Method for producing a solid catalyst component for olefin polymerization, method for producing a catalyst for olefin polymerization, and method for producing an olefin polymer

Abstract

To provide a method for producing a solid catalyst component for olefin polymerization, which enables reduction of the amount of fine powder contained in a solid catalyst component for olefin polymerization as a first invention, and a method for producing a solid catalyst component for olefin polymerization, which enables suppression of reduction of polymerization activity caused by being applied with heat as a second invention.SOLUTION: The first invention is a method for producing a solid catalyst component for olefin polymerization including a process of reacting a magnesium compound with a titanium halide compound so that the maximum exothermic rate per one mole of the magnesium compound is 18 W or lower. The second invention is a method for producing a solid catalyst component for olefin polymerization including a process of reacting a magnesium compound with a titanium halide compound so that the total exothermic amount per one mole of the titanium compound is 6 kJ-90 kJ.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Known catalysts for olefin polymerization include those containing a solid catalyst component for olefin polymerization containing titanium atoms, magnesium atoms, and halogen atoms. Patent Document 1, for example, discloses a method for producing such a solid catalyst component for olefin polymerization, which comprises a step of supplying a powder of a magnesium compound to a solution containing a titanium halide compound and a solvent. This production method can produce a powdery solid catalyst component for olefin polymerization. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2018 / 025862 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the solid catalyst component for olefin polymerization obtained by the above-mentioned production method contains a large amount of fine powder. When a catalyst is formed using the solid catalyst component for olefin polymerization containing such fine powder and an olefin is polymerized using the catalyst, the resulting polymer contains a large amount of fine powder. If a large amount of fine powder contained in such a polymer is contained in the gas discharged from a polymer polymerization vessel, there is a risk of a large load being placed on equipment (such as a dust collector or a heat exchanger) that treats such gas.

[0005] Furthermore, when heat is applied to a solid catalyst component for olefin polymerization due to the influence of the storage environment, the environment during transportation, etc., the amount of polymer polymerized per unit amount (polymerization activity) may decrease.

[0006] Therefore, an object of the first invention is to provide a method for producing a solid catalyst component for olefin polymerization that can reduce the amount of fine powder in the solid catalyst component for olefin polymerization, a method for producing an olefin polymerization catalyst containing the solid catalyst component for olefin polymerization, and a method for producing an olefin polymer using the olefin polymerization catalyst.

[0007] Another object of the second invention is to provide a method for producing a solid catalyst component for olefin polymerization that can suppress a decrease in polymerization activity due to the application of heat to the solid catalyst component for olefin polymerization, a method for producing an olefin polymerization catalyst containing the solid catalyst component for olefin polymerization, and a method for producing an olefin polymer using the olefin polymerization catalyst. [Means for solving the problem]

[0008] The method for producing a solid catalyst component for olefin polymerization according to the first invention comprises the steps of: 1. A method for producing a solid catalyst component for olefin polymerization, comprising reacting a magnesium compound with a titanium halide compound to produce a solid catalyst component for olefin polymerization, the method comprising: The method includes a step of reacting a magnesium compound with a titanium halide compound so that the maximum heat generation rate per 1 mol of the magnesium compound is 18 W or less.

[0009] The method for producing an olefin polymerization catalyst according to the first invention comprises the steps of: The method includes a mixing step of mixing the solid catalyst component for olefin polymerization obtained by the above-mentioned method for producing a solid catalyst component for olefin polymerization with an organoaluminum compound.

[0010] The method for producing an olefin polymer according to the first invention comprises the steps of: Olefins are polymerized in the presence of the above-mentioned olefin polymerization catalyst.

[0011] A method for producing a solid catalyst component for olefin polymerization according to a second aspect of the present invention comprises the steps of: 1. A method for producing a solid catalyst component for olefin polymerization, comprising reacting a magnesium compound with a titanium halide compound to produce a solid catalyst component for olefin polymerization, the method comprising: The method includes a step of reacting a magnesium compound with a titanium halide compound so that the total calorific value per 1 mol of the titanium compound is 6 kJ to 90 kJ.

[0012] A method for producing an olefin polymerization catalyst according to a second aspect of the present invention comprises the steps of: The method includes a mixing step of mixing the solid catalyst component for olefin polymerization obtained by the above-mentioned method for producing a solid catalyst component for olefin polymerization with an organoaluminum compound.

[0013] The method for producing an olefin polymer according to the second invention comprises the steps of: Olefins are polymerized in the presence of the above-described olefin polymerization catalyst. [Effects of the Invention]

[0014] According to the first invention, it is possible to provide a method for producing a solid catalyst component for olefin polymerization that can reduce the amount of fine powder in the solid catalyst component for olefin polymerization, a method for producing an olefin polymerization catalyst containing the solid catalyst component for olefin polymerization, and a method for producing an olefin polymer using the olefin polymerization catalyst.

[0015] According to the second invention, there is provided a method for producing a solid catalyst component for olefin polymerization, which can suppress a decrease in polymerization activity due to the application of heat to the solid catalyst component for olefin polymerization. Also provided are a method for producing an olefin polymerization catalyst containing the solid catalyst component for olefin polymerization, and a method for producing an olefin polymer using the olefin polymerization catalyst. DETAILED DESCRIPTION OF THE INVENTION

[0016] First Embodiment The first embodiment (embodiment of the first invention) will be described below.

[0017] <Method of manufacturing a solid catalyst component for olefin polymerization> The method for producing a solid catalyst component for olefin polymerization according to this embodiment involves reacting a magnesium compound with a titanium halide compound to produce a solid catalyst component for olefin polymerization containing titanium atoms, magnesium atoms, and halogen atoms (preferably a solid catalyst component for olefin polymerization further containing an internal electron donor). The method for producing a solid catalyst component for olefin polymerization according to this embodiment also includes a step (I) of supplying a titanium halide compound to a magnesium compound mixture containing a magnesium compound and a solvent to obtain a slurry containing a solid product. The solid product is a reaction product of the titanium halide compound and the magnesium compound.

[0018] The titanium halide compound refers to a compound containing a halogen atom and a titanium atom, with at least one halogen atom being bonded to the titanium atom. Examples of the titanium halide compound include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; monoalkoxytitanium trihalides such as methoxytitanium trichloride, ethoxytitanium trichloride, n-propoxytitanium trichloride, n-butoxytitanium trichloride, and ethoxytitanium tribromide; dihalogenated dialkoxytitanium dichloride such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-n-propoxytitanium dichloride, and diethoxytitanium dibromide; monohalogenated trialkoxytitanium such as trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride, and tri-n-butoxytitanium chloride. Titanium tetrahalide or monoalkoxytitanium trihalide is preferred, titanium tetrahalide is more preferred, and titanium tetrachloride is even more preferred. The titanium halide compounds may be used alone or in combination of two or more.

[0019] The amount of the titanium halide compound used in step (I) is preferably 0.01 mol to 100 mol, more preferably 0.03 mol to 50 mol, still more preferably 0.05 mol to 30 mol, per 1 mol of the total magnesium atoms in the magnesium compound used in step (I).

[0020] The magnesium compound may be any compound containing magnesium atoms, and specific examples include compounds represented by the following formulas (i) to (iii). MgR 1 k X 2-k ···(i) Mg(OR 1 ) m X 2-m ···(ii) MgX2·nR 1 OH···(iii) (In the formula, k is a number satisfying 0 ≦ k ≦ 2; m is a number satisfying 0 < m ≦ 2; n is a number satisfying 0 ≦ n ≦ 3; R 1 is a hydrocarbyl group having 1 to 20 carbon atoms; X is a halogen atom.)

[0021] Examples of R 1 in formulas (i) to (iii) include, for example, an alkyl group, an aralkyl group, an aryl group, an alkenyl group, etc. Also, some or all of the hydrogen atoms contained in these groups may be substituted with a halogen atom, a hydrocarbyloxy group, a nitro group, a sulfonyl group, a silyl group, etc. R 1Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, and 2-ethylhexyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. R is preferably a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. 1 Examples of the aralkyl group include a benzyl group and a phenethyl group, and preferably an aralkyl group having 7 to 20 carbon atoms. 1 Examples of the aryl group include a phenyl group, a naphthyl group, and a tolyl group, and preferably an aryl group having 6 to 20 carbon atoms. 1 Examples of the alkenyl group include linear alkenyl groups such as vinyl, allyl, 3-butenyl, and 5-hexenyl; branched alkenyl groups such as isobutenyl and 4-methyl-3-pentenyl; and cyclic alkenyl groups such as 2-cyclohexenyl and 3-cyclohexenyl. Of these, linear alkenyl groups having 2 to 20 carbon atoms or branched alkenyl groups having 3 to 20 carbon atoms are preferred. 1 may be the same or different.

[0022] Examples of X in the above formulas (i) to (iii) include a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, etc., and a chlorine atom is preferred. Multiple Xs may be the same or different.

[0023] Specific examples of the magnesium compounds of formulas (i) to (iii) include dialkylmagnesium such as dimethylmagnesium, diethylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, dicyclohexylmagnesium, and butyloctylmagnesium; magnesium dialkoxides such as magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium dibutoxide, magnesium dihexyloxide, magnesium dioctyloxide, and magnesium dicyclohexyloxide; methylmagnesium chloride, ethylmagnesium chloride, isopropylmagnesium chloride, n-butylmagnesium chloride, t-butylmagnesium chloride, hexylmagnesium chloride, isobutylmagnesium chloride, benzylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, isopropylmagnesium chloride, Examples of the magnesium halides include alkylmagnesium halides such as methylmagnesium bromide, n-butylmagnesium bromide, t-butylmagnesium bromide, hexylmagnesium bromide, iso-butylmagnesium bromide, benzylmagnesium bromide, methylmagnesium iodide, ethylmagnesium iodide, iso-propylmagnesium iodide, n-butylmagnesium iodide, t-butylmagnesium iodide, hexylmagnesium iodide, iso-butylmagnesium iodide, and benzylmagnesium iodide; alkoxymagnesium halides such as methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, and hexyloxymagnesium chloride; aryloxymagnesium halides such as phenyloxymagnesium chloride; and magnesium halides such as magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide.

[0024] Among these, magnesium halides or magnesium dialkoxides are preferred. As the magnesium halide, magnesium chloride is preferred. As the magnesium dialkoxide, magnesium dialkoxides having an alkyl group with 1 to 20 carbon atoms are preferred, magnesium dialkoxides having an alkyl group with 1 to 10 carbon atoms are more preferred, and magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium di(isopropoxide), or magnesium dibutoxide are particularly preferred.

[0025] Commercially available magnesium halide may be used as is. Alternatively, commercially available magnesium halide may be dissolved in alcohol, the resulting solution dropped into a hydrocarbon liquid, and the resulting precipitate separated from the liquid. Alternatively, magnesium halide produced according to the methods described in U.S. Pat. No. 6,825,146, WO 1998 / 044009, WO 2003 / 000754, WO 2003 / 000757, or WO 2003 / 085006 may be used.

[0026] Examples of methods for producing magnesium dialkoxide include a method of contacting metallic magnesium with an alcohol in the presence of a catalyst (e.g., JP-A-4-368391, JP-A-3-74341, JP-A-8-73388, and WO 2013 / 058193). Examples of alcohols include methanol, ethanol, propanol, butanol, and octanol. Examples of catalysts include halogens such as iodine, chlorine, and bromine; magnesium halides such as magnesium iodide and magnesium chloride; and the like, with iodine being preferred.

[0027] The magnesium compound may be supported on a support material. Examples of the support material include porous inorganic oxides such as SiO2, Al2O3, MgO, TiO2, and ZrO2; and organic porous polymers such as polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol dimethacrylic acid copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyethylene, and polypropylene. Among these, porous inorganic oxides are preferred, and SiO2 is more preferred.

[0028] When a porous support material is used from the viewpoint of effectively immobilizing the magnesium compound on the support material, the porous support material should have a total volume of pores with a pore radius of 10 to 780 nm, as determined by mercury intrusion porosimetry in accordance with ISO 15901-1:2005, of 0.3 cm 3 / g or more is preferable, and 0.4 cm 3 / g or more is more preferable. Furthermore, the porous carrier material is one in which the total volume of pores with a pore radius of 10 to 780 nm is preferably 25% or more, more preferably 30% or more, of the total volume of pores with a pore radius of 2 to 100 μm.

[0029] The magnesium compounds exemplified above may be used alone or in combination of two or more. Preferably, the magnesium compounds are in the form of powder without being mixed with a solvent.

[0030] The content of the magnesium compound in the magnesium compound mixture is preferably 0.001 to 1.0 mg, more preferably 0.05 to 0.5 mg, and even more preferably 0.1 to 0.3 mg per mL of the solvent contained in the magnesium compound mixture.

[0031] The solvent constituting the magnesium compound mixture is preferably inert to the solid product (specifically, the solid catalyst component for olefin polymerization) produced in step (I). Examples of the solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and decane; aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane, cyclopentane, methylcyclohexane, and decalin; halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene; and ether compounds such as diethyl ether, dibutyl ether, diisoamyl ether, and tetrahydrofuran. Among these, aromatic hydrocarbons or halogenated hydrocarbons are preferred, and toluene is more preferred. The solvents may be used alone or in combination of two or more.

[0032] The internal electron donor refers to an organic compound capable of donating an electron pair to one or more metal atoms contained in the solid catalyst component for olefin polymerization, and specific examples thereof include monoester compounds, dicarboxylic acid ester compounds, diol diester compounds, β-alkoxy ester compounds, and diether compounds.

[0033] The monoester compound refers to an organic compound having one ester bond (-CO-O-) in the molecule, and is preferably, for example, an aromatic carboxylic acid ester compound or an aliphatic carboxylic acid ester compound. Examples of the aromatic carboxylic acid ester compound include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, octyl benzoate, methyl toluate, ethyl toluate, propyl toluate, butyl toluate, pentyl toluate, hexyl toluate, and octyl toluate.Examples of the aliphatic carboxylic acid ester compounds include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, octyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, pentyl propionate, hexyl propionate, octyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, pentyl butyrate, hexyl butyrate, octyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, pentyl valerate, hexyl valerate, and valeric acid. Octyl, methyl caproate, ethyl caproate, propyl caproate, butyl caproate, pentyl caproate, hexyl caproate, octyl caproate, methyl enanthate, ethyl enanthate, propyl enanthate, butyl enanthate, pentyl enanthate, hexyl enanthate, octyl enanthate, methyl caprylate, ethyl caprylate, propyl caprylate, butyl caprylate, pentyl caprylate, hexyl caprylate, octyl caprylate, methyl pelargonate, ethyl pelargonate, propyl pelargonate, pelargonate Butyl myristate, Pentyl pelargonate, Hexyl pelargonate, Octyl pelargonate, Methyl caprate, Ethyl caprate, Propyl caprate, Butyl caprate, Pentyl caprate, Hexyl caprate, Octyl caprate, Methyl laurate, Ethyl laurate, Propyl laurate, Butyl laurate, Pentyl laurate, Hexyl laurate, Octyl laurate, Methyl myristate, Ethyl myristate, Propyl myristate, Butyl myristate, Pentyl myristate, Hexyl myristate, Myristate Examples thereof include octyl riscite, methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate, pentyl palmitate, hexyl palmitate, octyl palmitate, methyl margarate, ethyl margarate, propyl margarate, butyl margarate, pentyl margarate, hexyl margarate, octyl margarate, methyl stearate, ethyl stearate, propyl stearate, butyl stearate, pentyl stearate, hexyl stearate, and octyl stearate.

[0034] The dicarboxylic acid ester compound is a compound having two ester bonds (-CO-O-) in the molecule, and means a compound having a structure in which two carboxyl groups of a dicarboxylic acid are esterified with a monohydric alcohol. For example, an aromatic dicarboxylic acid ester compound or an aliphatic dicarboxylic acid ester compound is preferred. The aromatic dicarboxylic acid ester compound is a compound that can be synthesized from, for example, an aromatic dicarboxylic acid or an aromatic dicarboxylic acid dihalide and a monohydric alcohol. Specific examples include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-tert-butyl phthalate, dipentyl phthalate, dihexyl phthalate, dioctyl phthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, dipentyl isophthalate, dihexyl isophthalate, dioctyl isophthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dipentyl terephthalate, dihexyl terephthalate, and dioctyl terephthalate. The aliphatic dicarboxylic acid ester compound is a compound that can be synthesized from, for example, an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid dihalide and a monohydric alcohol, and specific examples thereof include dimethyl ethanedioate, diethyl ethanedioate, dipropyl ethanedioate, dibutyl ethanedioate, dipentyl ethanedioate, dihexyl ethanedioate, dioctyl ethanedioate, dimethyl propanedioate, diethyl propanedioate, dipropyl propanedioate, dibutyl propanedioate, dipentyl propanedioate, dihexyl propanedioate, dioctyl propanedioate, dimethyl butanedioate, Diethyl butanedioate, dipropyl butanedioate, dibutyl butanedioate, dipentyl butanedioate, dihexyl butanedioate, dioctyl butanedioate, dimethyl penanedioate, diethyl penanedioate, dipropyl penanedioate, dibutyl penanedioate, dipentyl penanedioate, dihexyl penanedioate, dioctyl penanedioate, dimethyl hexanedioate, diethyl hexanedioate, dipropyl hexanedioate, dibutyl hexanedioate, dipentyl hexanedioate, dihexyl hexanedioate, dioctyl hexanedioate, dimethyl (E)-but-2-enedioate,Diethyl (E)-but-2-enedioate, dipropyl (E)-but-2-enedioate, dibutyl (E)-but-2-enedioate, dipentyl (E)-but-2-enedioate, dihexyl (E)-but-2-enedioate, dioctyl (E)-but-2-enedioate, dimethyl (Z)-but-2-enedioate, diethyl (Z)-but-2-enedioate, dipropyl (Z)-but-2-enedioate, dibutyl (Z)-but-2-enedioate, dipentyl (Z)-but-2-enedioate, dihexyl (Z)-but-2-enedioate, dioctyl (Z)-but-2-enedioate, cyclohexyl Dimethyl cyclohexane-1,2-dicarboxylate, Diethyl cyclohexane-1,2-dicarboxylate, Dipropyl cyclohexane-1,2-dicarboxylate, Dibutyl cyclohexane-1,2-dicarboxylate, Dipentyl cyclohexane-1,2-dicarboxylate, Dihexyl cyclohexane-1,2-dicarboxylate, Dioctyl cyclohexane-1,2-dicarboxylate, Dimethyl 1,2-cyclohexene-1,2-dicarboxylate, Diethyl 1,2-cyclohexene-1,2-dicarboxylate, Dipropyl 1,2-cyclohexene-1,2-dicarboxylate, 1,2-cyclohexene-1,2-dicarboxylate Dibutyl 1,2-cyclohexene-1,2-dicarboxylate, Dipentyl 1,2-cyclohexene-1,2-dicarboxylate, Dihexyl 1,2-cyclohexene-1,2-dicarboxylate, Dioctyl 1,2-cyclohexene-1,2-dicarboxylate, Dimethyl 3-methylcyclohexane-1,2-dicarboxylate, Diethyl 3-methylcyclohexane-1,2-dicarboxylate, Dipropyl 3-methylcyclohexane-1,2-dicarboxylate, Dibutyl 3-methylcyclohexane-1,2-dicarboxylate, Dipentyl 3-methylcyclohexane-1,2-dicarboxylate, 3 -Dihexyl methylcyclohexane-1,2-dicarboxylate, dioctyl 3-methylcyclohexane-1,2-dicarboxylate, dimethyl 3,6-dimethylcyclohexane-1,2-dicarboxylate, diethyl 3,6-dimethylcyclohexane-1,2-dicarboxylate, dipropyl 3,6-dimethylcyclohexane-1,2-dicarboxylate, dibutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate, dipentyl 3,6-dimethylcyclohexane-1,2-dicarboxylate, dihexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate, 3,Examples include dioctyl 6-dimethylcyclohexane-1,2-dicarboxylate.

[0035] The diol diester compound is a compound having two ester bonds (-CO-O-) in the molecule, and means a compound having a structure in which each of the two hydroxyl groups of the diol is esterified with a carboxyl group of a monocarboxylic acid or dicarboxylic acid, and examples thereof include 1,2-dibenzoate propane, 1,2-diacetyloxypropane, 1,2-dibenzoate butane, 1,2-diacetyloxybutane, 1,2-dibenzoate cyclohexane, 1,2-diacetyloxycyclohexane, and 1,3-dibenzoate propane. Examples of the alkyl esters include 1,3-diacetyloxypropane, 2,4-dibenzoate pentane, 2,4-diacetyloxypentane, 1,2-dibenzoate cyclopentane, 1,2-diacetyloxycyclopentane, 1,2-dibenzoate-4-tert-butyl-6-methylbenzene, 1,2-diacetyloxy-4-tert-butyl-6-methylbenzene, 1,3-dibenzoate-4-tert-butyl-6-methylbenzene, and 1,3-diacetyloxy-4-tert-butyl-6-methylbenzene.

[0036] The β-alkoxy ester compound means a compound having an alkoxycarbonyl group and an alkoxy group at the β-position of the alkoxycarbonyl group, and examples thereof include methyl 2-methoxymethyl-3,3-dimethylbutanoate, ethyl 2-methoxymethyl-3,3-dimethylbutanoate, propyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, pentyl 2-methoxymethyl-3,3-dimethylbutanoate, hexyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl ...butyl 2-methoxymethyl-3,3-dimethylbutanoate, pentyl 2-methoxymethyl-3,3-dimethylbutanoate, hexyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, hexyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, Octyl 3-dimethylbutanoate, Methyl 3-methoxy-2-phenylpropionate, Ethyl 3-methoxy-2-phenylpropionate, Propyl 3-methoxy-2-phenylpropionate, Butyl 3-methoxy-2-phenylpropionate, Pentyl 3-methoxy-2-phenylpropionate, Hexyl 3-methoxy-2-phenylpropionate, Octyl 3-methoxy-2-phenylpropionate, Methyl 2-ethoxymethyl-3,3-dimethylbutanoate, Ethyl 2-ethoxymethyl-3,3-dimethylbutanoate, 2-Ethoxymethyl Propyl 3,3-dimethylbutanoate, Butyl 2-ethoxymethyl-3,3-dimethylbutanoate, Pentyl 2-ethoxymethyl-3,3-dimethylbutanoate, Hexyl 2-ethoxymethyl-3,3-dimethylbutanoate, Octyl 2-ethoxymethyl-3,3-dimethylbutanoate, Methyl 3-ethoxy-2-phenylpropionate, Ethyl 3-ethoxy-2-phenylpropionate, Propyl 3-ethoxy-2-phenylpropionate, Butyl 3-ethoxy-2-phenylpropionate, Pentyl 3-ethoxy-2-phenylpropionate , hexyl 3-ethoxy-2-phenylpropionate, octyl 3-ethoxy-2-phenylpropionate, methyl 2-propyloxymethyl-3,3-dimethylbutanoate, ethyl 2-propyloxymethyl-3,3-dimethylbutanoate, propyl 2-propyloxymethyl-3,3-dimethylbutanoate, butyl 2-propyloxymethyl-3,3-dimethylbutanoate, pentyl 2-propyloxymethyl-3,3-dimethylbutanoate, hexyl 2-propyloxymethyl-3,3-dimethylbutanoate, 2-propyloxymethyl-3,Examples of suitable esters include octyl 3-dimethylbutanoate, methyl 3-propyloxy-2-phenylpropionate, ethyl 3-propyloxy-2-phenylpropionate, propyl 3-propyloxy-2-phenylpropionate, butyl 3-propyloxy-2-phenylpropionate, pentyl 3-propyloxy-2-phenylpropionate, hexyl 3-propyloxy-2-phenylpropionate, octyl 3-propyloxy-2-phenylpropionate, methyl 2-methoxybenzenecarboxylate, ethyl 2-methoxybenzenecarboxylate, propyl 2-methoxybenzenecarboxylate, butyl 2-methoxybenzenecarboxylate, pentyl 2-methoxybenzenecarboxylate, hexyl 2-methoxybenzenecarboxylate, octyl 2-methoxybenzenecarboxylate, methyl 2-ethoxybenzenecarboxylate, ethyl 2-ethoxybenzenecarboxylate, propyl 2-ethoxybenzenecarboxylate, butyl 2-ethoxybenzenecarboxylate, pentyl 2-ethoxybenzenecarboxylate, hexyl 2-ethoxybenzenecarboxylate, and octyl 2-ethoxybenzenecarboxylate.

[0037] The diether compound means a compound having two ether bonds in the molecule, and examples thereof include 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-dipropyloxypropane, 1,2-dibutoxypropane, 1,2-di-tert-butoxypropane, 1,2-diphenoxypropane, 1,2-dibenzyloxypropane, 1,2-dimethoxybutane, 1,2-diethoxybutane, 1,2-dipropyloxybutane, 1,2-dibutoxybutane, 1,2-di-tert-butoxybutane, 1,2-diphenoxybutane, and 1,2-dibenzyloxypropane. cyclohexane, 1,2-dimethoxycyclohexane, 1,2-diethoxycyclohexane, 1,2-dipropyloxycyclohexane, 1,2-dibutoxycyclohexane, 1,2-di-tert-butoxycyclohexane, 1,2-diphenoxycyclohexane, 1,2-dibenzyloxycyclohexane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-dipropyloxypropane, 1,3-dibutoxypropane, 1,3-di-tert-butoxypropane, 1,3-diphenoxypropane, 1,3-dibenzyloxypropane, 2,4-Dimethoxypentane, 2,4-diethoxypentane, 2,4-dipropyloxypentane, 2,4-dibutoxypentane, 2,4-di-tert-butoxypentane, 2,4-diphenoxypentane, 2,4-dibenzyloxypentane, 1,2-dimethoxycyclopentane, 1,2-diethoxycyclopentane, 1,2-dipropyloxycyclopentane, 1,2-dibutoxycyclopentane, 1,2-di-tert-butoxycyclopentane, 1,2-diphenoxycyclopentane, 1,2-dibenzyloxycyclopentane, 9,9-bi bis(methoxymethyl)fluorene, 9,9-bis(ethoxymethyl)fluorene, 9,9-bis(propyloxymethyl)fluorene, 9,9-bis(butoxymethyl)fluorene, 9,9-bis-tert-butoxymethylfluorene, 9,9-bis(phenoxymethyl)fluorene, 9,9-bis(benzyloxymethyl)fluorene, 1,2-dimethoxybenzene, 1,2-diethoxybenzene, 1,2-dipropyloxybenzene, 1,2-dibutoxybenzene, 1,2-di-tert-butoxybenzene, 1,2-diphenoxybenzene, 1,Examples include 2-dibenzyloxybenzene.

[0038] Further examples include the internal electron donors described in JP-A-2011-246699.

[0039] Among them, preferred examples of the internal electron donor include a dicarboxylic acid ester compound, a diol diester compound, a β-alkoxy ester compound, etc. The internal electron donors may be used alone or in combination of two or more.

[0040] The amount of the internal electron donor used is preferably 0.001 to 5 mol, more preferably 0.01 to 0.5 mol, per mol of total magnesium atoms in the magnesium compound used in step (I).

[0041] The method for producing a solid catalyst component for olefin polymerization according to this embodiment comprises a step of reacting a magnesium compound with a titanium halide compound so that the maximum heat release rate per mole of the magnesium compound is 18 W or less, preferably 10 W or less. The maximum heat release rate is based on the heat of reaction between the magnesium compound and the titanium halide compound during step (I). The maximum heat release rate can be determined by the method described in the Examples below. The maximum heat release rate can be adjusted by adjusting at least one of the temperature in a reaction vessel in which step (I) is carried out, the concentration of the substances, and the feed rate of the titanium halide compound, which will be described later.

[0042] Step (I) comprises a step (hereinafter also referred to as the "first supply step") of maintaining the supply rate of the titanium halide compound relative to 1 mole of the magnesium compound at 0.01 mol / min or less, preferably 0.005 mol / min or less, and more preferably 0.003 mol / min or less until at least 1 mol of the titanium halide compound is supplied per 1 mole of the magnesium compound. Step (I) comprises at least one of a step of satisfying the above-mentioned maximum heat release rate and a step of satisfying the above-mentioned supply rate of the titanium halide compound. This can reduce the amount of fine powder in the resulting solid catalyst component for olefin polymerization. In the first supply step, the supply rate of the titanium halide compound relative to 1 mole of the magnesium compound may be 0.0005 mol / min or more, or may be 0.001 mol / min or more. By performing the first supply step, the reaction between the magnesium compound and the titanium halide compound can be carried out within the above-mentioned maximum heat release rate range.

[0043] Furthermore, step (I) may include a step (hereinafter also referred to as the "second supply step") in which, after supplying at least 1 mol of the titanium halide compound relative to the magnesium compound (i.e., after the first supply step), the supply rate of the titanium halide compound relative to 1 mol of the magnesium compound is increased to a rate of preferably more than 0.01 mol / min, more preferably 0.025 mol / min or more, and even more preferably 0.04 mol / min or more. This increases the supply rate of the titanium halide compound after supplying at least 1 mol of the titanium halide compound relative to the magnesium compound, allowing the titanium halide compound to be supplied rapidly. Note that in the second supply step, the supply rate of the titanium halide compound relative to 1 mol of the magnesium compound may be 10 mol / min or less, or may be 1 mol / min or less.

[0044] Step (I) is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.

[0045] The titanium halide compound may be supplied to the magnesium compound mixture continuously or intermittently (for example, dropwise). The titanium halide compound may be supplied to the magnesium compound mixture in a state where it is mixed with a solvent (for example, a solvent that can constitute the magnesium compound mixture), or may be supplied to the magnesium compound mixture without being mixed with a solvent.

[0046] Examples of the method for contacting the components in step (I) include known methods such as a slurry method and a mechanical pulverization method (for example, a method in which the components are contacted while being pulverized using a ball mill).

[0047] The temperature in step (I) is preferably −20° C. to 50° C., more preferably −10° C. to 20° C., and even more preferably −5° C. to 10° C. The total time for step (I) (total time for mixing the magnesium compound mixture and the titanium halide compound) is preferably 0.01 to 48 hours, more preferably 0.1 to 36 hours, and even more preferably 0.5 to 24 hours.

[0048] The solvent contained in the slurry obtained in step (I) includes the solvent in the magnesium compound mixture. Furthermore, when the titanium halide compound is mixed with a solvent and used in the form of a solution, the solvent contained in the slurry obtained in step (I) may also include the solvent in the solution. Furthermore, the solvent contained in the slurry obtained in step (I) may also include a solvent added alone during step (I) (e.g., a solvent that can constitute the magnesium compound mixture).

[0049] When producing a solid catalyst component for olefin polymerization containing an internal electron donor, the timing of supplying the internal electron donor is not particularly limited. For example, the internal electron donor may be supplied to a reactor in which step (I) is carried out prior to step (I). Alternatively, the internal electron donor may be supplied to a magnesium compound mixed solution. As another example, the titanium halide compound and the internal electron donor may be mixed together. Alternatively, the internal electron donor may be supplied to a reactor during step (I), or may be supplied to a slurry containing a solid product after step (I). A combination of these methods may also be used.

[0050] From the viewpoint of improving the particle properties of the resulting solid catalyst component for olefin polymerization, it is preferable to supply the internal electron donor to the slurry containing the solid product after step (I). In such a case, the method for producing a solid catalyst component for olefin polymerization according to this embodiment includes step (II) of supplying the internal electron donor to the slurry containing the solid product obtained in step (I).

[0051] Regardless of the timing of supplying the internal electron donor, the temperature at which the solid product produced in step (I) and the internal electron donor are reacted with each other is preferably −20° C. to 150° C., more preferably −5° C. to 135° C., and even more preferably 30° C. to 120° C. The reaction time is preferably 0.1 to 12 hours, more preferably 0.5 to 10 hours. The reaction between the solid product and the internal electron donor is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas.

[0052] Steps (I) and (II) are preferably carried out with stirring, with the peripheral speed v of the stirring blades represented by the following formula (1) preferably in the range of 0.1 to 10 m / sec, more preferably in the range of 0.5 to 5.0 m / sec, and even more preferably in the range of 1.0 to 3.0 m / sec. v = n × d (1) (In the formula, n represents the rotation speed of the stirring impeller (rad / sec), and d represents the blade diameter of the stirring impeller (m).)

[0053] The solid product obtained in step (I) (preferably, a solid obtained by carrying out steps (I) and (II)) can be used as a solid catalyst component for olefin polymerization. Alternatively, the solid product obtained in step (I) (preferably, a solid obtained by carrying out steps (I) and (II)) can be used as a precursor, and the precursor can be further contacted with one or more of a titanium halide compound, a magnesium compound, and an internal electron donor to obtain a solid, which can be used as a solid catalyst component for olefin polymerization.

[0054] The above-mentioned solid catalyst component or precursor for olefin polymerization is preferably washed with a washing solvent to remove unnecessary substances. The washing solvent is preferably inert to the solid catalyst component or precursor for olefin polymerization. Examples of the washing solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane; and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene. Among these, aromatic hydrocarbons and halogenated hydrocarbons are particularly preferred. The amount of the washing solvent used per 1 g of the solid catalyst component or precursor for olefin polymerization in one contact step can be, for example, 0.1 mL to 1,000 mL, preferably 1 mL to 100 mL. Washing is performed, for example, 1 to 5 times per contact step. The washing temperature is, for example, −50 to 150°C, preferably 0 to 140°C, and more preferably 60 to 135°C. The washing time is preferably 1 to 120 minutes, more preferably 2 to 60 minutes.

[0055] When the solid catalyst component for olefin polymerization is obtained by contacting the precursor with one or more of a titanium halide compound, a magnesium compound, and an internal electron donor, the method for producing the solid catalyst component for olefin polymerization according to this embodiment includes a step (III) of contacting the precursor with one or more of a titanium halide compound, a magnesium compound, and an internal electron donor.

[0056] Step (III) is preferably carried out in a solvent. The solvent in step (III) is the same as that in step (I). When a titanium halide compound is contacted in step (III), the amount of the titanium halide compound is, for example, 0.1 to 10 mL / mL, preferably 0.1 to 1.0 mL / mL, per mL of the solvent used in step (III). When a magnesium compound is contacted in step (III), the amount of the magnesium compound is, for example, 0.01 to 10 g / mL, preferably 0.1 to 1.0 g / mL, per mL of the solvent used in step (III). When an internal electron donor is contacted in step (III), the amount of the internal electron donor is, for example, 0.001 to 5 mL / mL, preferably 0.005 to 0.5 mL / mL, more preferably 0.01 to 0.1 mL / mL, per mL of the solvent used in step (III).

[0057] The types of the titanium halide compound, magnesium compound and internal electron donor in step (III) may be the same as or different from those in step (I) or (II).

[0058] The temperature in step (III) is, for example, -20°C to 150°C, preferably -5°C to 130°C, and more preferably in the range of 40°C to 120°C. The time for step (III) is, for example, 0.1 to 12 hours, and preferably 1 to 8 hours. The precursor is contacted with one or more of a titanium halide compound, a magnesium compound, and an internal electron donor in an inert gas atmosphere such as nitrogen gas or argon gas. Step (III) may be performed once or repeatedly.

[0059] After the reaction in step (III) is completed, the obtained solid can be used as a solid catalyst component for olefin polymerization. The solid catalyst component for olefin polymerization is preferably washed with a washing solvent as described above. After washing, the solid catalyst component may be dried (for example, dried under reduced pressure).

[0060] The solid catalyst component for olefin polymerization produced as described above can be used to form an olefin polymerization catalyst, and olefin polymerization can be carried out using the olefin polymerization catalyst, thereby making it possible to obtain an olefin polymer having a relatively high stereoregularity. Furthermore, when such an olefin polymerization catalyst is used to produce a particulate olefin polymer by, for example, a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like, polymer particles having a relatively small amount of fine powder can be obtained.

[0061] <Solid catalyst component for olefin polymerization> The solid catalyst component for olefin polymerization produced by the above-mentioned production method exists as a solid content at least in toluene, and can form an olefin polymerization catalyst by being combined with an olefin polymerization cocatalyst such as an organoaluminum compound.

[0062] Such a solid catalyst component for olefin polymerization contains a titanium atom, a magnesium atom, and a halogen atom, and preferably contains at least one internal electron donor selected from the group consisting of a monoester compound, an aliphatic dicarboxylic acid ester compound, a diol diester compound, a β-alkoxy ester compound, and a diether compound.

[0063] Furthermore, the solid catalyst component for olefin polymerization preferably satisfies the following requirements (I) to (IV). (I) a total pore volume of 0.95 to 1.80 mL / g, as measured by mercury porosimetry in accordance with standard ISO 15901-1:2005, and a specific surface area of ​​60 to 170 m, as measured by mercury porosimetry in accordance with standard ISO 15901-1:2005; 2 / g. (II) In accordance with the ISO13320:2009 standard, the cumulative percentage of particles 10 μm or smaller in the volume-based particle size distribution measured by laser diffraction and scattering is 6.5% or less. (III) In accordance with the ISO15472:2001 standard, among the peak components obtained by waveform separation of peaks assigned to the 1s orbital of oxygen atoms obtained by X-ray photoelectron spectroscopy, the ratio (G / F) of the area of ​​the peak component (F) having a peak top binding energy in the range of 532 eV to 534 eV is 0.33 or less. (IV) The titanium content is 1.50 to 3.40 wt%.

[0064] A part or all of the titanium atoms in the solid catalyst component for olefin polymerization are derived from the above-mentioned titanium halide compound.A part or all of the halogen atoms in the solid catalyst component for olefin polymerization are derived from the above-mentioned titanium halide compound.

[0065] A part or all of the magnesium atoms in the solid catalyst component for olefin polymerization are derived from the above magnesium compound, and a part of the halogen atoms in the solid catalyst component for olefin polymerization may be derived from the above magnesium compound.

[0066] The explanation of the monoester compound, aliphatic dicarboxylic acid ester compound, diol diester compound, β-alkoxy ester compound, and diether compound as the internal electron donor is the same as above. As an example, the internal electron donor is preferably a diol diester compound or a β-alkoxy ester compound, more preferably a β-alkoxy ester compound, and even more preferably ethyl 2-ethoxymethyl-3,3-dimethylbutanoate.

[0067] The above requirement (I) is explained below. The total pore volume is preferably 0.95 to 1.80 mL / g, more preferably 1.00 to 1.70 mL / g, and even more preferably 1.10 to 1.60 mL / g. When the total pore volume is 0.95 mL / g or more, polymer productivity is improved. When the total pore volume is 1.80 mL / g or less, sufficient catalyst particle strength can be ensured. The specific surface area is preferably 60 to 170 m 2 / g, more preferably 80 to 150m 2 / g, and more preferably 88 to 130m 2 / g. The specific surface area is 60m 2 / g or more, the sticky components contained in the resulting polymer can be reduced. 2 When the SiO 2 content is 1 / g or less, sufficient catalyst particle strength can be ensured.

[0068] The above requirement (II) will be explained below. The cumulative percentage is preferably 6.5% or less, more preferably 6.2% or less, even more preferably 6.0% or less, and particularly preferably 5.5% or less. When the cumulative percentage is 6.5% or less, fouling problems in the polymerization process can be suppressed.

[0069] The above requirement (III) will be explained below. The ratio (G / F) is preferably 0.33 or less, more preferably 0.30 or less, and even more preferably 0.28 or less. When the ratio (G / F) is 0.33 or less, the generation of sticky components during polymerization can be suppressed.

[0070] The above requirement (IV) will be explained below. The titanium content is preferably 1.50 to 3.40 wt%, more preferably 1.6 to 3.0 wt%. When the titanium content is 3.40 wt% or less, the sticky components contained in the obtained polymer can be reduced, and when the titanium content is 1.5 wt% or more, the productivity of the polymer can be improved.

[0071] The content of titanium atoms in the solid catalyst component for olefin polymerization is preferably 1.5 to 3.4 mass%, more preferably 1.8 to 3.0 mass%. The content of titanium atoms can be determined, for example, by the method described in the Examples below.

[0072] The content of the internal electron donor in the solid catalyst component for olefin polymerization is preferably 5 to 20 mass %, more preferably 10 to 15 mass %. The content of the internal electron donor can be determined, for example, by the method described later in the Examples.

[0073] The content of alkoxy groups in the solid catalyst component for olefin polymerization is preferably 2.0 mass % or less, more preferably 1.5 mass % or less. The content of alkoxy groups can be determined, for example, by the method described in the Examples below.

[0074] <Olefin polymerization catalyst> An olefin polymerization catalyst can be produced by contacting the above-mentioned solid catalyst component for olefin polymerization with an organoaluminum compound (preferably, an organoaluminum compound and an external electron donor). That is, the method for producing an olefin polymerization catalyst comprises a mixing step of mixing the above-mentioned solid catalyst component for olefin polymerization with an organoaluminum compound (preferably, an organoaluminum compound and an external electron donor). Therefore, the olefin polymerization catalyst produced by such a method comprises the above-mentioned solid catalyst component for olefin polymerization and an organoaluminum compound, and preferably further comprises an external electron donor.

[0075] The method for contacting the solid catalyst component for olefin polymerization with an organoaluminum compound (preferably, a method for contacting three components including these two components and an external electron donor) is not particularly limited as long as an olefin polymerization catalyst is produced. The contact can be carried out in the presence or absence of a solvent. The three components may be contacted to form an olefin polymerization catalyst, and the olefin polymerization catalyst may be supplied to a polymerization vessel in which olefins are polymerized. Alternatively, the components may be supplied separately to a polymerization vessel and contacted in the polymerization vessel to form an olefin polymerization catalyst. Alternatively, a contact mixture of any two components and the remaining component may be supplied separately to a polymerization vessel and contacted in the polymerization vessel to form an olefin polymerization catalyst.

[0076] The organoaluminum compound is a compound having one or more carbon-aluminum bonds, and specific examples thereof include the compounds described in JP-A-10-212319. Among them, preferred are trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane, and more preferred are triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, or tetraethyldialumoxane.

[0077] The organoaluminum compounds may be used either alone or in combination of two or more.

[0078] The amount of the organoaluminum compound used is preferably 0.01 to 1000 μmol, more preferably 0.1 to 500 μmol, per mg of the solid catalyst component for olefin polymerization.

[0079] Examples of external electron donors include compounds described in Japanese Patent No. 2950168, JP 2006-96936 A, JP 2009-173870 A, and JP 2010-168545 A. Among these, oxygen-containing compounds or nitrogen-containing compounds are preferred. Examples of oxygen-containing compounds include alkoxysilanes, ethers, esters, and ketones. Among these, alkoxysilanes or ethers are preferred.

[0080] The alkoxy silicon as the external electron donor is preferably a compound represented by any one of the following formulae (iv) to (vi). R 2 h Si(OR 3 ) 4-h (iv) Si(OR 4 )3(NR 5 R 6 )···(v) Si(OR 4 )3(NR 7 )···(vi) [In the formula, R 2 is a hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom; R 3 is a hydrocarbyl group having 1 to 20 carbon atoms; and h is an integer satisfying the condition 0≦h<4. 2 and R 3 If one or both of these exist multiple times, multiple R 2 and R 3 R may be the same or different. 4 is a hydrocarbyl group having 1 to 6 carbon atoms; R 5 and R 6 is a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms; NR 7 is a cyclic amino group having 5 to 20 carbon atoms.]

[0081] R in the above formula (iv) 2 and R 3Examples of the hydrocarbyl group include an alkyl group, an aralkyl group, an aryl group, and an alkenyl group. 2 and R 3 Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, and 2-ethylhexyl; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, preferably linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. 2 and R 3 Examples of the aralkyl group include a benzyl group and a phenethyl group, and preferably an aralkyl group having 7 to 20 carbon atoms. 2 and R 3 Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group, and preferably an aryl group having 6 to 20 carbon atoms. 2 and R 3 Examples of the alkenyl group include linear alkenyl groups such as vinyl, allyl, 3-butenyl, and 5-hexenyl; branched alkenyl groups such as isobutenyl and 5-methyl-3-pentenyl; and cyclic alkenyl groups such as 2-cyclohexenyl and 3-cyclohexenyl, and preferably alkenyl groups having 2 to 10 carbon atoms.

[0082] Specific examples of alkoxysilanes represented by formula (iv) above include cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, di-isopropyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, iso-butyltriethoxysilane, vinyltriethoxysilane, sec-butyltriethoxysilane, cyclohexyltriethoxysilane, and cyclopentyltriethoxysilane.

[0083] R in the above formulas (v) and (vi) 4 Examples of the hydrocarbyl group in R include an alkyl group and an alkenyl group. 4 Examples of the alkyl group in R include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, and neopentyl groups; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups, and are preferably linear alkyl groups having 1 to 6 carbon atoms. 4 Examples of the alkenyl group include linear alkenyl groups such as vinyl, allyl, 3-butenyl, and 5-hexenyl; branched alkenyl groups such as isobutenyl and 5-methyl-3-pentenyl; and cyclic alkenyl groups such as 2-cyclohexenyl and 3-cyclohexenyl. Of these, linear alkenyl groups having 2 to 6 carbon atoms are preferred, and methyl or ethyl groups are particularly preferred.

[0084] R in the above formula (v) 5 and R 6 Examples of the hydrocarbyl group include an alkyl group and an alkenyl group. 5 and R 6Examples of the alkyl group include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, and neopentyl groups; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups, and preferably linear alkyl groups having 1 to 6 carbon atoms. 5 and R 6 Examples of the alkenyl group include linear alkenyl groups such as vinyl, allyl, 3-butenyl, and 5-hexenyl; branched alkenyl groups such as isobutenyl and 5-methyl-3-pentenyl; and cyclic alkenyl groups such as 2-cyclohexenyl and 3-cyclohexenyl. Of these, linear alkenyl groups having 2 to 6 carbon atoms are preferred, and methyl or ethyl groups are particularly preferred.

[0085] Specific examples of alkoxysilanes represented by the above formula (v) include dimethylaminotrimethoxysilane, diethylaminotrimethoxysilane, di-n-propylaminotrimethoxysilane, dimethylaminotriethoxysilane, diethylaminotriethoxysilane, di-n-propylaminotriethoxysilane, methylethylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, tert-butylaminotriethoxysilane, di-isopropylaminotriethoxysilane, and methyl-isopropylaminotriethoxysilane.

[0086] NR in the above formula (vi) 7 Examples of the cyclic amino group include a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, a 1,2,3,4-tetrahydroisoquinolino group, and an octamethyleneimino group.

[0087] Specific examples of the alkoxy silicon represented by the above formula (vi) include perhydroquinolinotriethoxysilane, perhydroisoquinolinotriethoxysilane, 1,2,3,4-tetrahydroquinolinotriethoxysilane, 1,2,3,4-tetrahydroisoquinolinotriethoxysilane, and octamethyleneiminotriethoxysilane.

[0088] The external electron donor ether is preferably a cyclic ether compound, which is a heterocyclic compound having at least one -COC- bond in the ring structure, preferably a cyclic ether compound having at least one -COCOC- bond in the ring structure, more preferably 1,3-dioxolane or 1,3-dioxane.

[0089] The external electron donors may be used alone or in combination of two or more.

[0090] The amount of the external electron donor used is preferably 0.0001 to 1000 μmol, more preferably 0.001 to 500 μmol, and even more preferably 0.01 to 150 μmol, per mg of the solid catalyst component for olefin polymerization.

[0091] When the above-mentioned olefin polymerization catalyst is used to polymerize an olefin, a polymer having a relatively high stereoregularity can be obtained.

[0092] <Olefin polymer> An olefin polymer can be obtained by polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst.

[0093] Examples of olefins include ethylene and α-olefins having 3 or more carbon atoms. Examples of α-olefins include linear monoolefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene; branched monoolefins such as 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene; cyclic monoolefins such as vinylcyclohexane; and combinations of two or more of these. Among these, it is preferable to use ethylene or propylene alone, or it is preferable to use multiple olefins containing ethylene or propylene as the main component. The combination of multiple olefins may include a combination of two or more olefins, or may include a combination of an olefin and a compound having a polyunsaturated bond, such as a conjugated diene or a non-conjugated diene.

[0094] The olefin polymer is preferably an ethylene homopolymer, a propylene homopolymer, a 1-butene homopolymer, a 1-pentene homopolymer, a 1-hexene homopolymer, an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, a propylene-1-butene copolymer, a propylene-1-hexene copolymer, an ethylene-propylene-1-butene copolymer, an ethylene-propylene-1-hexene copolymer, or a polymer obtained by multistage polymerization of any of these.

[0095] In the production of the above olefin polymer, when the olefin polymerization catalyst is formed, it is preferable to carry out the following steps. (i) A step of polymerizing a small amount of olefin in the presence of a solid catalyst component for olefin polymerization and an organoaluminum compound to produce a catalyst component the surface of which is covered with a polymer of the olefin (hereinafter also referred to as a prepolymerized catalyst component). (ii) contacting the prepolymerized catalyst component with an organoaluminum compound and an external electron donor; The olefin used in step (i) may be the same as or different from the olefin polymerized in the polymerization of olefins using an olefin polymerization catalyst (hereinafter also referred to as "main polymerization"). In order to adjust the molecular weight of the olefin polymer produced in step (i), a chain transfer agent such as hydrogen or an external electron donor may be used.

[0096] The polymerization in step (i) (hereinafter also referred to as "prepolymerization") may be preferably slurry polymerization using an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, or toluene as a solvent.

[0097] The amount of the organoaluminum compound used in the above step (i) is preferably 0.5 mol to 700 mol, more preferably 0.8 mol to 500 mol, and particularly preferably 1 mol to 200 mol per mol of titanium atom in the solid catalyst component for olefin polymerization used in step (i).

[0098] The amount of the olefin to be prepolymerized is preferably 0.01 g to 1000 g, more preferably 0.05 g to 500 g, and particularly preferably 0.1 g to 200 g per gram of the solid catalyst component for olefin polymerization used in step (i).

[0099] The slurry concentration of the solid catalyst component for olefin polymerization in the slurry polymerization in the above step (i) is preferably 1 to 500 g-solid catalyst component for olefin polymerization / liter-solvent, more preferably 3 to 300 g-solid catalyst component for olefin polymerization / liter-solvent.

[0100] The temperature of the prepolymerization is preferably -20°C to 100°C, more preferably 0°C to 80°C. The partial pressure of the olefin in the gas phase during the prepolymerization is preferably 0.01 MPa to 2 MPa, more preferably 0.1 MPa to 1 MPa, although this does not apply to olefins that are liquid at the pressure and temperature of the prepolymerization. The time of the prepolymerization is preferably 2 minutes to 15 hours.

[0101] In the prepolymerization, the solid catalyst component for olefin polymerization, the organoaluminum compound, and the olefin can be supplied to the prepolymerization vessel by the following methods (1) and (2). (1) A method in which a solid catalyst component for olefin polymerization and an organoaluminum compound are fed to a prepolymerization reactor, and then an olefin is fed to the prepolymerization reactor. (2) A method in which a solid catalyst component for olefin polymerization and an olefin are fed to a prepolymerization reactor, and then an organoaluminum compound is fed to the prepolymerization reactor.

[0102] In the prepolymerization, the following methods (1) and (2) can be exemplified as methods for feeding the olefin to the prepolymerization vessel. (1) A method in which olefins are sequentially fed into the prepolymerization reactor so as to maintain the pressure in the prepolymerization reactor at a predetermined pressure. (2) A method in which the entire amount of a predetermined amount of olefin is fed into a prepolymerization reactor in one lump sum.

[0103] The amount of the external electron donor used in the prepolymerization is preferably 0.01 mol to 400 mol, more preferably 0.02 mol to 200 mol, and particularly preferably 0.03 mol to 100 mol, relative to 1 mol of titanium atoms contained in the solid catalyst component for olefin polymerization. The amount of the external electron donor used in the prepolymerization is preferably 0.003 mol to 5 mol, more preferably 0.005 mol to 3 mol, and particularly preferably 0.01 mol to 2 mol, relative to 1 mol of the organoaluminum compound.

[0104] Examples of methods for supplying an external electron donor to a prepolymerization reactor in prepolymerization include the following methods (1) and (2). (1) A method in which an external electron donor is supplied alone to a prepolymerization reactor. (2) A method in which a contact mixture of an external electron donor and an organoaluminum compound is supplied to a prepolymerization vessel.

[0105] When the above steps (i) and (ii) are carried out, the amount of the organoaluminum compound used in the main polymerization is preferably 1 mol to 1000 mol, particularly preferably 5 mol to 600 mol, per 1 mol of titanium atoms in the solid catalyst component for olefin polymerization.

[0106] When an external electron donor is used in the main polymerization, the amount of the external electron donor used is preferably 0.1 mol to 2000 mol, more preferably 0.3 mol to 1000 mol, and particularly preferably 0.5 mol to 800 mol per mol of titanium atom contained in the solid catalyst component for olefin polymerization. Also, when an external electron donor is used in the main polymerization, the amount of the external electron donor used is preferably 0.001 mol to 5 mol, more preferably 0.005 mol to 3 mol, and particularly preferably 0.01 mol to 1 mol per mol of the organoaluminum compound.

[0107] The temperature of the main polymerization is preferably -30°C to 300°C, more preferably 20°C to 180°C. The polymerization pressure is not particularly limited, and from the viewpoint of industrial and economical reasons, it is preferably atmospheric pressure to 10 MPa, more preferably about 200 kPa to 5 MPa. The polymerization may be a batch or continuous system, and examples of the polymerization method include slurry polymerization or solution polymerization using an inert hydrocarbon such as propane, butane, isobutane, pentane, hexane, heptane, or octane as a solvent, bulk polymerization using an olefin that is liquid at the polymerization temperature as a medium, and gas-phase polymerization.

[0108] In order to adjust the molecular weight of the polymer obtained by this polymerization, a chain transfer agent (for example, hydrogen or an alkyl zinc such as dimethyl zinc or diethyl zinc) may be used.

[0109] When an olefin polymerization catalyst is formed using the solid catalyst component for olefin polymerization according to the above embodiment and an olefin is polymerized using the olefin polymerization catalyst, a polymer having high stereoregularity (specifically, isotactic stereoregularity) can be obtained.

[0110] The amount of xylene-soluble components can be used as a measure of isotactic stereoregularity. The amount of xylene-soluble components in the olefin polymer obtained by polymerizing an olefin using the olefin polymerization catalyst according to the above embodiment is preferably 2.0 mass% or less, more preferably 1.5 mass% or less, and even more preferably 1.0 mass% or less. The amount of xylene-soluble components can be determined, for example, by the method described in the Examples below.

[0111] Furthermore, when a particulate olefin polymer is produced by gas phase polymerization using the solid catalyst component for olefin polymerization (specifically, the olefin polymerization catalyst) according to the above embodiment, polymer particles with a small amount of fine powder can be obtained. The amount of fine powder (1 mm or less) in the olefin polymer is preferably 4.0 mass % or less, more preferably 3.0 mass % or less.

[0112] Second Embodiment The second embodiment (embodiment of the second invention) will be described below. The second embodiment differs from the first embodiment in the following points, but the other configurations are common to both. Therefore, the common configurations will not be described repeatedly.

[0113] The method for producing a solid catalyst component for olefin polymerization according to the second embodiment includes a step of reacting a magnesium compound with a titanium halide compound so that the total calorific value per mole of the titanium compound is 6 kJ to 90 kJ, preferably 20 kJ to 90 kJ, and more preferably 30 kJ to 90 kJ. This step can suppress a decrease in polymerization activity due to the addition of heat to the resulting solid catalyst component for olefin polymerization. The total calorific value is based on the heat of reaction between the magnesium compound and the titanium halide compound in the step (XI) described below. The total calorific value can be calculated by multiplying the heat release rate by the heat release time, specifically by the method described in the Examples below. The total calorific value can be adjusted by the efficiency of converting the magnesium compound to magnesium halide. Specifically, the conversion efficiency can be increased in the step (XI) by adjusting at least one of the following (a) to (c): (a) Increase the reaction temperature. (b) Increase the feed rate of the titanium halide compound. (c) Increasing the concentration of the titanium halide compound and / or magnesium halide compound in the solvent.

[0114] Similarly to step (I) in the first embodiment, the method for producing a solid catalyst component for olefin polymerization according to the second embodiment preferably includes step (XI) of supplying a titanium halide compound to a magnesium compound mixture containing a magnesium compound and a solvent to obtain a slurry containing a solid product. Similarly to step (I) in the first embodiment, step (XI) includes a step (first supply step) of maintaining the supply rate of the titanium halide compound relative to the magnesium compound at a predetermined rate until a predetermined amount of the titanium halide compound relative to the magnesium compound has been supplied. In the second embodiment, the first supply step maintains the supply rate of the titanium halide compound relative to 1 mole of the magnesium compound at a rate of preferably 0.005 mol / min to 3.8 mol / min, more preferably 0.008 mol / min to 3.8 mol / min, until at least 0.5 mol of the titanium halide compound relative to 1 mole of the magnesium compound has been supplied.

[0115] In the second embodiment, step (XI), like step (I) in the first embodiment, may include a step (second supply step) of maintaining the supply rate of the titanium halide compound relative to the magnesium compound at a predetermined rate after supplying a predetermined amount of the titanium halide compound relative to the magnesium compound (after the first supply step). In the second embodiment, after supplying at least 0.5 mol of the titanium halide compound relative to the magnesium compound (i.e., after the first supply step), the supply rate of the titanium halide compound relative to 1 mol of the magnesium compound is preferably maintained at 1.0 mol / min to 5.0 mol / min, more preferably 1.0 mol / min to 4.8 mol / min, and even more preferably 2.0 mol / min to 4.0 mol / min. This increases the supply rate of the titanium halide compound relative to 1 mol of the magnesium compound after supplying at least 0.5 mol of the titanium halide compound relative to the magnesium compound, allowing for rapid supply of the titanium halide compound.

[0116] Furthermore, from the viewpoint of improving the particle properties of the resulting solid catalyst component for olefin polymerization, the method for producing the solid catalyst component for olefin polymerization according to the second embodiment preferably includes a step (XII) of supplying an internal electron donor to the slurry containing the solid product obtained in the step (XI), similarly to the step (II) in the first embodiment.

[0117] The magnesium compound, titanium halide compound, and internal electron donor that can be used in the method for producing a solid catalyst component for olefin polymerization according to the second embodiment are the same as those in the first embodiment. The magnesium compound used in the second embodiment is preferably a compound obtained by reacting a magnesium dialkoxide with a silicon halide compound. The silicon halide is preferably R n Six 4-n (wherein R represents hydrogen, an alkyl group, a haloalkyl group, an alkoxy group, or an aryl group; n represents an integer of 0 to 4; and X represents a chlorine atom, a bromine atom, or an iodine atom). The titanium halide compound used in the second embodiment is preferably a titanium tetrahalide. Examples of titanium tetrahalides include titanium tetrachloro, titanium tetraiodo, and titanium tetrabromo. The internal electron donor used in the second embodiment is preferably tetrahydrofuran.

[0118] In the method for producing a solid catalyst component for olefin polymerization according to the second embodiment, the maximum heat generation rate per 1 mol of the magnesium compound in the step of reacting the magnesium compound with the titanium halide compound is not particularly limited, and may be, for example, 18 W or less, as in the first embodiment, or may be more than 18 W.

[0119] The solid catalyst component for olefin polymerization produced by the above-described production method can be mixed with an organoaluminum compound (preferably an organoaluminum compound and an external electron donor) to produce an olefin polymerization catalyst, as in the first embodiment. That is, the method for producing an olefin polymerization catalyst according to the second embodiment, as in the first embodiment, comprises a mixing step of mixing the solid catalyst component for olefin polymerization with an organoaluminum compound (preferably an organoaluminum compound and an external electron donor). Examples of the organoaluminum compound and external electron donor that can be used in the method for producing an olefin polymerization catalyst according to the second embodiment are the same as those in the first embodiment.

[0120] Furthermore, as in the first embodiment, an olefin polymer can be obtained by polymerizing an olefin in the presence of the olefin polymerization catalyst produced by the above-mentioned production method. That is, the production method for an olefin polymer according to the second embodiment involves polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst. Examples of olefins used in the production method for an olefin polymer according to the second embodiment include the same olefins as those used in the first embodiment. [Example]

[0121] The first invention will be described in more detail below using examples and comparative examples, but the first invention is not limited to the following examples.

[0122] [Calculation of heat generation rate] The heat release rate (Q [W]) during the reaction of magnesium compounds with titanium halide compounds depends on the temperature difference between the inlet and outlet of the reactor jacket (ΔT [℃]) and the flow rate of the coolant (F [m 3 / s]), specific heat of the refrigerant (Cp [J / m 3·°C]) using the following formula (2). The largest average value of the heat generation rates every 10 minutes was defined as the maximum heat generation rate. The jacket of the reaction vessel accommodates the reaction vessel and is configured to allow a coolant to flow between it and the reaction vessel, and is equipped with an inlet for flowing the coolant into the reaction vessel and an outlet for flowing the coolant out from between it and the reaction vessel. Q = Cp × F × ΔT (2)

[0123] [Composition analysis of solid catalyst components for olefin polymerization] (1) Titanium atom content Approximately 20 mg of the solid catalyst component for olefin polymerization was decomposed with approximately 30 mL of 2N diluted sulfuric acid. Then, 3 mL of an excess of 3 mass% hydrogen peroxide solution was added. The characteristic absorption at 410 nm of the resulting liquid sample was measured using a JASCO V-650 UV-Visible Spectrophotometer in accordance with JIS K0115:2004, and the titanium atom content was determined based on a separately prepared calibration curve.

[0124] (2) Alkoxy group content Approximately 2 g of the solid catalyst component for olefin polymerization was decomposed in 100 mL of water. The amount of alcohol corresponding to the alkoxy groups in the resulting liquid sample was then determined using the gas chromatography internal standard method in accordance with JIS K0114:2012, and the result was converted into the alkoxy group content.

[0125] (3) Content of internal electron donor Approximately 300 mg of the solid catalyst component for olefin polymerization was dissolved in 100 mL of N,N-dimethylacetamide. Then, the amount of internal electron donor in the solution was determined by the gas chromatography internal standard method according to JIS K0114:2012.

[0126] (4) Median particle size (D50) of the solid catalyst component for olefin polymerization and cumulative percentage of components with particle sizes of 10 μm or less The median particle size (D50) and cumulative percentage of particles with a particle size of 10 μm or less were analyzed by laser diffraction and scattering in accordance with ISO 13320:2009. A laser diffraction particle size analyzer (Malvern Instruments, "Mastersizer 3000") was used. The refractive index was 1.49 for toluene and 1.53-0.1i for solid catalyst components for olefin polymerization. Toluene solvent, whose moisture content had been removed using alumina or other methods, was introduced into a dispersing device (Hydro MV) with a nitrogen-sealed opening, filling the circulating system, including the measurement cell, with the solvent. The stirring speed was set to 2,000 rpm, and the particle size was measured by introducing the powder sample to achieve a scattering intensity of 3–10% while circulating the solvent in the measurement cell without ultrasonic dispersion. The median particle size (D50) and cumulative percentage of particles with a particle size of 10 μm or less were calculated from the resulting particle size volume distribution chart. Samples were handled to avoid contact with air and moisture, and no pretreatment was performed.

[0127] [Polymer analysis] (1) Polymerization activity The mass of the polymer obtained per unit mass of the solid catalyst component for olefin polymerization used in the polymerization reaction was taken as the polymerization activity (unit: g-polymer / g-solid catalyst component).

[0128] (2) Xylene soluble component content (CXS: unit = mass%) The amount of 20° C. xylene soluble component (hereinafter abbreviated as CXS) of the olefin polymer was measured as follows. 1 g of the polymer was dissolved in 200 mL of boiling xylene, and then the solution was gradually cooled to 50°C, then immersed in ice water and cooled to 20°C with stirring, and left at 20°C for 3 hours. The precipitated polymer was filtered off, and the mass percentage of the polymer remaining in the filtrate was taken as CXS.

[0129] (3) Intrinsic viscosity ([η]: unit = dL / g) The intrinsic viscosity (hereinafter abbreviated as [η]) of the olefin polymer was measured as follows. Using an Ubbelohde viscometer, the reduced viscosity of three samples with concentrations of 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL was measured. The intrinsic viscosity was calculated using the calculation method described in page 491 of the reference book "Polymer Solutions, Polymer Experiments 11" (published by Kyoritsu Publishing Co., Ltd. in 1982). That is, the reduced viscosity was plotted against the concentration, and the intrinsic viscosity was calculated by extrapolation to zero. Tetralin was used as the solvent, and the measurement was carried out at a temperature of 135°C.

[0130] [Example 1] (1) Synthesis of solid catalyst components for olefin polymerization The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (52.8 L) and magnesium diethoxide (11 kg) were added to the reaction vessel and stirred to obtain a suspension. Thereafter, the temperature inside the reaction vessel was kept below 0°C, and while stirring, titanium tetrachloride (11.55 L) was added to the reaction vessel over 7 hours (first supply step). The titanium tetrachloride supply rate (initial supply rate), titanium tetrachloride supply amount (initial supply amount), and maximum heat release rate in the first supply step are shown in Table 1 below. Next, titanium tetrachloride (21.45 L) was added over 3 hours (second supply step). The titanium tetrachloride supply rate in the second supply step was 0.012 mol / min per 1 mol of magnesium diethoxide. Thereafter, the temperature inside the reaction vessel was kept below 2°C for 120 minutes. Next, ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.77 kg) was added to the reaction vessel while maintaining the temperature inside the vessel at 2°C or below. The temperature inside the reaction vessel was then lowered to 10°C or below and maintained for 120 minutes. Next, toluene (14.3 L) was added to the reaction vessel, the temperature inside the reaction vessel was then raised to 60°C, and ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (4.0 kg) was added. The temperature inside the reaction vessel was then raised to 110°C and the mixture was stirred for 3 hours. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the solid was washed three times with 83 L of toluene at 95°C. Then, toluene (34 L) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 60°C, and titanium tetrachloride (22 L) and ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.95 kg) were added. The temperature inside the reaction vessel was then raised to 110°C and the mixture was stirred for 30 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the solid was washed three times with 83 L of toluene at 60°C, then three times with hexane (83 L), and then dried to obtain a solid catalyst component for olefin polymerization (11.0 kg). This solid catalyst component for olefin polymerization had a titanium atom content of 2.46 mass%, an ethoxy group content of 0.66 mass%, and an internal electron donor content of 12.11 mass%. Furthermore, the median particle size of this solid catalyst component for olefin polymerization, as measured by a laser diffraction / scattering method, was 55.5 μm, and the cumulative percentage of components with particle sizes of 10 μm or less was 3.0%. The analytical results of this solid catalyst component for olefin polymerization are shown in Table 1 below.

[0131] (2) Propylene polymerization A 3-L autoclave equipped with a stirrer was thoroughly dried and then evacuated. Then, 2.63 mmol of triethylaluminum (organoaluminum compound), 0.26 mmol of cyclohexylethyldimethoxysilane (external electron donor), and 5.55 mg of the solid catalyst component for olefin polymerization synthesized in Example 1(1) above were added to the autoclave. Next, 780 g of propylene and 0.2 MPa of hydrogen were added to the autoclave. The temperature of the autoclave was raised to 80°C, and propylene was polymerized at 80°C for 1 hour. After the polymerization reaction was completed, unreacted monomer was purged to obtain a propylene polymer. The amount of polymer produced per unit amount of catalyst (polymerization activity) was 50,600 g of polymer / g of solid catalyst component. The CXS of this polymer was 0.58 wt%, and [η] was 1.29 dL / g. The analytical results of the obtained polymer are shown in Table 2 below.

[0132] [Example 2] (1) Synthesis of solid catalyst components for olefin polymerization The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (52.8 L) and magnesium diethoxide (11 kg) were added to the reaction vessel and stirred to obtain a suspension. Thereafter, the temperature inside the reaction vessel was kept below 0°C, and titanium tetrachloride (11 L) was added to the reaction vessel over 2 hours while stirring (first supply step). The titanium tetrachloride supply rate (initial supply rate), titanium tetrachloride supply amount (initial supply amount), and maximum heat release rate in the first supply step are shown in Table 1 below. Next, titanium tetrachloride (22 L) was added over 8 hours (second supply step). The titanium tetrachloride supply rate in the second supply step was 0.043 mol / min per 1 mol of magnesium diethoxide. Thereafter, the temperature inside the reaction vessel was kept below 2°C for 120 minutes. Next, ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.77 kg) was added to the reaction vessel while maintaining the temperature inside the vessel at 2°C or below. The temperature inside the reaction vessel was then lowered to 10°C or below and maintained for 120 minutes. Next, toluene (14.3 L) was added to the reaction vessel, the temperature inside the reaction vessel was then raised to 60°C, and ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (4.0 kg) was added. The temperature inside the reaction vessel was then raised to 110°C and the mixture was stirred for 3 hours. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the solid was washed three times with 83 L of toluene at 95°C. Then, toluene (34 L) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 60°C, and titanium tetrachloride (22 L) and ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.95 kg) were added. The temperature inside the reaction vessel was then raised to 110°C and the mixture was stirred for 30 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the solid was washed three times with 83 L of toluene at 60°C, then three times with hexane (83 L), and then dried to obtain a solid catalyst component for olefin polymerization (10.6 kg). This solid catalyst component for olefin polymerization had a titanium atom content of 2.41 mass%, an ethoxy group content of 0.64 mass%, and an internal electron donor content of 12.36 mass%. Furthermore, the median particle size of this solid catalyst component for olefin polymerization, as measured by a laser diffraction / scattering method, was 54.7 μm, and the cumulative percentage of components with particle sizes of 10 μm or less was 4.0%. The analytical results of this solid catalyst component for olefin polymerization are shown in Table 1 below.

[0133] (2) Propylene polymerization Propylene polymerization was carried out in the same manner as in Example 1, except that the solid catalyst component for olefin polymerization synthesized in Example 2(1) above was used. The amount of polymer produced per catalyst unit amount (polymerization activity) was 50,100 g-polymer / g-solid catalyst component. The CXS of this polymer was 0.63 wt%, and [η] was 1.23 dL / g. The analytical results of the obtained polymer are shown in Table 2 below.

[0134] [Comparative Example 1] (1) Synthesis of solid catalyst components for olefin polymerization The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (33.4 L) and magnesium diethoxide (6.6 kg) were added to the reaction vessel and stirred to obtain a suspension. Thereafter, the temperature inside the reaction vessel was lowered to 0°C or below, and titanium tetrachloride (19.8 L) was added to the reaction vessel over 2 hours while stirring (comparative supply step). The titanium tetrachloride supply rate (initial supply rate), titanium tetrachloride supply amount (initial supply amount), and maximum heat generation rate in the comparative supply step are shown in Table 1 below. Next, the temperature inside the reaction vessel was lowered to 2°C or below and maintained for 120 minutes. Subsequently, while maintaining the temperature inside the vessel at 2°C or below, ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.45 kg) was added to the reaction vessel. Next, the temperature inside the reaction vessel was lowered to 10°C or below and maintained for 120 minutes. Subsequently, toluene (7.0 L) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 60°C, and ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (2.4 kg) was added. Next, the temperature inside the reaction vessel was raised to 110°C and stirred for 3 hours. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the solid was washed three times with 50 L of toluene at 95°C. Subsequently, toluene (30.3 L) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 60°C, and titanium tetrachloride (15 L) and ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.56 kg) were added. Next, the temperature inside the reaction vessel was raised to 110°C and the mixture was stirred for 60 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the solid was washed three times with 50 L of toluene at 60°C, then three times with hexane (50 L), and then dried to obtain a solid catalyst component for olefin polymerization (5.9 kg). This solid catalyst component for olefin polymerization had a titanium atom content of 2.07 mass%, an ethoxy group content of 0.40 mass%, and an internal electron donor content of 12.60 mass%. Furthermore, the median particle size of this solid catalyst component for olefin polymerization, as measured by a laser diffraction / scattering method, was 63.0 μm, and the cumulative percentage of components with particle sizes of 10 μm or less was 13.0%. The analytical results of the solid catalyst component for olefin polymerization are shown in Table 1 below.

[0135] (2) Propylene polymerization Propylene polymerization was carried out in the same manner as in Example 1, except that the solid catalyst component for olefin polymerization synthesized in Comparative Example 1(1) above was used. The amount of polymer produced per catalyst unit amount (polymerization activity) was 59,400 g-polymer / g-solid catalyst component. The CXS of this polymer was 0.76 wt%, and [η] was 1.13 dL / g. The analytical results of the obtained polymer are shown in Table 2 below.

[0136] [Table 1]

[0137] [Table 2]

[0138] <Summary> From Table 1, it can be seen that the "cumulative percentage of components having a particle size of 10 μm or less" is smaller in each Example than in Comparative Example 1. In other words, it can be seen that the solid catalyst component for olefin polymerization synthesized in each Example contains fewer relatively fine particles than in each Comparative Example. In other words, by setting the maximum heat release rate within a predetermined range, as in the first invention, it is possible to suppress the generation of a relatively fine powdery solid catalyst component for olefin polymerization.

[0139] The second invention will be described in more detail below using examples and comparative examples, but the second invention is not limited to the following examples.

[0140] [Calculation of heat generation rate] The heat generation rate (Q [kW]) when reacting a magnesium compound with a titanium halide compound is determined by the temperature difference between the inside temperature of the reaction vessel and the coolant temperature of the jacket (ΔT [℃]), the heat transfer area (S [m 2 ]) and the overall heat transfer coefficient (U[kJ / m 2·°C·s]) was calculated using the following formula (11). The largest value for the heat release rate per second was taken as the maximum heat release rate. The heat transfer area refers to the contact area between the reactants and the reactor, and was calculated from the volume of the reactants and the shape of the reactor. The overall heat transfer coefficient was calculated as U = 0.05 kJ / m using the following formula (X) on page 104 of "Applied Chemistry Series 4: Fundamentals of Chemical Engineering, 2006". 2 ·℃·s was calculated. Q = U × S × ΔT (11) 1 / U=1 / h1+L / k+1 / h2 (X) h1: Heat transfer coefficient of refrigerant [W / m 2 / K] h2: Heat transfer coefficient of reactants [W / m 2 / K] L: Jacket thickness [m] ·k: Heat transfer coefficient of the jacket [W / m / K]

[0141] [Heat generation time measurement] The difference between the internal temperature of the reaction vessel and the temperature of the jacket coolant when no reaction was taking place was measured, and the time it took for the temperature to exceed the reference temperature when the titanium halide compound was supplied was taken as the heat generation time (t [s]).

[0142] [Total heat generation calculation] The total calorific value (Q') was calculated using the following formula (12): Q is the heat release rate. Q' = Q × t (12)

[0143] [Polymerization activity of olefin polymerization catalysts] The amount of olefin polymer (ethylene polymer) produced per unit amount of the solid catalyst component for olefin polymerization was calculated as the polymerization activity. The thermal stability of the solid catalyst component for olefin polymerization was evaluated by calculating the amount of olefin polymer produced per unit amount of the solid catalyst component for olefin polymerization stored (heat-treated) in an incubator at 70°C for 24 hours as the polymerization activity, and by the rate of decrease from the polymerization activity of the component that was not heat-treated.

[0144] [Bulk density of olefin polymer] The bulk density of the olefin polymer was measured using a bulk specific gravity measuring instrument (K6721 manufactured by Tsutsui Rikagaku Kikai) in accordance with JIS K-6721 (1966).

[0145] [Example 11] Synthesis of solid catalyst components for olefin polymerization 11 The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (120 mL) and magnesium diethoxide (33 g) were added to the reaction vessel and stirred to obtain a suspension. Thereafter, the temperature in the reaction vessel was raised to 40°C, and silicon tetrachloride (10 mL) was added to the reaction vessel over 5 seconds while stirring. Thereafter, the temperature in the reaction vessel was maintained at 40°C and stirring was continued for 3 hours (first chlorination step, exothermic reaction). The resulting reaction mixture was maintained at 40°C, and toluene (100 mL) was added and stirred for 5 minutes, followed by solid-liquid separation. Toluene (129 mL) was added to the reaction vessel containing the obtained solid. The temperature inside the reaction vessel was then raised to 45°C, and titanium tetrachloride (25 mL) was added. After the dropwise addition was completed, the temperature was maintained at 45°C and the mixture was stirred for 20 minutes (first titanium supply step, exothermic reaction). The titanium tetrachloride supply rate, titanium tetrachloride supply amount, reactor internal temperature at the time of heat generation, maximum temperature difference (ΔT = reactor internal temperature - jacket coolant temperature), heat generation time, and total heat generation amount in the first titanium supply step are shown in Table 3 below. The temperature inside the reaction vessel was then raised to 110°C and the mixture was stirred for 30 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the obtained solid was washed four times with toluene (129 mL) at 110°C. Then, toluene (129 mL) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 50°C, and tetrahydrofuran (12 mL) was added. Next, the jacket temperature was raised to 50°C and the mixture was stirred for 1 hour. The reaction mixture was subjected to solid-liquid separation at 50°C, and the resulting solid was washed once with toluene (129 mL) at 50°C, then washed twice with hexane (129 mL), and then vacuum dried to obtain a solid catalyst component for olefin polymerization 11 (39 g).

[0146] Synthesis of ethylene-butene copolymer 11 A 3-L autoclave equipped with a stirrer was thoroughly dried and then evacuated. Then, 0.12 MPa of hydrogen, 100 g of butene, and 652 g of butane were added to the autoclave. The autoclave was heated to 70°C, and 0.6 MPa of ethylene, 3 mmol of triisobutylaluminum (an organoaluminum compound), and approximately 60 mg of solid catalyst component 11 for olefin polymerization were added to the autoclave. Ethylene was then supplied to maintain a constant pressure in the system, and ethylene and butene were copolymerized at 70°C for 2 hours. After the polymerization reaction was completed, unreacted monomer was purged to obtain ethylene-butene copolymer 11. The amount of polymer produced per unit amount of solid catalyst component for olefin polymerization was calculated as the polymerization activity. The results are shown in Table 4 below.

[0147] [Example 12] Synthesis of solid catalyst component 12 for olefin polymerization The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (120 mL) and magnesium diethoxide (33 g) were added to the reaction vessel and stirred to obtain a suspension. Thereafter, the temperature in the reaction vessel was raised to 40°C, and silicon tetrachloride (10 mL) was added to the reaction vessel over 5 seconds while stirring. Thereafter, the temperature in the reaction vessel was maintained at 40°C and stirring was continued for 3 hours (first chlorination step, exothermic reaction). The resulting reaction mixture was maintained at 40°C, and toluene (100 mL) was added and stirred for 5 minutes, followed by solid-liquid separation. Toluene (129 mL) was added to the reaction vessel containing the obtained solid. The temperature inside the reaction vessel was then raised to 45°C, and titanium tetrachloride (10 mL) was added. After the dropwise addition was completed, the temperature was maintained at 45°C and the mixture was stirred for 20 minutes (first titanium supply step, exothermic reaction). The titanium tetrachloride supply rate, titanium tetrachloride supply amount, reactor internal temperature at the time of heat generation, maximum temperature difference (ΔT = reactor internal temperature - jacket coolant temperature), heat generation time, and total heat generation amount in the first titanium supply step are shown in Table 3 below. The temperature inside the reaction vessel was then raised to 110°C and the mixture was stirred for 30 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the obtained solid was washed once with toluene (129 mL) at 110°C. Toluene (129 mL) was then added to the reaction vessel, the temperature inside the reaction vessel was raised to 40°C, and titanium tetrachloride (15 mL, 90 mL / min) was added (second titanium supply step, ΔT = 0, so no heat generation occurred). The temperature inside the reaction vessel was then raised to 110°C and stirred for 60 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed four times with toluene (129 mL) at 110°C. Then, toluene (129 mL) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 50°C, and tetrahydrofuran (12 mL) was added. Next, the jacket temperature was raised to 50°C and the mixture was stirred for 1 hour. The reaction mixture was subjected to solid-liquid separation at 50°C, and the resulting solid was washed once with toluene (129 mL) at 50°C, then washed twice with hexane (129 mL), and then vacuum dried to obtain a solid catalyst component for olefin polymerization 12 (39 g).

[0148] Synthesis of ethylene-butene copolymer 12 A 3-L autoclave equipped with a stirrer was thoroughly dried and then evacuated. Then, 0.12 MPa of hydrogen, 100 g of butene, and 652 g of butane were added to the autoclave. The autoclave was heated to 70°C, and 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (an organoaluminum compound), and approximately 20 mg of the solid catalyst component for olefin polymerization 12 were added to the autoclave. Ethylene was then supplied to maintain a constant pressure in the system, and ethylene and butene were copolymerized at 70°C for 2 hours. After the polymerization reaction was completed, unreacted monomer was purged to obtain an ethylene-butene copolymer 12. The amount of polymer produced per unit amount of the solid catalyst component for olefin polymerization was calculated as the polymerization activity. The results are shown in Table 4 below.

[0149] [Example 13] Synthesis of solid catalyst components 13 for olefin polymerization The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (120 mL) and magnesium diethoxide (33 g) were added to the reaction vessel and stirred to obtain a suspension. The temperature inside the reaction vessel was then raised to 40°C, and silicon tetrachloride (10 mL) was added to the reaction vessel over 5 seconds while stirring. The temperature inside the reaction vessel was then maintained at 40°C and stirred for 3 hours (first chlorination step, exothermic reaction). The temperature inside the reaction vessel was then raised to 105°C and stirred for 30 minutes. The temperature inside the reaction vessel was then raised to 20°C, titanium tetrachloride (5 mL) was added, and the mixture was stirred for 60 minutes while maintaining the temperature at 20°C (first titanium supply step, exothermic reaction). The titanium tetrachloride supply rate, titanium tetrachloride supply amount, reactor internal temperature at the time of heat generation, maximum temperature difference (ΔT = reactor internal temperature - jacket coolant temperature), heat generation time, and total heat generation amount in the first titanium supply step are shown in Table 3 below. The temperature inside the reaction vessel was then raised to 105°C, and the mixture was stirred for 30 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 105°C, and the resulting solid was washed once with toluene (129 mL) at 105°C. Toluene (129 mL) was then added to the reaction vessel, the temperature inside the reaction vessel was raised to 40°C, and titanium tetrachloride (15 mL, 90 mL / min) was added (second titanium supply step, ΔT = 0, so no heat was generated). The temperature inside the reaction vessel was then raised to 110°C and stirred for 120 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed three times with toluene (129 mL) at 110°C. Then, toluene (129 mL) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 50°C, and tetrahydrofuran (9 mL) was added. Next, the jacket temperature was raised to 50°C and the mixture was stirred for 30 minutes, and then raised to 70°C and stirred for 30 minutes. The reaction mixture was subjected to solid-liquid separation at 70°C, and the resulting solid was washed twice with toluene (129 mL) at 70°C, then twice with hexane (129 mL), and then vacuum dried to obtain a solid catalyst component for olefin polymerization 13 (38 g).

[0150] Synthesis of ethylene-butene copolymer 13 A 3-L autoclave equipped with a stirrer was thoroughly dried and then evacuated. Then, 0.12 MPa of hydrogen, 100 g of butene, and 652 g of butane were added to the autoclave. The autoclave was heated to 70°C, and 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (an organoaluminum compound), and approximately 20 mg of the solid catalyst component for olefin polymerization 13 were added to the autoclave. Ethylene was then supplied to maintain a constant pressure in the system, and ethylene and butene were copolymerized at 70°C for 2 hours. After the polymerization reaction was completed, unreacted monomer was purged to obtain an ethylene-butene copolymer 13. The amount of polymer produced per unit amount of the solid catalyst component for olefin polymerization was calculated as the polymerization activity. The results are shown in Table 4 below.

[0151] [Example 14] Synthesis of solid catalyst component 14 for olefin polymerization The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (120 mL) and magnesium diethoxide (33 g) were added to the reaction vessel and stirred to obtain a suspension. The temperature inside the reaction vessel was then raised to 40°C, and silicon tetrachloride (10 mL) was added to the reaction vessel over 5 seconds while stirring. The temperature inside the reaction vessel was then maintained at 40°C and stirred for 3 hours (first chlorination step, exothermic reaction). Thereafter, while maintaining the temperature inside the reaction vessel at 40°C, titanium tetrachloride (10 mL) was added and stirred for 10 minutes (first titanium supply step, exothermic reaction). The titanium tetrachloride supply rate, titanium tetrachloride supply amount, reactor internal temperature at the time of heat generation, maximum temperature difference (ΔT = reactor internal temperature - jacket coolant temperature), heat generation time, and total heat generation amount in the first titanium supply step are shown in Table 3 below. The temperature inside the reaction vessel was then raised to 105°C and stirred for 60 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 105°C, and the resulting solid was washed once with toluene (129 mL) at 105°C. Toluene (129 mL) was then added to the reaction vessel, the temperature inside the reaction vessel was raised to 40°C, and titanium tetrachloride (10 mL, 60 mL / min) was added (second titanium supply step, ΔT = 0, so no heat was generated). The temperature inside the reaction vessel was then raised to 110°C and stirred for 120 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed three times with toluene (129 mL) at 110°C. Then, toluene (129 mL) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 50°C, and tetrahydrofuran (6 mL) was added. Next, the jacket temperature was raised to 50°C and the mixture was stirred for 30 minutes, and then raised to 70°C and stirred for 30 minutes. The reaction mixture was subjected to solid-liquid separation at 70°C, and the resulting solid was washed twice with toluene (129 mL) at 70°C, then washed twice with hexane (129 mL), and then vacuum dried to obtain a solid catalyst component for olefin polymerization 14 (36 g).

[0152] Synthesis of ethylene-butene copolymer 14 A 3-L autoclave equipped with a stirrer was thoroughly dried and then evacuated. Then, 0.12 MPa of hydrogen, 100 g of butene, and 652 g of butane were added to the autoclave. The autoclave was heated to 70°C, and 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (an organoaluminum compound), and approximately 20 mg of solid catalyst component 14 for olefin polymerization were added to the autoclave. Ethylene was then supplied to maintain a constant pressure in the system, and ethylene and butene were copolymerized at 70°C for 2 hours. After the polymerization reaction was completed, unreacted monomer was purged to obtain ethylene-butene copolymer 14. The amount of polymer produced per unit amount of solid catalyst component for olefin polymerization was calculated as the polymerization activity. The results are shown in Table 4 below.

[0153] [Comparative Example 11] Synthesis of solid catalyst component C11 for olefin polymerization The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (120 mL) and magnesium diethoxide (33 g) were added to the reaction vessel and stirred to obtain a suspension. The temperature inside the reaction vessel was then raised to 30°C, and silicon tetrachloride (14 mL) was added to the reaction vessel over 5 seconds while stirring. The temperature inside the reaction vessel was then maintained at 30°C and stirred for 2 hours (first chlorination step, exothermic reaction). The temperature inside the reaction vessel was then raised to 105°C and stirred for 60 minutes. The resulting reaction mixture was maintained at 105°C, and the supernatant was removed. The resulting solid was then washed once with toluene (216 mL) at 105°C (cleaning and removing the supernatant). The temperature inside the reaction vessel was then raised to 35°C, and titanium tetrachloride (15 mL) was added (first titanium supply step, exothermic reaction). The titanium tetrachloride supply rate, titanium tetrachloride supply amount, reactor internal temperature at the time of heat generation, maximum temperature difference (ΔT = reactor internal temperature - jacket coolant temperature), heat generation time, and total heat generation amount in the first titanium supply step are shown in Table 3 below. The temperature inside the reaction vessel was then raised to 110°C, and the mixture was stirred for 120 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed four times with toluene (129 mL) at 110°C, and then washed twice with hexane (129 mL) at 30°C. Then, hexane (129 mL) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 30°C, and tetrahydrofuran (12 mL) was added. Then, the temperature inside the reaction vessel was raised to 30°C and the mixture was stirred for 30 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 30°C, and the resulting solid was washed twice with hexane (129 mL) and then vacuum dried to obtain a solid catalyst component for olefin polymerization C11 (40 g).

[0154] Synthesis of ethylene-butene copolymer C11 A 3-L autoclave equipped with a stirrer was thoroughly dried and then evacuated. Then, 0.12 MPa of hydrogen, 100 g of butene, and 652 g of butane were added to the autoclave. The autoclave was heated to 70°C, and 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (an organoaluminum compound), and approximately 20 mg of the solid catalyst component C11 for olefin polymerization were added to the autoclave. Ethylene was then supplied to maintain a constant pressure in the system, and ethylene and butene were copolymerized at 70°C for 2 hours. After the polymerization reaction was completed, unreacted monomer was purged to obtain an ethylene-butene copolymer C11. The amount of polymer produced per unit amount of the solid catalyst component for olefin polymerization was calculated as the polymerization activity. The results are shown in Table 4 below.

[0155] [Comparative Example 12] Synthesis of solid catalyst component C12 for olefin polymerization The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (120 mL) and magnesium diethoxide (33 g) were added to the reaction vessel and stirred to obtain a suspension. The temperature inside the reaction vessel was then raised to 30°C, and silicon tetrachloride (14 mL) was added to the reaction vessel over 5 seconds while stirring. The temperature inside the reaction vessel was then raised to 30°C and stirred for 3 hours (first chlorination step, exothermic reaction). The temperature inside the reaction vessel was then raised to 105°C and stirred for 60 minutes. The resulting reaction mixture was maintained at 105°C, and toluene (216 mL) was added and stirred, and the supernatant was removed. The resulting solid was then washed once with toluene (126 mL) at 105°C (cleaning and removal of the supernatant). The temperature inside the reaction vessel was then raised to 35°C, and titanium tetrachloride (20 mL) was added (first titanium supply step, exothermic reaction). The titanium tetrachloride supply rate, titanium tetrachloride supply amount, reactor internal temperature at the time of heat generation, maximum temperature difference (ΔT = reactor internal temperature - jacket coolant temperature), heat generation time, and total heat generation amount in the first titanium supply step are shown in Table 3 below. The temperature inside the reaction vessel was then raised to 110°C, and the mixture was stirred for 120 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed four times with toluene (129 mL) at 110°C, and then washed twice with hexane (129 mL) at 30°C. Then, hexane (129 mL) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 30°C, and tetrahydrofuran (12 mL) was added. Then, the temperature inside the reaction vessel was raised to 30°C and stirred for 30 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 30°C, and the resulting solid was washed twice with hexane (129 mL) and then vacuum dried to obtain a solid catalyst component for olefin polymerization C12 (41 g).

[0156] Synthesis of ethylene-butene copolymer C12 A 3-L autoclave equipped with a stirrer was thoroughly dried and then evacuated. Then, 0.12 MPa of hydrogen, 100 g of butene, and 652 g of butane were added to the autoclave. The autoclave was heated to 70°C, and 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (an organoaluminum compound), and approximately 20 mg of the solid catalyst component C12 for olefin polymerization were added to the autoclave. Ethylene was then supplied to maintain a constant pressure in the system, and ethylene and butene were copolymerized at 70°C for 2 hours. After the polymerization reaction was completed, unreacted monomer was purged to obtain ethylene-butene copolymer C12. The amount of polymer produced per unit amount of the solid catalyst component for olefin polymerization was calculated as the polymerization activity. The results are shown in Table 4 below.

[0157] [Comparative Example 13] Synthesis of solid catalyst component C13 for olefin polymerization The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (120 mL) and magnesium diethoxide (33 g) were added to the reaction vessel and stirred to obtain a suspension. The temperature inside the reaction vessel was then raised to 40°C, and silicon tetrachloride (10 mL) was added to the reaction vessel over 5 seconds while stirring. The temperature inside the reaction vessel was then raised to 40°C and stirred for 3 hours (first chlorination step, exothermic reaction). The temperature inside the reaction vessel was then raised to 105°C and stirred for 60 minutes. While maintaining the reaction mixture at 105°C, toluene (216 mL) was added, stirred, and the supernatant was removed. The resulting solid was then washed once with toluene (126 mL) at 105°C (cleaning and removing the supernatant). The temperature inside the reaction vessel was then raised to 35°C, and titanium tetrachloride (15 mL) was added (first titanium supply step, exothermic reaction). The titanium tetrachloride supply rate, titanium tetrachloride supply amount, reactor internal temperature at the time of heat generation, maximum temperature difference (ΔT = reactor internal temperature - jacket coolant temperature), heat generation time, and total heat generation amount in the first titanium supply step are shown in Table 3 below. The temperature inside the reaction vessel was then raised to 110°C, and the mixture was stirred for 120 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed four times with toluene (129 mL) at 110°C, and then washed twice with hexane (129 mL) at 30°C. Then, hexane (129 mL) was added to the reaction vessel, the temperature inside the reaction vessel was raised to 30°C, and tetrahydrofuran (6 mL) was added. Then, the temperature inside the reaction vessel was raised to 30°C and stirred for 30 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 30°C, and the resulting solid was washed twice with hexane (129 mL) and then vacuum dried to obtain a solid catalyst component for olefin polymerization C13 (36 g).

[0158] Synthesis of ethylene-butene copolymer C13 A 3-L autoclave equipped with a stirrer was thoroughly dried and then evacuated. Then, 0.12 MPa of hydrogen, 100 g of butene, and 652 g of butane were added to the autoclave. The autoclave was heated to 70°C, and 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (an organoaluminum compound), and approximately 20 mg of the solid catalyst component C13 for olefin polymerization were added to the autoclave. Ethylene was then supplied to maintain a constant pressure in the system, and ethylene and butene were copolymerized at 70°C for 2 hours. After the polymerization reaction was completed, unreacted monomer was purged to obtain ethylene-butene copolymer C13. The amount of polymer produced per unit amount of the solid catalyst component for olefin polymerization was calculated as the polymerization activity. The results are shown in Table 4 below.

[0159] [Comparative Example 14] Synthesis of solid catalyst component C14 for olefin polymerization The gas in a reaction vessel equipped with a stirrer was replaced with nitrogen gas. Next, toluene (120 mL) and magnesium diethoxide (33 g) were added to the reaction vessel and stirred to obtain a suspension. The temperature inside the reaction vessel was then raised to 30°C, and silicon tetrachloride (14 mL) was added to the reaction vessel over 5 seconds while stirring. The temperature inside the reaction vessel was then raised to 30°C and stirred for 3 hours (first chlorination step, exothermic reaction). The temperature inside the reaction vessel was then raised to 105°C and stirred for 60 minutes. The resulting reaction mixture was maintained at 105°C, and toluene (216 mL) was added and stirred, and the supernatant was removed. The resulting solid was then washed once with toluene (126 mL) at 105°C (cleaning and removal of the supernatant). The temperature inside the reaction vessel was then raised to 35°C, and titanium tetrachloride (20 mL) was added (first titanium supply step, exothermic reaction). The titanium tetrachloride supply rate, titanium tetrachloride supply amount, reactor internal temperature at the time of heat generation, maximum temperature difference (ΔT = reactor internal temperature - jacket coolant temperature), heat generation time, and total heat generation amount in the first titanium supply step are shown in Table 3 below. The temperature inside the reaction vessel was then raised to 110°C, and the mixture was stirred for 120 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed four times with toluene (129 mL) at 110°C, and then washed twice with hexane (129 mL) at 30°C. Toluene (129 mL) was then added to the reaction vessel, the temperature inside the reaction vessel was raised to 40°C, and titanium tetrachloride (15 mL, 3 mL / min) was added (second titanium supply step, ΔT = 0, so no heat was generated). The temperature inside the reaction vessel was then raised to 110°C and stirred for 60 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed four times with toluene (129 mL) at 110°C. Toluene (129 mL) was then added to the reaction vessel, the temperature inside the reaction vessel was then raised to 30°C, and tetrahydrofuran (12 mL) was added. The temperature inside the reaction vessel was then raised to 30°C and stirred for 30 minutes. The resulting reaction mixture was subjected to solid-liquid separation at 30°C, and the resulting solid was washed once with toluene (129 mL), then washed twice with hexane (129 mL), and then vacuum dried to obtain a solid catalyst component for olefin polymerization C14 (41 g).

[0160] Synthesis of ethylene-butene copolymer C14 A 3-L autoclave equipped with a stirrer was thoroughly dried and then evacuated. Then, 0.12 MPa of hydrogen, 100 g of butene, and 652 g of butane were added to the autoclave. The autoclave was heated to 70°C, and 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (an organoaluminum compound), and approximately 20 mg of the solid catalyst component C14 for olefin polymerization were added to the autoclave. Ethylene was then supplied to maintain a constant pressure in the system, and ethylene and butene were copolymerized at 70°C for 2 hours. After the polymerization reaction was completed, unreacted monomer was purged to obtain ethylene-butene copolymer C14. The amount of polymer produced per unit amount of the solid catalyst component for olefin polymerization was calculated as the polymerization activity. The results are shown in Table 4 below.

[0161] [Table 3]

[0162] [Table 4]

[0163] <Summary> Tables 3 and 4 show that Examples with higher total calorific values ​​exhibit a lower rate of decrease in polymerization activity than Comparative Examples. In other words, by including a step of reacting a magnesium compound with a titanium halide compound so that the total calorific value per mole of titanium compound falls within a predetermined range, as in the second invention, it is possible to suppress a decrease in polymerization activity due to the application of heat to the solid catalyst component for olefin polymerization. Furthermore, Tables 3 and 4 show that each Example produces an olefin polymer with a bulk density of 0.300 g / mL or higher and a small rate of decrease in bulk density. In other words, by including a step of reacting a magnesium compound with a titanium halide compound so that the total calorific value per mole of titanium compound falls within a predetermined range, it is possible to suppress a decrease in bulk density of the resulting olefin polymer even when heat is applied to the solid catalyst component for olefin polymerization.

Claims

1. 1. A method for producing a solid catalyst component for olefin polymerization, comprising reacting a magnesium compound with a titanium halide compound to produce a solid catalyst component for olefin polymerization, the method comprising: a step of reacting a magnesium compound with a titanium halide compound so that the total calorific value per 1 mol of the titanium compound is 6 kJ to 90 kJ; a step (XI) of supplying a titanium halide compound to a magnesium compound mixed liquid containing a magnesium compound and a solvent to obtain a slurry containing a solid product; The step (XI) is maintaining a supply rate of the titanium halide compound relative to 1 mol of the magnesium compound at 0.005 mol / min to 3.8 mol / min until at least 0.5 mol of the titanium halide compound relative to 1 mol of the magnesium compound has been supplied; a step of supplying at least 0.5 mol of a titanium halide compound per 1 mol of a magnesium compound, and then maintaining the supply rate of the titanium halide compound per 1 mol of the magnesium compound at 1.0 mol / min to 5.0 mol / min; A method for producing a solid catalyst component for olefin polymerization, comprising:

2. 2. The method for producing a solid catalyst component for olefin polymerization according to claim 1, further comprising a step (XII) of supplying an internal electron donor to the slurry obtained in the step (XI).

3. 3. The method for producing a solid catalyst component for olefin polymerization according to claim 2, wherein the internal electron donor is tetrahydrofuran.

4. 4. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the magnesium compound is a compound obtained by reacting a magnesium dialkoxide with a silicon halide compound.

5. 5. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein the titanium halide compound is titanium tetrahalide.

6. A method for producing a catalyst for olefin polymerization, comprising a mixing step of mixing the solid catalyst component for olefin polymerization obtained by the method for producing a solid catalyst component for olefin polymerization according to any one of claims 1 to 5 with an organoaluminum compound.

7. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of an olefin polymerization catalyst produced by the method for producing an olefin polymerization catalyst according to claim 6.

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