in JP-A-2006-225449.

[0114] The solid catalyst component for olefin polymerization (A) and the organoaluminum compound (B) represented by the general formula (1) can be mixed under any conditions as long as the effects of the present invention are not significantly impaired, and may be mixed under conditions in the absence of oxygen. Examples of the mixing temperature include the temperatures exemplified as the polymerization temperature of α-olefins described below. The device used for mixing may be a conventionally known device having stirring and temperature control functions.

[0115] In the method for producing a propylene-based polymer of the present invention, propylene may be homopolymerized or copolymerized in the presence of the solid catalyst component (A) for olefin polymerization obtained by the production method of the present invention and the organoaluminum compound (B) represented by the general formula (1) without adding the organoaluminum compound represented by the general formula (2). In the process for producing a propylene polymer of the present invention, the solid catalyst component (A) for olefin polymerization supports the organoaluminum compound (a5) represented by the general formula (2), and it is believed that the organoaluminum compound (a5) donates electrons to active species and sterically controls the space around the active species in the solid catalyst component (A) for olefin polymerization. Therefore, the process for producing a propylene polymer of the present invention can reduce amorphous components and produce a propylene polymer with improved stereoregularity, compared to adding the organoaluminum compound represented by the general formula (2) in addition to the organoaluminum compound (B) represented by the general formula (1) during polymerization.

[0116] 2. Method for producing propylene polymer The method for producing a propylene polymer of the present invention is characterized by homopolymerizing or copolymerizing propylene in the presence of the olefin polymerization catalyst.

[0117] Propylene polymerization may be carried out by slurry polymerization using a hydrocarbon solvent, liquid phase solventless polymerization using substantially no solvent, or gas phase polymerization. In the case of slurry polymerization, a hydrocarbon solvent such as pentane, hexane, heptane, or cyclohexane is used as the polymerization solvent. The polymerization method to be employed may be any method such as continuous polymerization, batch polymerization or multi-stage polymerization. The polymerization temperature is usually about 30° C. to 200° C., preferably 50° C. to 150° C., and hydrogen may be used as a molecular weight regulator.

[0118] The polymerization of propylene may be homopolymerization of propylene or copolymerization of propylene with a monomer copolymerizable with propylene. Examples of the monomer copolymerizable with propylene include ethylene, α-olefins having 4 to 22 carbon atoms, dienes, and styrenes, and specific examples thereof include monomers other than propylene listed as the prepolymerized monomers. The copolymerization of propylene with a copolymerizable monomer may be random copolymerization, or block copolymerization in which propylene is homopolymerized in the first stage and then random copolymerized in the second stage can also be carried out. The monomer copolymerizable with propylene can be used in an amount of up to 15% by weight in random copolymerization and up to 50% by weight in block copolymerization. Among these, propylene homopolymerization and block copolymerization are preferred, and propylene homopolymerization and block copolymerization in which the first stage is propylene homopolymerization are most preferred.

[0119] 3. Propylene polymers The index of the propylene polymer obtained by the production method of the present invention is not particularly limited and can be appropriately adjusted depending on various applications.

[0120] 3-1.MFR(g / 10min) The MFR of the propylene polymer obtained by the production method of the present invention is preferably within the range of 0.01 g / 10 min to 10,000 g / 10 min, and particularly preferably within the range of 0.1 g / 10 min to 1,000 g / 10 min.

[0121] 3-2. Melting point (℃) The propylene polymer obtained by the production method of the present invention preferably has high stereoregularity. The degree of stereoregularity of a propylene polymer can be evaluated by measuring the melting point. The propylene polymer obtained by the production method of the present invention preferably has a melting point of 162.6°C or higher and 166.0°C or lower. If the melting point is within the above range, the propylene polymer has a desired rigidity.

[0122] 3-3.40℃ soluble content (mass%) The propylene polymer obtained by the production method of the present invention is characterized by an extremely small amount of amorphous components, high stereoregularity, and good odor and color. The preferred range of the 40°C soluble content as an amorphous component of a propylene polymer generally varies depending on the application. For example, in applications where hard molded articles are preferred, such as general injection molding, the upper limit of the 40°C soluble content of polypropylene is preferably 1.5 mass% or less, more preferably 1.4 mass% or less.

[0123] The propylene polymer obtained by the production method of the present invention has an extremely small amount of amorphous components and high stereoregularity, and therefore has high density, rigidity, heat resistance, and other excellent properties. Furthermore, the propylene polymer obtained by the production method of the present invention can be produced in high yield, and is particularly suitable for use as an industrial material such as an automobile part or a home appliance part, which are required to have high rigidity and high heat resistance, or as a packaging material, etc., since the propylene polymer is less sticky. [Example]

[0124] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The methods for measuring the various physical properties in the present invention are shown below. (1) Titanium content: The sample was accurately weighed, hydrolyzed, and measured by colorimetry. For samples after prepolymerization, the titanium content was calculated using the weight excluding the prepolymerized polymer. (2) Alkoxysilane compound content: The sample was accurately weighed and decomposed in methanol. The silicon compound concentration in the resulting methanol solution was determined by comparison with a standard sample using gas chromatography. The silicon compound content in the sample was calculated from the silicon compound concentration in methanol and the weight of the sample. For samples after prepolymerization, the content was calculated using the weight excluding the prepolymerized polymer. (3) Polymer bulk density: The bulk density of the powder sample was measured using an apparatus conforming to ASTM D1895-69. (4) MFR: Using a melt indexer manufactured by Takara Corporation, evaluation was carried out under the conditions of 230°C and 21.18N in accordance with JIS-K6921.

[0125] (5) 40℃ soluble content (TREF) 40℃ soluble content (TREF): The amount of soluble matter at 40°C measured by TREF is as follows. The sample was dissolved in orthodichlorobenzene at 140°C to prepare a solution, which was then introduced into a temperature rising elution fractionation chromatography (TREF) column at 140°C, cooled to 100°C at a rate of 8°C / min, then cooled to 40°C at a rate of 4°C / min, and then held at 40°C for 10 minutes. The solvent, orthodichlorobenzene, was then passed through the column at a flow rate of 1 mL / min, and the components dissolved in orthodichlorobenzene at 40°C in the TREF column were eluted for 10 minutes to determine the 40°C soluble components. The TREF device configuration used is as follows: 〔Device〕 (TREF section) TREF column: 4.3mmφ x 150mm stainless steel column Column packing material: 100 μm surface-deactivated glass beads Heating method: Aluminum heat block Cooling method: Peltier element (Peltier element is water-cooled) Temperature distribution: ±0.5℃ Temperature controller: Chino Corporation Digital Program Controller KP1000 (valve oven) Heating method: Air bath oven Temperature during measurement: 140℃ Temperature distribution: ±1℃ Valve: 6-way valve, 4-way valve (Sample injection section) Injection method: Loop injection method Injection volume: Loop size 0.1 ml Inlet heating method: Aluminum heat block Temperature during measurement: 140℃ (Detection unit) Detector: Fixed wavelength infrared detector FOXBORO MIRAN 1A Detection wavelength: 3.42 μm High-temperature flow cell: Micro flow cell for LC-IR, optical path length 1.5 mm, window shape 2φ x 4 mm long round, synthetic sapphire window plate Temperature during measurement: 140℃ (Pump section) Liquid transfer pump: Senshu Scientific SSC-3461 pump [Measurement conditions] Solvent: o-dichlorobenzene (containing 0.5 mg / ml BHT) Sample concentration: 5mg / ml Sample injection volume: 0.1 ml Solvent flow rate: 1 ml / min

[0126] Example 1 [Preparation of solid component (a1)] A 10 L autoclave equipped with a stirrer was thoroughly purged with nitrogen, and 2 L of purified toluene was introduced. 200 g of Mg(OEt)2 and 1 L of TiCl4 were added at room temperature. The temperature was raised to 90°C, and 50 mL of di-n-butyl phthalate was added. The temperature was then raised to 110°C and the reaction was carried out for 3 hours. The reaction product was thoroughly washed with purified toluene. Next, purified toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl4 was added at room temperature, and the temperature was raised to 110°C and the reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified toluene. Next, purified toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl4 was added at room temperature, and the temperature was raised to 110°C and the reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified toluene. Next, purified toluene was introduced to adjust the total liquid volume to 2 L. 1 L of TiCl4 was added at room temperature, and the temperature was raised to 110°C and the reaction was carried out for 2 hours. The reaction product was thoroughly washed with purified toluene. Furthermore, purified n-heptane was used to replace toluene with n-heptane to obtain a slurry of solid component (a1). A portion of this slurry was sampled and dried. Analysis revealed that solid component (a1) contained 560 μmol / g of Ti.

[0127] [Preparation of Contact Product (1)] A 500 ml round-bottom flask equipped with a stirrer was thoroughly purged with nitrogen, and 4.0 g of the above-mentioned solid component (a1) slurry was introduced as solid component (a1). Purified n-heptane was added to adjust the liquid level to 25 ml. To this, 1.0 ml of dimethyldivinylsilane as component (a2), 0.8 ml of t-Bu(Me)Si(OMe)2 as component (a3), and 1740 mg of an n-heptane-diluted solution of Et3Al as Et3Al as component (a4) were added, and the reaction was carried out at 40 °C for 2 hours. The reaction product was thoroughly washed with purified n-heptane to obtain contact product (1). A portion of the resulting slurry was sampled and dried. Analysis revealed that contact product (1) contained 380 μmol / g of Ti and 260 μmol / g of t-Bu(Me)Si(OMe)2.

[0128] [Preparation of Contact Product (2)] Purified n-heptane was added to the contact product (1) obtained above to adjust the liquid level to 25 ml. To this was added 1.0 ml of dimethyldivinylsilane (component (a2)), 0.8 ml of t-Bu(Me)Si(OMe)2 (component (a3)), 700 mg of an n-heptane diluted solution of Et3Al (Et3Al) (component (a4)), and 2100 mg of an n-heptane slurry of Et2Al-O(CH2)2-OAlEt2 (Et2Al-O(CH2)2-OAlEt2) (component (a5)). The reaction was carried out at 40°C for 2 hours. The reaction product was thoroughly washed with purified n-heptane to obtain contact product (2).

[0129] [Prepolymerization] Purified n-heptane was introduced into the contact product (2) obtained above to adjust the liquid level to 150 ml. After cooling the slurry to below 10°C, 600 mg of EtAl diluted in n-heptane was added, and 8 g of propylene was fed over 20 minutes. After the propylene feed was completed, the reaction was continued for another 10 minutes. Next, the gas phase was thoroughly purged with nitrogen, and the reaction product was thoroughly washed with purified n-heptane and vacuum dried to obtain a prepolymerized contact product (2).

[0130] [Propylene polymerization] A 3.0 L stainless steel autoclave equipped with stirring and a temperature control device was heated and dried under vacuum, cooled to room temperature, and substituted with propylene. Then, 550 mg of EtAl and 8000 mL of hydrogen were introduced, followed by 1000 g of liquid propylene. The internal temperature was adjusted to 70°C, and 5 mg of the prepolymerized contact product (2) was injected to polymerize propylene. After 1 hour, 10 mL of ethanol was injected to terminate the polymerization. The resulting polymer was recovered and analyzed. The results are shown in Table 1.

[0131] Example 2 A polymer was obtained in the same manner as in Example 1 [Preparation of Contact Product (2)], except that EtAl-O(CH)-OAlEt was replaced with EtAl-O(CH)-OAlEt in an amount of 2200 mg. The results are shown in Table 1.

[0132] Example 3 A polymer was obtained in the same manner as in Example 1 [Preparation of Contact Product (2)], except that EtAl-O(CH)-OAlEt was replaced with EtAl-O(C(CH))-OAlEt in an amount of 2600 mg. The results are shown in Table 1.

[0133] (Comparative Example 1) [Prepolymerization treatment] A 500 ml round-bottom flask equipped with a stirrer was thoroughly purged with nitrogen, and 4 g of the contact product (1) obtained in Example 1 was introduced. Purified n-heptane was introduced to adjust the liquid level to 150 ml. After the slurry was cooled to below 10°C, 600 mg of a diluted n-heptane solution of EtAl was added as EtAl, and 8 g of propylene was fed over 20 minutes. After the propylene feed was completed, the reaction was continued for another 10 minutes. Next, the gas phase was thoroughly purged with nitrogen, and the reaction product was thoroughly washed with purified n-heptane and vacuum dried to obtain a prepolymerized contact product (1).

[0134] [Propylene polymerization] A 3.0 L stainless steel autoclave equipped with stirring and a temperature control device was heated and dried under vacuum, cooled to room temperature, and substituted with propylene. Then, 550 mg of EtAl and 8000 mL of hydrogen were introduced, followed by 1000 g of liquid propylene. The internal temperature was adjusted to 70°C, and 5 mg of the prepolymerized contact product (1) was injected to polymerize propylene. After 1 hour, 10 mL of ethanol was injected to terminate the polymerization. The resulting polymer was recovered and analyzed. The results are shown in Table 2.

[0135] (Comparative Example 2) A polymer was obtained in the same manner as in Comparative Example 1 [Propylene polymerization], except that 219 mg of Et3Al and 667 mg of Et2Al-O(CH2)2-OAlEt2 were used instead of 550 mg of Et3Al. The results are shown in Table 2.

[0136] (Comparative Example 3) [Preparation of Contact Product] A 500 ml round-bottom flask equipped with a stirrer was thoroughly purged with nitrogen, and 4.0 g of the solid component (a1) slurry from Example 1 was introduced. Purified n-heptane was added to adjust the liquid level to 25 ml. To this flask were added 1.0 ml of dimethyldivinylsilane (component (a2)), 0.8 ml of t-Bu(Me)Si(OMe)2 (component (a3)), 700 mg of an n-heptane diluted solution of EtAl (EtAl) (component (a4)), and 2100 mg of an n-heptane slurry of EtAl-O(CH2)2-OAlEt2 (EtAl-O(CH2)2-OAlEt2) (component (a5)). The reaction was carried out at 40°C for 2 hours. The reaction product was thoroughly washed with purified n-heptane to obtain the contact product.

[0137] [Prepolymerization] Purified n-heptane was added to the contact product obtained above to adjust the liquid level to 150 ml. After cooling the slurry to below 10°C, 600 mg of EtAl diluted in n-heptane was added, and 8 g of propylene was fed over 20 minutes. After the propylene feed was completed, the reaction was continued for another 10 minutes. Next, the gas phase was thoroughly purged with nitrogen, and the reaction product was thoroughly washed with purified n-heptane and vacuum dried to obtain a prepolymerized contact product.

[0138] [Propylene polymerization] A 3.0 L stainless steel autoclave equipped with stirring and temperature control was heated and dried under vacuum, cooled to room temperature, and substituted with propylene. Then, 550 mg of EtAl and 8000 ml of hydrogen were introduced, followed by 1000 g of liquid propylene. The internal temperature was adjusted to 70°C, and 5 mg of the prepolymerized contact product was injected to polymerize propylene. After 1 hour, 10 ml of ethanol was injected to terminate the polymerization. The resulting polymer was recovered and analyzed. The results are shown in Table 2.

[0139] Comparative Example 4 A polymer was obtained in the same manner as in Example 1 [Preparation of Contact Product (2)], except that component (a5) was not added and only component (a4) in an amount of 600 mg as EtAl was added. The results are shown in Table 2.

[0140] (Comparative Example 5) A polymer was obtained in the same manner as in Example 1 [Preparation of Contact Product (2)], except that component (a2) was not added. The results are shown in Table 2.

[0141] [Table 1]

[0142] [Table 2]

[0143] As is clear from Tables 1 and 2, a comparative study of the Examples and Comparative Examples revealed that polypropylene with a low content of solubles at 40°C (amorphous components) can be obtained by polymerizing propylene in the presence of a catalyst containing the solid catalyst component for olefin polymerization produced by the production method of the present invention. Specifically, when Examples 1 to 3 are compared with Comparative Example 1, it is found that by using a solid catalyst component for olefin polymerization produced by obtaining contact product (1), and then contacting a component containing the contact product (1) with component (a2), a silane compound having an alkenyl group, and component (a5), an organoaluminum compound, a polypropylene was obtained in which the content of the 40°C soluble component (amorphous component) was reduced from 1.9% by mass to 1.4 or 1.5% by mass while maintaining high activity, and the degree of reduction in the 40°C soluble component (amorphous component) was found to be significant. In Comparative Example 2 (corresponding to Patent Document 12, a prior art), in which EtAl and EtAl-O(CH)-OAlEt were used as organoaluminum compounds during polymerization, the 40°C solubles (amorphous components) decreased from 1.9 mass% to 1.8 mass% compared to Comparative Example 1, but the degree of decrease was smaller than in the Examples. Furthermore, in Comparative Example 3, in which a solid catalyst component for olefin polymerization was used that was produced by contacting the solid component (a1) with the components (a2), (a3), (a4), and (a5) without obtaining the contact product (1), the content of the dialkoxysilane compound (a3) ​​was also low, and the 40°C-soluble component (amorphous component) was found to be higher than in Comparative Example 1. In Comparative Example 4, which used a solid catalyst component for olefin polymerization produced without contacting the organoaluminum compound of component (a5) in step 2 after obtaining the contact product (1), the content of the 40°C soluble component (amorphous component) decreased from 1.9 mass% to 1.8 mass% compared to Comparative Example 1, but almost no effect of reducing the 40°C soluble component (amorphous component) was observed. In Comparative Example 5, in which a solid catalyst component for olefin polymerization was used that was produced without contacting the component (a2), a silane compound having an alkenyl group, in step 2 after obtaining the contact product (1), the content of the 40°C soluble component (amorphous component) decreased from 1.9 mass % to 1.7 mass % compared to Comparative Example 1, but it was found that the effect of reducing the 40°C soluble component (amorphous component) was smaller. Therefore, the methods for producing a solid catalyst component for olefin polymerization and a propylene polymer according to the examples of the present invention are methods for producing an α-olefin polymerization catalyst that can yield a propylene polymer with an extremely small amount of solubles at 40°C (amorphous components), and methods for producing a propylene polymer with a small amount of amorphous components and high stereoregularity, and can be said to have achieved superior results compared to the comparative examples.

Claims

1. Step 1: contacting the following components (a1), (a2), (a3), and (a4) to obtain a contact product (1); and Step 2 of contacting a component containing the contact product (1) with the following components (a2) and (a5) to obtain a contact product (2): Component (a1): A solid component containing titanium, magnesium, a halogen, and an electron donor as essential components. Component (a2): Silane compound having an alkenyl group Component (a3): Alkoxysilane compound (however, different from a silane compound having an alkenyl group). Component (a4): an organoaluminum compound represented by the following general formula (1): General formula (1) R ３－ａ AlX ａ (wherein, each R independently represents a hydrocarbon group having 1 to 20 carbon atoms, each X independently represents a hydrogen atom or a halogen atom, and a represents a number satisfying 0≦a≦2.) Component (a5): an organoaluminum compound represented by the following general formula (2): 【Chemical 1】 (where R １ ~R ４ each independently represents a hydrocarbon group having 1 to 20 carbon atoms; R ５ represents a divalent hydrocarbon group having 1 to 20 carbon atoms.

2. 2. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the component (a2) is a vinylsilane compound and / or the component (a3) ​​is a compound represented by the following general formula (3): General formula (3) R ６ R ７ ｍ Si(OR ８ ) ｎ (where R ６ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. ７ R each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group. ８ each independently represents a hydrocarbon group, m is 0, 1 or 2, n is 1, 2 or 3, and m+n=3 is satisfied.

3. 3. A method for producing a propylene-based polymer, comprising homopolymerizing or copolymerizing propylene in the presence of the solid catalyst component (A) for olefin polymerization obtained by the method according to claim 1 or 2 and an organoaluminum compound (B) represented by the following general formula (1): General formula (1) R ３－ａ AlX ａ (wherein, each R independently represents a hydrocarbon group having 1 to 20 carbon atoms, each X independently represents a hydrogen atom or a halogen atom, and a represents a number satisfying 0≦a≦2.)

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