JP2023046195A - Method for producing solid catalyst component for olefin polymerization, method for producing catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

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 The present invention relates to a method for producing a solid catalyst component for olefin polymerization, a method for producing an olefin polymerization catalyst, and a method for producing an olefin polymer.

As catalysts used for olefin polymerization, those containing solid catalyst components for olefin polymerization containing titanium atoms, magnesium atoms and halogen atoms are known. As a method for producing such a solid catalyst component for olefin polymerization, for example, Patent Document 1 discloses a method comprising a step of supplying powder of a magnesium compound to a solution containing a titanium halide compound and a solvent. . In such a production method, a powdery solid catalyst component for olefin polymerization can be obtained.

WO2018/025862

However, the solid catalyst component for olefin polymerization obtained by the production method described above contains a large amount of fine powder. When a catalyst is formed using such a solid catalyst component for olefin polymerization containing fine powder, and olefin is polymerized using the catalyst, the obtained polymer contains a large amount of fine powder. If a large amount of such fine powder contained in the polymer is contained in the gas discharged from the polymer polymerization tank, there is a risk that a large load will be imposed on the equipment (dust collector, heat exchanger, etc.) that processes such gas. .

In addition, when heat is applied to the solid catalyst component for olefin polymerization, the amount of polymer polymerized per unit amount (polymerization activity) may decrease due to the influence of the storage environment, transport environment, and the like.

Therefore, the first invention provides 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, Another object of the present invention is to provide a method for producing an olefin polymer using the olefin polymerization catalyst.

Further, the second invention is 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, and an olefin polymerization method containing the solid catalyst component for olefin polymerization. An object of the present invention is to provide a method for producing a catalyst for olefin polymerization and a method for producing an olefin polymer using the catalyst for olefin polymerization.

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

A method for producing an olefin polymerization catalyst according to the first invention comprises:
A mixing step of mixing the solid catalyst component for olefin polymerization obtained by the above-described method for producing a solid catalyst component for olefin polymerization and the organoaluminum compound is provided.

A method for producing an olefin polymer according to the first invention comprises:
An olefin is polymerized in the presence of the olefin polymerization catalyst.

A method for producing a solid catalyst component for olefin polymerization according to the second invention comprises:
A method for producing a solid catalyst component for olefin polymerization, comprising reacting a magnesium compound and a titanium halide compound to produce a solid catalyst component for olefin polymerization, comprising:
A step of reacting the magnesium compound and the halogenated titanium compound is provided so that the total calorific value per 1 mol of the titanium compound is 6 kJ to 90 kJ.

A method for producing an olefin polymerization catalyst according to the second invention comprises:
A mixing step of mixing the solid catalyst component for olefin polymerization obtained by the above-described method for producing a solid catalyst component for olefin polymerization and the organoaluminum compound is provided.

The method for producing an olefin polymer according to the second invention comprises:
The olefin is polymerized in the presence of the olefin polymerization catalyst described above.

According to the first invention, it is possible to provide a method for producing a solid catalyst component for olefin polymerization, which can reduce the amount of fine powder in the solid catalyst component for olefin polymerization. It is also possible to provide 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.

According to the second invention, it is possible to provide 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. It is also possible to provide 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.

<First embodiment>
A first embodiment (embodiment of the first invention) will be described below.

<Method for producing solid catalyst component for olefin polymerization>
In the method for producing a solid catalyst component for olefin polymerization according to the present embodiment, a magnesium compound and a titanium halide compound are reacted to obtain a solid catalyst component for olefin polymerization containing a titanium atom, a magnesium atom, and a halogen atom (preferably , a solid catalyst component for olefin polymerization further comprising an internal electron donor). Further, the method for producing a solid catalyst component for olefin polymerization according to the present embodiment includes the 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. have The solid product is the reaction product of the titanium halide compound and the magnesium compound.

A titanium halide compound means a compound containing a halogen atom and a titanium atom, with at least one halogen atom bonded to the titanium atom. Examples of titanium halide compounds include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide; methoxytitanium trichloride, ethoxytitanium trichloride, n-propoxytitanium trichloride and n-butoxytitanium. trihalogenated monoalkoxytitanium such as trichloride and ethoxytitanium tribromide; Alkoxytitanium; monohalogenated trialkoxytitanium such as trimethoxytitanium chloride, triethoxytitanium chloride, triiso-propoxytitanium 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 halogenated titanium compounds may be used alone or in combination of two or more.

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, and more preferably 0.03 mol to 50 mol, per 1 mol of total magnesium atoms in the magnesium compound used in step (I). It is preferably from 0.05 mol to 30 mol.

The magnesium compound may be any compound containing a magnesium atom, and specific examples thereof 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)
MgX _2.nR ¹ OH (iii)
(Wherein, k is a number that satisfies 0 ≤ k ≤ 2; m is a number that satisfies 0 < m ≤ 2 ^; n is a number that satisfies 0 ≤ n ≤ 3; a hydrocarbyl group having 1 to 20 atoms; X is a halogen atom.)

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

Examples of X in the above formulas (i) to (iii) include a chlorine atom, a bromine atom, an iodine atom, a fluorine atom and the like, preferably a chlorine atom. Multiple X's may be the same or different.

Specific examples of magnesium compounds of formulas (i) to (iii) include dimethylmagnesium, diethylmagnesium, diiso-propylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, dicyclohexylmagnesium, butyl dialkylmagnesium such as octylmagnesium; magnesium dialkoxides such as magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium dibutoxide, magnesium dihexyloxide, magnesium dioctyloxide, and magnesium dicyclohexyloxide; methylmagnesium chloride, ethylmagnesium chloride, iso-propylmagnesium chloride, n-butylmagnesium chloride, t-butylmagnesium chloride, hexylmagnesium chloride, iso-butylmagnesium chloride, benzylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, iso-propylmagnesium 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 alkylmagnesium halides such as iodide, hexylmagnesium iodide, iso-butylmagnesium iodide, and benzylmagnesium iodide; Halides; aryloxymagnesium halides such as phenyloxymagnesium chloride; magnesium halides such as magnesium fluoride, magnesium chloride, magnesium bromide and magnesium iodide;

Among them, magnesium halide or magnesium dialkoxide is preferred. The magnesium halide is preferably magnesium chloride. The magnesium dialkoxide is preferably a magnesium dialkoxide having an alkyl group having 1 to 20 carbon atoms, more preferably a magnesium dialkoxide having an alkyl group having 1 to 10 carbon atoms, and particularly preferably magnesium dimethoxy. magnesium diethoxide, magnesium dipropoxide, magnesium di(iso-propoxide), or magnesium dibutoxide.

A commercially available magnesium halide may be used as it is. Alternatively, commercially available magnesium halide may be dissolved in alcohol, the resulting solution may be added dropwise to a hydrocarbon liquid, and the resulting precipitate may be separated from the liquid and used. or in U.S. Pat. No. 6,825,146, WO 1998/044009, WO 2003/000754, WO 2003/000757, or WO 2003/085006 Magnesium halide produced according to the described method or the like may also be used.

As a method for producing magnesium dialkoxide, for example, a method of contacting metallic magnesium and alcohol in the presence of a catalyst (for example, JP-A-4-368391, JP-A-3-74341, JP-A-8-73388, , and International Publication No. 2013/058193 pamphlet). Alcohols include, for example, methanol, ethanol, propanol, butanol, octanol, and the like. Examples of the catalyst include halogens such as iodine, chlorine and bromine; magnesium halides such as magnesium iodide and magnesium chloride; iodine is preferred.

The magnesium compound may be supported on a carrier material. Examples of the carrier material include porous inorganic oxides such as SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ and ZrO ₂ ; 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, polypropylene and other organic porous polymers. Among these, porous inorganic oxides are preferred, and SiO ₂ is more preferred.

From the viewpoint of effectively immobilizing the magnesium compound on the carrier material, when a porous carrier material is used, the porous carrier material has pores determined by mercury porosimetry according to the standard ISO15901-1:2005. The total volume of pores with radii of 10 to 780 nm is preferably 0.3 cm ³ /g or more, more preferably 0.4 cm ³ /g or more. As the porous carrier material, the total volume of pores with a pore radius of 10 to 780 nm is preferably 25% or more of the total volume of pores with a pore radius of 2 to 100 μm, More preferably 30% or more.

The magnesium compounds exemplified above may be used alone, or two or more of them may be used in combination. Moreover, such a magnesium compound is preferably in the form of powder without being mixed with a solvent.

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, still more preferably 0, per 1 mL of the solvent contained in the magnesium compound mixture. .1 to 0.3 mg.

The solvent that constitutes the magnesium compound mixture is preferably inert to the solid product produced in step (I) (specifically, the solid catalyst component for olefin polymerization). Examples of solvents 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 them, 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.

The internal electron donor means an organic compound capable of donating an electron pair to one or more metal atoms contained in the solid catalyst component for olefin polymerization, specifically monoester compounds and dicarboxylic acid ester compounds. , diol diester compounds, β-alkoxyester compounds, diether compounds and the like.

A monoester compound means 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 aromatic carboxylic acid ester compounds include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, octyl benzoate, methyl toluate, ethyl toluate, and propyl toluate. , butyl toluate, pentyl toluate, hexyl toluate, octyl toluate and the like. Examples of 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, and propionic acid. Pentyl, 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, octyl valerate, methyl caproate, ethyl caproate, propyl caproate, butyl caproate, pentyl caproate, hexyl caproate, octyl caproate, methyl enanthate, ethyl enanthate, propyl enanthate, enanthate Butyl acid, 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, butyl pelargonate, pentyl pelargonate, hexyl pelargonate, octyl pelargonate, methyl caprate, ethyl caprate, propyl caprate, butyl caprate, pentyl caprate, hexyl caprate, octyl caprate, laurin Methyl acid, ethyl laurate, propyl laurate, butyl laurate, pentyl laurate, hexyl laurate, octyl laurate, methyl myristate, ethyl myristate, propyl myristate, butyl myristate, pentyl myristate, hexyl myristate , octyl myristate, methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate, pentyl palmitate, hexyl palmitate, octyl palmitate, methyl margarate, ethyl margarate, propyl margarate, butyl margarate, margarine pentyl stearate, hexyl margarate, octyl margarate, methyl stearate, ethyl stearate, propyl stearate, butyl stearate, pentyl stearate, hexyl stearate, octyl stearate and the like.

A 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. However, for example, an aromatic dicarboxylic acid ester compound or an aliphatic dicarboxylic acid ester compound is preferred. The aromatic dicarboxylic acid ester compound is, for example, a compound that can be synthesized from an aromatic dicarboxylic acid or an aromatic dicarboxylic acid dihalide and a monohydric alcohol, and specifically includes dimethyl phthalate, diethyl phthalate, and 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, isophthalate Dipentyl acid, dihexyl isophthalate, dioctyl isophthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dipentyl terephthalate, dihexyl terephthalate, dioctyl terephthalate and the like. The aliphatic dicarboxylic acid ester compound is, for example, a compound that can be synthesized from an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid dihalide and a monohydric alcohol, and specifically includes dimethyl ethanedioate, diethyl ethanedioate, ethane dipropyl diacid, dibutyl ethanedioate, dipentyl ethanedioate, dihexyl ethanedioate, dioctyl ethanedioate, dimethyl propanedioate, diethyl propanedioate, dipropyl propanedioate, dibutyl propanedioate, dipentyl propanedioate, propane dihexyl diacid, dioctyl propanedioate, dimethyl butanedioate, diethyl butanedioate, dipropyl butanedioate, dibutyl butanedioate, dipentyl butanedioate, dihexyl butanedioate, dioctyl butanedioate, dimethyl pentanedioate, pentane diethyl diacid, dipropyl pentanedioate, dibutyl pentanedioate, dipentyl pentanedioate, dihexyl pentanedioate, dioctyl pentanedioate, dimethyl hexanedioate, diethyl hexanedioate, dipropyl hexanedioate, dibutyl hexanedioate, hexane dipentyl diacid, dihexyl hexanedioate, dioctyl hexanedioate, dimethyl (E)-but-2-enedioate, diethyl (E)-but-2-enedioate, (E)-but-2-enediate dipropyl acid, (E)-but-2-enedioic acid dibutyl, (E)-but-2-enedioic acid dipentyl, (E)-but-2-enedioic acid dihexyl, (E)-but-2- Dioctyl endioate, (Z)-but-2-enedioate dimethyl, (Z)-but-2-enedioate diethyl, (Z)-but-2-enedioate dipropyl, (Z)-buta- dibutyl 2-enedioate, (Z)-but-2-enedioate dipentyl, (Z)-but-2-enedioate dihexyl, (Z)-but-2-enedioate dioctyl, cyclohexane-1, dimethyl 2-dicarboxylate, diethyl cyclohexane-1,2-dicarboxylate, dipropyl cyclohexane-1,2-dicarboxylate, dibutyl cyclohexane-1,2-dicarboxylate, dipentyl cyclohexane-1,2-dicarboxylate, cyclohexane-1, dihexyl 2-dicarboxylate, dioctyl cyclohexane-1,2-dicarboxylate, dimethyl 1,2-cyclohexene-1,2-dicarboxylate, diethyl 1,2-cyclohexene-1,2-dicarboxylate, 1,2-cyclohexene- dipropyl 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, 3-methylcyclohexane-1,2-dicarboxylic acid dipropyl acid, dibutyl 3-methylcyclohexane-1,2-dicarboxylate, dipentyl 3-methylcyclohexane-1,2-dicarboxylate, dihexyl 3-methylcyclohexane-1,2-dicarboxylate, 3-methylcyclohexane-1,2 -dioctyl 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, 3,6-dimethyl Dioctyl cyclohexane-1,2-dicarboxylate and the like can be mentioned.

A diol diester compound is a compound having two ester bonds (—CO—O—) in the molecule, and has a structure in which each of the two hydroxyl groups of the diol esterifies the carboxyl group of a monocarboxylic acid or dicarboxylic acid. for example, 1,2-dibenzoate propane, 1,2-diacetyloxypropane, 1,2-dibenzoate butane, 1,2-diacetyloxybutane, 1,2-dibenzoate cyclohexane, 1, 2-diacetyloxycyclohexane, 1,3-dibenzoatepropane, 1,3-diacetyloxypropane, 2,4-dibenzoatepentane, 2,4-diacetyloxypentane, 1,2-dibenzoatecyclopentane, 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, 1,3-diacetyloxy-4-tert-butyl-6-methylbenzene and the like.

The β-alkoxyester compound means a compound having an alkoxycarbonyl group and an alkoxy group at the β-position of the alkoxycarbonyl group. ethyl methyl-3,3-dimethylbutanoate, propyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, 2-methoxymethyl-3,3-dimethylbutane pentyl acid, hexyl 2-methoxymethyl-3,3-dimethylbutanoate, octyl 2-methoxymethyl-3,3-dimethylbutanoate, methyl 3-methoxy-2-phenylpropionate, 3-methoxy-2-phenylpropionate ethyl acetate, propyl 3-methoxy-2-phenylpropionate, butyl 3-methoxy-2-phenylpropionate, pentyl 3-methoxy-2-phenylpropionate, hexyl 3-methoxy-2-phenylpropionate, 3-methoxy -octyl 2-phenylpropionate, methyl 2-ethoxymethyl-3,3-dimethylbutanoate, ethyl 2-ethoxymethyl-3,3-dimethylbutanoate, propyl 2-ethoxymethyl-3,3-dimethylbutanoate, Butyl 2-ethoxymethyl-3,3-dimethylbutanoate, Pentyl 2-ethoxymethyl-3,3-dimethylbutanoate, Hexyl 2-ethoxymethyl-3,3-dimethylbutanoate, 2-ethoxymethyl-3,3 -octyl 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, 2- Ethyl propyloxymethyl-3,3-dimethylbutanoate, Propyl 2-propyloxymethyl-3,3-dimethylbutanoate, Butyl 2-propyloxymethyl-3,3-dimethylbutanoate, 2-Propyloxymethyl-3 , pentyl 3-dimethylbutanoate, hexyl 2-propyloxymethyl-3,3-dimethylbutanoate, octyl 2-propyloxymethyl-3,3-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, 3- hexyl propyloxy-2-phenylpropionate, octyl 3-propyloxy-2-phenylpropionate, methyl 2-methoxybenzenecarboxylate, ethyl 2-methoxybenzenecarboxylate, propyl 2-methoxybenzenecarboxylate, 2-methoxybenzene Butyl carboxylate, pentyl 2-methoxybenzenecarboxylate, hexyl 2-methoxybenzenecarboxylate, octyl 2-methoxybenzenecarboxylate, methyl 2-ethoxybenzenecarboxylate, ethyl 2-ethoxybenzenecarboxylate, 2-ethoxybenzenecarboxylic acid propyl, butyl 2-ethoxybenzenecarboxylate, pentyl 2-ethoxybenzenecarboxylate, hexyl 2-ethoxybenzenecarboxylate, octyl 2-ethoxybenzenecarboxylate and the like.

A diether compound means a compound having two ether bonds in the molecule, such as 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-dipropyloxypropane, 1,2-dibutoxy Propane, 1,2-di-tert-butoxypropane, 1,2-diphenoxypropane, 1,2-dibenzyloxypropane, 1,2-dimethoxybutane, 1,2-diethoxybutane, 1,2-di Propyloxybutane, 1,2-dibutoxybutane, 1,2-di-tert-butoxybutane, 1,2-diphenoxybutane, 1,2-dibenzyloxybutane, 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-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, 1,2-dibenzyloxybenzene and the like.

In addition, internal electron donors described in JP-A-2011-246699 can also be exemplified.

Among them, preferred internal electron donors include dicarboxylic acid ester compounds, diol diester compounds, β-alkoxyester compounds and the like. The internal electron donors may be used singly or in combination of two or more.

The amount of internal electron donor to be used is preferably 0.001 to 5 mol, more preferably 0.01 to 0.5 mol, per 1 mol of total magnesium atoms in the magnesium compound used in step (I).

In the method for producing a solid catalyst component for olefin polymerization according to the present embodiment, a magnesium compound and a titanium halide compound are reacted so that the maximum heat release rate per 1 mol of the magnesium compound is 18 W or less, preferably 10 W or less. It comprises a step of causing The maximum exothermic 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 obtained by the method described in [Example] below. The maximum exothermic rate can be adjusted by adjusting at least one of the temperature in the reaction vessel in which step (I) is performed, the concentration of substances, and the supply rate of the titanium halide compound described below.

In step (I), the supply rate of the titanium halide compound to 1 mol of the magnesium compound is 0.01 mol/min or less, preferably 0.005 mol/min or less, until at least 1 mol of the titanium halide compound is supplied to 1 mol of the magnesium compound. , more preferably 0.003 mol/min or less (hereinafter also referred to as "first supply step"). The step (I) includes at least one of the step of satisfying the maximum heat release rate and the step of satisfying the supply rate of the titanium halide compound. As a result, the amount of fine powder in the resulting solid catalyst component for olefin polymerization can be reduced. In the first supply step, the supply rate of the titanium halide compound with respect to 1 mol of the magnesium compound may be 0.0005 mol/min or more, or 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 performed within the maximum heat release rate range described above.

In step (I), after supplying at least 1 mol of the titanium halide compound to the magnesium compound (that is, after the first supply step), the supply rate of the titanium halide compound to 1 mol of the magnesium compound is preferably 0 .01 mol/min, more preferably 0.025 mol/min or more, more preferably 0.04 mol/min or more (hereinafter also referred to as "second supply step"). good too. As a result, after at least 1 mol of the titanium halide compound is supplied to the magnesium compound, the supply rate of the titanium halide compound increases, so that the titanium halide compound can be rapidly supplied. In the second supply step, the supply rate of the titanium halide compound with respect to 1 mol of the magnesium compound may be 10 mol/min or less, or 1 mol/min or less.

Step (I) is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.

The supply of the titanium halide compound to the magnesium compound mixed solution may be continuous or intermittent (for example, dropping mode). The titanium halide compound may be supplied to the magnesium compound mixture in a state of being 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 the solvent. may be supplied.

Examples of methods for contacting each component in step (I) include known methods such as a slurry method and a mechanical pulverization method (for example, a method of contacting while pulverizing the components with a ball mill).

The temperature in step (I) is preferably -20°C to 50°C, more preferably -10°C to 20°C, even more preferably -5°C to 10°C. The total time of step (I) (the total mixing time of the magnesium compound mixed solution and the titanium halide compound) is preferably 0.01 to 48 hours, more preferably 0.1 to 36 hours, still more preferably 0.5 to 24 hours.

The solvent contained in the slurry obtained in step (I) includes the solvent in the magnesium compound mixture. The solvent contained in the slurry obtained in step (I) may also contain the solvent in the solution when the titanium halide compound is mixed with the solvent and used in the form of a solution. In addition, the solvent contained in the slurry obtained in step (I) may include the solvent added alone during step (I) (for example, the solvent capable of constituting the magnesium compound mixed solution).

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, prior to step (I), an internal electron donor may be supplied into the reactor in which step (I) is performed. Alternatively, an internal electron donor may be supplied to the magnesium compound mixed solution. As another example, a titanium halide compound and an internal electron donor may be mixed. Alternatively, the internal electron donor may be fed into the reactor during step (I), or the internal electron donor may be fed to the slurry containing the solid product after step (I). A combination of these may also be used.

From the viewpoint of improving the particle properties of the resulting solid catalyst component for olefin polymerization, the internal electron donor is preferably supplied 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 the present embodiment has step (II) of supplying an internal electron donor to the slurry containing the solid product obtained in step (I).

Regardless of the timing of supply of 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, and more It is preferably -5°C to 135°C, 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 under an inert gas atmosphere such as nitrogen gas or argon gas.

Step (I) and step (II) are preferably carried out with stirring. For stirring, the peripheral speed v of the stirring blade represented by the following formula (1) is preferably in the range of 0.1 to 10 m / sec, more preferably in the range of 0.5 to 5.0 m / sec, further preferably It is carried out in the range of 1.0 to 3.0 m/sec.

v=n×d (1)
(In the formula, n represents the rotation speed (rad/sec) of the stirring blade, and d represents the blade diameter (m) of the stirring blade.)

The solid product obtained in step (I) (preferably the solid obtained by performing steps (I) and (II)) can be used as a solid catalyst component for olefin polymerization. Further, the solid product obtained in step (I) (preferably the solid obtained by performing steps (I) and (II)) is used as a precursor, and the precursor is combined with a titanium halide compound and a magnesium compound. The solid resulting from further contact with one or more of the internal electron donors may be the solid catalyst component for olefin polymerization.

The solid catalyst component or precursor for olefin polymerization described above is preferably washed with a washing solvent in order to remove unwanted substances. The solvent for washing is preferably inert to the solid catalyst components or precursors for olefin polymerization, for example aliphatic hydrocarbons such as pentane, hexane, heptane, octane; aromatic solvents such as benzene, toluene, xylene; group hydrocarbons; alicyclic hydrocarbons such as cyclohexane and cyclopentane; and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene. Among them, aromatic hydrocarbons or halogenated hydrocarbons are particularly preferred. The amount of the washing solvent used can be, for example, 0.1 mL to 1000 mL, preferably 1 mL to 100 mL, per 1 g of solid catalyst component for olefin polymerization or precursor per one-step contact. Washing is performed, for example, 1-5 times per step of contact. The washing temperature is, for example, -50 to 150°C, preferably 0 to 140°C, more preferably 60 to 135°C. The washing time is preferably 1 to 120 minutes, more preferably 2 to 60 minutes.

When the above precursor is brought into contact with one or more of a titanium halide compound, a magnesium compound and an internal electron donor to obtain a solid catalyst component for olefin polymerization, the solid catalyst component for olefin polymerization according to the present embodiment is has a step (III) of contacting the above precursor with one or more of a titanium halide compound, a magnesium compound and an internal electron donor.

Step (III) is preferably carried out in a solvent. The description of the solvent in step (III) is the same as the description of the solvent in step (I). When the 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 1 mL of the solvent used in step (III). 0 mL/mL. When the 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 1 mL of the solvent used in step (III). be. When the 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 0.005 mL/mL, per 1 mL of the solvent used in step (III). 5 mL/mL, more preferably 0.01-0.1 mL/mL.

The types of 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).

The temperature in step (III) is, for example, -20°C to 150°C, preferably -5°C to 130°C, more preferably 40°C to 120°C. The time for step (III) is, for example, 0.1 to 12 hours, preferably 1 to 8 hours. The contact between the precursor and one or more of the titanium halide compound, the magnesium compound, and the internal electron donor is performed under an inert gas atmosphere such as nitrogen gas, argon gas, or the like. Step (III) may be repeated once or multiple times.

After completion of the reaction in step (III), the obtained solid can be used as a solid catalyst component for olefin polymerization. Such a solid catalyst component for olefin polymerization is preferably washed with a washing solvent in the same manner as described above. In addition, drying (for example, drying under reduced pressure) may be performed after washing.

An olefin polymer obtained by polymerizing an olefin by forming an olefin polymerization catalyst using the olefin polymerization solid catalyst component produced as described above and polymerizing an olefin using the olefin polymerization catalyst. stereoregularity can be made relatively high. Further, when such an olefin polymerization catalyst is used, for example, when a particulate olefin polymer is produced by a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method, or the like, the amount of fine particles is relatively small. Coalesced particles can be provided.

<Solid catalyst component for olefin polymerization>
The solid catalyst component for olefin polymerization produced by the above production method exists as a solid content in at least toluene, and is combined with an olefin polymerization co-catalyst such as an organoaluminum compound to form an olefin polymerization catalyst. can be done.

Such solid catalyst components for olefin polymerization contain titanium atoms, magnesium atoms and halogen atoms, and are preferably selected from monoester compounds, aliphatic dicarboxylic acid ester compounds, diol diester compounds, β-alkoxyester compounds and diether compounds. at least one internal electron donor selected from the group consisting of

Further, the solid catalyst component for olefin polymerization preferably satisfies the following requirements (I) to (IV).

(I) Total pore volume measured by mercury porosimetry according to standard ISO15901-1:2005 is 0.95 to 1.80 mL/g, and specific surface area measured by mercury porosimetry according to standard ISO15901-1:2005 is 60 to 170 m ² /g.
(II) According to the standard ISO13320:2009, the cumulative percentage of components having a particle size of 10 µm or less in the volume-based particle size distribution measured by a laser diffraction/scattering method is 6.5% or less.
(III) According to the standard ISO15472:2001, among the peak components obtained by waveform separation of the peak attributed to the 1s orbital of the oxygen atom obtained by X-ray photoelectron spectroscopy, the binding energy of the peak top is 532 eV or more and 534 eV or less The ratio (G/F) of the area (G) of the peak component whose binding energy is in the range of 529 eV or more and less than 532 eV to the area (F) of the peak component in the range is 0.33 or less.
(IV) The titanium content is 1.50-3.40 wt%.

Some or all of the titanium atoms in the solid catalyst component for olefin polymerization are derived from the titanium halide compound described above. Some or all of the halogen atoms in the solid catalyst component for olefin polymerization are derived from the titanium halide compound described above.

Some or all of the magnesium atoms in the solid catalyst component for olefin polymerization are derived from the above magnesium compound. Also, part of the halogen atoms in the solid catalyst component for olefin polymerization may be derived from the magnesium compound.

The description of the monoester compound, aliphatic dicarboxylic acid ester compound, diol diester compound, β-alkoxyester 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-alkoxyester compound, more preferably a β-alkoxyester compound, still more preferably ethyl 2-ethoxymethyl-3,3-dimethylbutanoate is.

Requirement (I) above will be explained below.
The total pore volume is preferably 0.95-1.80 mL/g, more preferably 1.00-1.70 mL/g, still more preferably 1.10-1.60 mL/g. A total pore volume of 0.95 mL/g or more improves the productivity of the polymer. When the total pore volume is 1.80 mL/g or less, sufficient catalyst particle strength can be secured.
The above specific surface area is preferably 60 to 170 m ² /g, more preferably 80 to 150 m ² /g, still more preferably 88 to 130 m ² /g. When the specific surface area is 60 m ² /g or more, the sticky component contained in the resulting polymer can be reduced. When the specific surface area is 170 m ² /g or less, sufficient catalyst particle strength can be secured.

Requirement (II) above 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 troubles in the polymerization process can be suppressed.

Requirement (III) above 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, generation of sticky components can be suppressed in polymerization.

Requirement (IV) above will be explained below.
The titanium content is preferably 1.50-3.40 wt%, more preferably 1.6-3.0 wt%. When the titanium content is 3.40 wt% or less, 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.

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

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

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

<Catalyst for Olefin Polymerization>
An olefin polymerization catalyst can be produced by contacting the above 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 solid catalyst component for olefin polymerization and an organoaluminum compound (preferably an organoaluminum compound and an external electron donor). Therefore, the olefin polymerization catalyst produced by such a method contains the solid catalyst component for olefin polymerization and the organoaluminum compound, and preferably further contains an external electron donor.

The method of contacting the solid catalyst component for olefin polymerization with the organoaluminum compound (preferably, the method of contacting three components including these two components and an external electron donor) is as long as the catalyst for olefin polymerization is produced. It is not particularly limited. Contacting can be carried out in the presence or absence of a solvent. Alternatively, the above three components may be brought into contact to form an olefin polymerization catalyst, and the olefin polymerization catalyst may be supplied to a polymerization vessel for olefin polymerization. Alternatively, the olefin polymerization catalyst may be formed by supplying each component separately to the polymerization tank and contacting them in the polymerization tank. Alternatively, the contact mixture of any two components and the remaining components may be fed separately to a polymerization vessel and contacted in the polymerization vessel to form the olefin polymerization catalyst.

The organoaluminum compound is a compound having one or more carbon-aluminum bonds, and specific examples include compounds described in JP-A-10-212319. Among them, preferably trialkylaluminum; a mixture of trialkylaluminum and dialkylaluminum halide; or an alkylalumoxane, more preferably triethylaluminum; triiso-butylaluminum; a mixture of triethylaluminum and diethylaluminum chloride; It is tetraethyldialumoxane.

The organoaluminum compounds may be used alone or in combination of two or more.

The amount of the organoaluminum compound used is preferably 0.01 to 1000 μmol, more preferably 0.1 to 500 μmol, per 1 mg of the solid catalyst component for olefin polymerization.

Examples of external electron donors include the compounds described in Japanese Patent No. 2950168, Japanese Patent Application Laid-Open No. 2006-96936, Japanese Patent Application Laid-Open No. 2009-173870, and Japanese Patent Application Laid-Open No. 2010-168545. Among them, oxygen-containing compounds or nitrogen-containing compounds are preferred. Examples of oxygen-containing compounds include alkoxy silicons, ethers, esters, and ketones. Among them, alkoxy silicon or ether is preferred.

Alkoxy silicon as an external electron donor is preferably a compound represented by any one of the following formulas (iv) to (vi).

R ² _h Si(OR ³ ) _4-h (iv)
Si( ^OR4 ) ₃ ( ^NR5R6 ) ( ^v )
Si( ^OR4 ) ₃ ( ^NR7 ) (vi)
[wherein 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; is an integer that satisfies When one or both of R ² and R ³ are present in plural, the plural R ² and R ³ may be the same or different from each other. R ⁴ is a hydrocarbyl group having 1 to 6 carbon atoms; R ⁵ and R ⁶ are a hydrogen atom or a hydrocarbyl group having 1 to 12 carbon atoms; NR ⁷ is a hydrocarbyl group having 5 to 12 carbon atoms; 20 cyclic amino groups. ]

Examples of hydrocarbyl groups for R ² and R ³ in the above formula (iv) include alkyl groups, aralkyl groups, aryl groups, alkenyl groups, etc. Examples of alkyl groups for R ² and R ³ include: Linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group; iso-propyl group, iso- Branched alkyl groups such as butyl group, tert-butyl group, iso-pentyl group, neopentyl group and 2-ethylhexyl group; A cyclic alkyl group and the like can be mentioned, and a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms is preferred. The aralkyl group for R ² and R ³ includes, for example, a benzyl group, a phenethyl group and the like, preferably an aralkyl group having 7 to 20 carbon atoms. Examples of the aryl group for R ² and R ³ include phenyl group, tolyl group, xylyl group and the like, preferably an aryl group having 6 to 20 carbon atoms. Examples of alkenyl groups for R ² and R ³ include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group and 5-hexenyl group; iso-butenyl group, 5-methyl-3-pentenyl group and the like. branched alkenyl groups; cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group, preferably alkenyl groups having 2 to 10 carbon atoms.

Specific examples of the alkoxy silicon represented by the above formula (iv) include cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diiso-propyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane. , phenyltrimethoxysilane, diphenyldimethoxysilane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, iso-butyltriethoxysilane, vinyltriethoxysilane, sec-butyl triethoxysilane, cyclohexyltriethoxysilane, cyclopentyltriethoxysilane and the like.

The hydrocarbyl group for R ⁴ in the above formulas (v) and (vi) includes an alkyl group, an alkenyl group, and the like, and the alkyl group for R ⁴ includes a methyl group, an ethyl group, an n-propyl group, an -linear alkyl groups such as butyl, n-pentyl and n-hexyl groups; branched alkyl groups such as iso-propyl, iso-butyl, tert-butyl, iso-pentyl and neopentyl; Cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group can be mentioned, and straight-chain alkyl groups having 1 to 6 carbon atoms are preferred. Examples of alkenyl groups for R ⁴ include linear alkenyl groups such as vinyl, allyl, 3-butenyl and 5-hexenyl groups; branched alkenyl groups such as iso-butenyl and 5-methyl-3-pentenyl groups. Group: cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group, preferably linear alkenyl groups having 2 to 6 carbon atoms, and particularly preferably methyl or ethyl groups.

Examples of hydrocarbyl groups for R ⁵ and R ⁶ in the above formula (v) include alkyl groups and alkenyl groups, and examples of alkyl groups for R ⁵ and R ⁶ include methyl group, ethyl group, Linear alkyl groups such as n-propyl group, n-butyl group, n-pentyl group, n-hexyl group; iso-propyl group, iso-butyl group, tert-butyl group, iso-pentyl group, neopentyl group, etc. branched alkyl groups; cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups, preferably linear alkyl groups having 1 to 6 carbon atoms. Alkenyl groups for R ⁵ and R ⁶ include linear alkenyl groups such as vinyl, allyl, 3-butenyl and 5-hexenyl; branched alkenyl groups such as iso-butenyl and 5-methyl-3-pentenyl. cyclic alkenyl groups; cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group, preferably linear alkenyl groups having 2 to 6 carbon atoms, particularly preferably methyl or ethyl groups; be.

Specific examples of the alkoxy silicon represented by the above formula (v) include dimethylaminotrimethoxysilane, diethylaminotrimethoxysilane, di-n-propylaminotrimethoxysilane, dimethylaminotriethoxysilane, diethylaminotriethoxysilane. , di-n-propylaminotriethoxysilane, methylethylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, tert-butylaminotriethoxysilane, diiso-propylaminotriethoxysilane, methyl iso-propylamino triethoxysilane and the like.

Examples of the cyclic amino group for NR ⁷ in the above formula (vi) include perhydroquinolino group, perhydroisoquinolino group, 1,2,3,4-tetrahydroquinolino group, 1,2,3,4- A tetrahydroisoquinolino group, an octamethyleneimino group, and the like can be mentioned.

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, octamethyleneiminotriethoxysilane and the like.

The external electron donor ether is preferably a cyclic ether compound. The cyclic ether compound is a heterocyclic compound having at least one —C—O—C— bond in the ring structure, preferably at least one —C—O—C—O—C— A cyclic ether compound having a bond, more preferably 1,3-dioxolane or 1,3-dioxane.

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

The amount of the external electron donor to be used is preferably 0.0001 to 1000 μmol, more preferably 0.001 to 500 μmol, still more preferably 0.01 to 150 μmol, per 1 mg of the solid catalyst component for olefin polymerization. be.

According to the olefin polymerization catalyst described above, when an olefin is polymerized using the catalyst, a polymer having relatively high stereoregularity can be obtained.

<Olefin polymer>
An olefin polymer can be obtained by polymerizing an olefin in the presence of the olefin polymerization catalyst.

Olefins include, for example, 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; 3-methyl-1-butene, 3- Branched chain monoolefins such as methyl-1-pentene and 4-methyl-1-pentene; cyclic monoolefins such as vinylcyclohexane; and combinations of two or more thereof. Among them, it is preferable to use ethylene or propylene alone, or it is preferable to use a plurality of kinds of olefins containing ethylene or propylene as a main component. The above combination of multiple types of olefins may include combinations of two or more types of olefins, and may include combinations of compounds having multiple unsaturated bonds, such as conjugated dienes and non-conjugated dienes, with olefins. .

The olefin polymer is preferably ethylene homopolymer, propylene homopolymer, 1-butene homopolymer, 1-pentene homopolymer, 1-hexene homopolymer, ethylene-propylene copolymer, ethylene-1-butene Copolymer, ethylene-1-hexene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer It is a polymer or a polymer obtained by multistage polymerization of these.

In the production of the above olefin polymer, the following steps are preferably carried out when forming the olefin polymerization catalyst.

(i) In the presence of a solid catalyst component for olefin polymerization and an organoaluminum compound, a small amount of olefin is polymerized to produce a catalyst component (hereinafter also referred to as prepolymerization catalyst component) whose surface is covered with the olefin polymer. The process of making
(ii) contacting the prepolymerization 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 during olefin polymerization using an olefin polymerization catalyst (hereinafter also referred to as "main polymerization"). may Chain transfer agents such as hydrogen may also be used to control the molecular weight of the olefin polymer produced in step (i), and external electron donors may also be used.

The polymerization in step (i) (hereinafter also referred to as “prepolymerization”) preferably uses an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, etc. Slurry polymerization using a solvent may be used.

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

The amount of olefin to be prepolymerized is preferably 0.01 g to 1000 g, more preferably 0.05 g to 500 g, particularly preferably 0.1 g to 200 g per 1 g of the solid catalyst component for olefin polymerization used in step (i). is.

The slurry concentration of the solid catalyst component for olefin polymerization in the slurry polymerization of the 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.

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 in the prepolymerization is preferably 0.01 MPa to 2 MPa, more preferably 0.1 MPa to 1 MPa. do not have. The prepolymerization time is preferably 2 minutes to 15 hours.

The following methods (1) and (2) can be exemplified as methods for supplying the solid catalyst component for olefin polymerization, the organoaluminum compound and the olefin to the prepolymerization tank in the prepolymerization.

(1) A method of supplying a solid catalyst component for olefin polymerization and an organoaluminum compound to a preliminary polymerization tank, and then supplying an olefin to the preliminary polymerization tank.
(2) A method in which the solid catalyst component for olefin polymerization and the olefin are supplied to the prepolymerization tank, and then the organoaluminum compound is supplied to the prepolymerization tank.

In the prepolymerization, the following methods (1) and (2) can be exemplified as the method of supplying the olefin to the prepolymerization tank.

(1) A method of sequentially supplying olefins to the prepolymerization tank so as to maintain the pressure in the prepolymerization tank at a predetermined level.
(2) A method in which a predetermined amount of olefin is supplied all at once to a prepolymerization tank.

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. The amount of the external electron donor used in prepolymerization is preferably 0.003 mol to 5 mol, more preferably 0.005 mol to 3 mol, particularly preferably 0.01 mol to 2 mol, per 1 mol of the organoaluminum compound.

The following methods (1) and (2) can be exemplified as the method of supplying the external electron donor to the prepolymerization tank in the prepolymerization.

(1) A method of supplying an external electron donor alone to a prepolymerization tank.
(2) A method of supplying a contact mixture of an external electron donor and an organoaluminum compound to a prepolymerization tank.

When performing the above step (i) and step (ii), the amount of the organoaluminum compound used in the main polymerization is preferably 1 mol to 1000 mol, particularly preferably 5 mol, per 1 mol of titanium atom in the solid catalyst component for olefin polymerization. ~600 mol.

When an external electron donor is used in the polymerization, the amount of the external electron donor used is preferably 0.1 mol to 2000 mol, more preferably 0.3 mol, per 1 mol of titanium atom contained in the solid catalyst component for olefin polymerization. to 1000 mol, particularly preferably 0.5 mol to 800 mol. Further, when an external electron donor is used in the polymerization, the amount of the external electron donor to be used is preferably 0.001 mol to 5 mol, more preferably 0.005 mol to 3 mol, particularly preferably 0, per 1 mol of the organoaluminum compound. 0.01 mol to 1 mol.

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 is preferably normal pressure to 10 MPa, more preferably about 200 kPa to 5 MPa, from the industrial and economical point of view. The polymerization may be batch or continuous, and the polymerization method may be a slurry polymerization method or a solution polymerization method using an inert hydrocarbon such as propane, butane, isobutane, pentane, hexane, heptane, or octane as a solvent, or a liquid state at the polymerization temperature. A bulk polymerization method using an olefin as a medium and a gas phase polymerization method can be exemplified.

A chain transfer agent (for example, hydrogen, alkyl zinc such as dimethyl zinc, diethyl zinc, etc.) may be used to adjust the molecular weight of the polymer obtained by this polymerization.

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, stereoregularity (specifically, isotactic stereo regularity) can be obtained.

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

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

<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 has other configurations in common. Therefore, the description of the common configuration will not be repeated.

In the method for producing a solid catalyst component for olefin polymerization according to the second embodiment, a magnesium compound and A step of reacting with a titanium halide compound is provided. As a result, it is possible to suppress the deterioration of the polymerization activity due to the application of heat to the obtained 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 during the step (XI) below. The total calorific value can be determined by multiplying the heat generation rate by the heat generation time, and specifically, it can be determined by the method described in [Examples] below. In addition, the total calorific value can be adjusted by the efficiency of converting the magnesium compound to magnesium halide. Specifically, in the following step (XI), at least one of (a) to (c) below is adjusted. By doing so, the conversion efficiency can be improved.

(a) Raise the reaction temperature.
(b) increasing the feed rate of the titanium halide compound;
(c) increasing the concentration of the halogenated titanium compound and/or magnesium compound in the solvent;

Further, in the method for producing a solid catalyst component for olefin polymerization according to the second embodiment, similarly to the step (I) in the first embodiment, a titanium halide compound is supplied to a magnesium compound mixture containing a magnesium compound and a solvent. to obtain a slurry containing the solid product (XI). In step (XI), similarly to step (I) in the first embodiment, the supply rate of the titanium halide compound to the magnesium compound is kept at a predetermined rate until a predetermined amount of the titanium halide compound is supplied to the magnesium compound. A step of maintaining the supply speed (first supply step) is provided. In the second embodiment, the first supply step preferably increases the supply rate of the titanium halide compound to 1 mol of the magnesium compound until at least 0.5 mol of the titanium halide compound is supplied to 1 mol of the magnesium compound, preferably 0.005 mol/mol. min to 3.8 mol/min, more preferably 0.008 mol/min to 3.8 mol/min.

Further, in the second embodiment, step (XI) is similar to step (I) in the first embodiment, after supplying a predetermined amount of the titanium halide compound to the magnesium compound (after the first supply step), A step of maintaining the supply rate of the titanium halide compound with respect to the magnesium compound at a predetermined supply rate (second supply step) may be provided. In the second embodiment, the second supply step supplies at least 0.5 mol of the titanium halide compound to the magnesium compound (that is, after the first supply step), and then supplies the titanium halide compound to 1 mol of the magnesium compound. The rate is preferably maintained between 1.0 mol/min and 5.0 mol/min, more preferably between 1.0 mol/min and 4.8 mol/min, even more preferably between 2.0 mol/min and 4.0 mol/min. As a result, after at least 0.5 mol of the titanium halide compound is supplied to the magnesium compound, the supply rate of the titanium halide compound increases, so that the titanium halide compound can be rapidly supplied.

Further, in the method for producing a solid catalyst component for olefin polymerization according to the second embodiment, the step ( It is preferred to have a step (XII) of supplying an internal electron donor to the slurry containing the solid product obtained in XI).

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 in the first embodiment. The magnesium compound used in the second embodiment is preferably a compound obtained by reacting magnesium dialkoxide and a silicon halide compound. Silicon halides include 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, X represents a chlorine atom, a bromine or an iodine atom), and the like. Further, the titanium halide compound used in the second embodiment is preferably titanium tetrahalide. Tetrahalogenated titanium includes tetrachlorotitanium, tetraiodotitanium, tetrabromotitanium, and the like. Furthermore, the internal electron donor used in the second embodiment is preferably tetrahydrofuran.

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

The solid catalyst component for olefin polymerization produced by the above-described production method is mixed with an organoaluminum compound (preferably an organoaluminum compound and an external electron donor) to obtain an olefin polymerization catalyst as in the first embodiment. can be manufactured. That is, in the method for producing an olefin polymerization catalyst according to the second embodiment, as in the first embodiment, a solid catalyst component for olefin polymerization and an organoaluminum compound (preferably an organoaluminum compound and an external electron donor) are prepared. A mixing step of mixing is provided. The organoaluminum compound and the 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 in the first embodiment.

Further, similarly to the first embodiment, an olefin polymer can be obtained by polymerizing an olefin in the presence of an olefin polymerization catalyst produced by the production method described above. That is, the method for producing an olefin polymer according to the second embodiment polymerizes an olefin in the presence of the above catalyst for olefin polymerization. Examples of the olefin used in the method for producing an olefin polymer according to the second embodiment include the same olefins as in the first embodiment.

Hereinafter, the first invention will be described more specifically using examples and comparative examples. The first invention is not limited to the following examples.

[Calculation of heat release rate]
The heat release rate (Q [W]) during the reaction between the magnesium compound and the titanium halogen compound depends on the temperature difference (ΔT [°C]) between the coolant at the jacket inlet and the jacket outlet of the reaction vessel, and the coolant flow rate (F [ ^m3 /s]), and the specific heat of the refrigerant (Cp [J/m ³ ·°C]), it was calculated by the following formula (2). The maximum heat release rate was defined as the largest average value of the heat release rate for every 10 minutes. The jacket of the reaction vessel accommodates the reaction vessel and is configured to allow the coolant to flow between it and the reaction vessel. and an outlet through which the refrigerant flows.

Q=Cp×F×ΔT (2)

[Composition analysis of solid catalyst component for olefin polymerization]
(1) Titanium Atom Content About 20 mg of the solid catalyst component for olefin polymerization was decomposed with about 30 mL of 2N dilute sulfuric acid. After that, 3 mL of excess 3% by mass hydrogen peroxide solution was added thereto. Then, the characteristic absorption at 410 nm of the obtained liquid sample was measured by a UV-visible spectrophotometer V-650 manufactured by JASCO Corporation in accordance with the standard JIS K0115: 2004, and titanium atoms based on a separately prepared calibration curve. was determined.

(2) Alkoxy Group Content About 2 g of the solid catalyst component for olefin polymerization was decomposed with 100 mL of water. After that, the amount of alcohol corresponding to the alkoxy group in the obtained liquid sample was determined using the gas chromatography internal standard method according to standard JIS K0114:2012, and the obtained result was converted to the alkoxy group content.

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

(4) Median particle size (D50) of solid catalyst component for olefin polymerization and cumulative percentage of components with a particle size of 10 µm or less According to the standard ISO13320:2009, the median particle size (D50) and the cumulative percentage of components with a particle size of 10 µm or less were measured by laser diffraction.・Analyzed by scattering method. A laser diffraction particle size distribution measuring device ("Mastersizer 3000" manufactured by Malvern) was used as a measuring device, and the refractive index was set to 1.49 for toluene and 1.53-0.1i for the solid catalyst component for olefin polymerization. A toluene solvent from which moisture had been previously removed with alumina or the like was put into a dispersing device (Hydro MV) whose opening was sealed with nitrogen, and the inside of the circulation system including the measurement cell was filled with the solvent. The stirring speed was set to 2,000 rpm, and while the solvent in the measurement cell was circulated without ultrasonic dispersion treatment, the powder sample was added so that the scattering intensity was 3 to 10%, and the particle size was measured. The median particle size (D50) and the cumulative percentage of components with a particle size of 10 µm or less were determined from the obtained particle size volume standard distribution diagram (chart). Samples were handled to avoid contact with air and moisture and were not pretreated.

[Analysis of polymer]
(1) Polymerization Activity The mass of the obtained polymer 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).

(2) Xylene soluble component amount (CXS: unit = mass%)
The amount of 20° C. xylene-soluble components (hereinafter abbreviated as CXS) of the olefin polymer was measured as follows.
After dissolving 1 g of the polymer in 200 mL of boiling xylene, the solution was gradually cooled to 50° C., then immersed in ice water, cooled to 20° C. with stirring, and left at 20° C. for 3 hours. The precipitated polymer was separated by filtration, and the mass percentage of the polymer remaining in the filtrate was defined as CXS.

(3) Intrinsic viscosity ([η]: unit = dL/g)
The intrinsic viscosity (hereinafter abbreviated as [η]) of the olefin polymer was measured as follows.
A Ubbelohde viscometer was used to measure the reduced viscosity of three samples with concentrations of 0.1 g/dL, 0.2 g/dL, and 0.5 g/dL. The intrinsic viscosity was obtained by the calculation method described in the reference document "Polymer Solution, Polymer Experiments 11" (published by Kyoritsu Shuppan Co., Ltd., 1982), Item 491. That is, the limiting viscosity was determined by an extrapolation method in which the reduced viscosity was plotted against the concentration and the concentration was extrapolated to zero. Measurements were carried out at a temperature of 135° C. using tetralin as a solvent.

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

(2) Polymerization of Propylene After thoroughly drying an autoclave with an internal volume of 3 L and equipped with a stirrer, the interior was evacuated. After that, 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 autoclaved. Added to 780 g of propylene and 0.2 MPa of hydrogen were then 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 completion of the polymerization reaction, unreacted monomers were purged to obtain a propylene polymer. The amount of polymer produced per unit amount of catalyst (polymerization activity) was 50,600 g-polymer/g-solid catalyst component. This polymer had a CXS of 0.58 wt % and a [η] of 1.29 dL/g. The analysis results of the obtained polymer are shown in Table 2 below.

[Example 2]
(1) Synthesis of Solid Catalyst Component for Olefin Polymerization The gas in a reactor equipped with a stirrer was replaced with nitrogen gas. Next, toluene (52.8 L) and magnesium diethoxide (11 kg) were added into the reactor and stirred to obtain a suspension. After that, titanium tetrachloride (11 L) was charged into the reaction vessel over 2 hours while stirring the temperature in the reaction vessel at 0° C. or lower (first supply step). The supply rate (initial supply rate) of titanium tetrachloride, the amount of titanium tetrachloride supplied (initial supply amount), and the maximum heat generation 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 supply rate of titanium tetrachloride in the second supply step was 0.043 mol/min per 1 mol of magnesium diethoxide. After that, the temperature in the reaction vessel was lowered to 2° C. or lower and held for 120 minutes.
Next, ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.77 kg) was added into the reaction vessel while maintaining the temperature in the vessel at 2° C. or lower. After that, the temperature in the reaction vessel was lowered to 10° C. or less and held for 120 minutes. Next, toluene (14.3 L) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 60° C., and ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (4.0 kg) was added. After that, the temperature in the reaction vessel was set to 110° C. and the mixture was stirred for 3 hours. After solid-liquid separation of the resulting reaction mixture was carried out at 110°C, the solid was washed with 83 L of toluene at 95°C three times. Then, toluene (34 L) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 60° C., and titanium tetrachloride (22 L) and ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.95 kg) were added. added. Next, the temperature inside the reaction vessel was set to 110° C. and the mixture was stirred for 30 minutes. The obtained reaction mixture was subjected to solid-liquid separation at 110° C., and the solid was washed with 83 L of toluene at 60° C. three times, then with 83 L of hexane three times, and then dried to obtain a solid for olefin polymerization. A catalyst component (10.6 kg) was obtained. This solid catalyst component for olefin polymerization had a titanium atom content of 2.41% by mass, an ethoxy group content of 0.64% by mass, and an internal electron donor content of 12.36% by mass. . The median particle diameter of this solid catalyst component for olefin polymerization was 54.7 μm as determined by the laser diffraction/scattering method, and the cumulative percentage of components with particle diameters of 10 μm or less was 4.0%. The analysis results of the solid catalyst component for olefin polymerization are shown in Table 1 below.

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

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

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

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

Hereinafter, the second invention will be described more specifically using examples and comparative examples. The second invention is not limited to the following examples.

[Calculation of heat release rate]
The heat release rate (Q [kW]) during the reaction between the magnesium compound and the titanium halogen compound depends on the temperature difference (ΔT [°C]) between the internal temperature of the reaction vessel and the coolant in the jacket, and the heat transfer area (S [m ² ] ) and the overall heat transfer coefficient (U [kJ/m ² ·°C · s]), it was calculated by the following equation (11). The maximum heat generation rate was defined as the maximum heat generation rate per second. The heat transfer area means the contact area between the reactants and the reactor, and was calculated from the volume of the reactants and the shape of the reactor. Further, the general heat transfer coefficient was calculated as U=0.05 kJ/m ² ·°C·s according to the following formula (X) on page 104 of "Applied Chemistry Series 4: Basics of Chemical Engineering, 2006".

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 reactant [W/m ² /K]
・L: Jacket thickness [m]
・k: Heat transfer coefficient of jacket [W/m/K]

[Exothermic time measurement]
Measure the temperature difference between the inner temperature of the reaction vessel and the cooling medium in the jacket when the reaction is not performed. t[s]).

[Total calorific value calculation]
The total calorific value (Q') was calculated by the following formula (12). Q is the exotherm rate described above.

Q′=Q×t (12)

[Polymerization Activity of Olefin Polymerization Catalyst]
The amount of olefin polymer (ethylene-based 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 calculated by calculating the amount of olefin polymer produced per unit amount of the solid catalyst component for olefin polymerization stored (heat-treated) in a thermostat at 70°C for 24 hours as the polymerization activity. , and the rate of decrease from the polymerization activity of those not subjected to heat treatment.

[Bulk Density of Olefin Polymer]
The bulk density of the olefin polymer was measured according to JIS K-6721 (1966) using a bulk specific gravity meter (K6721 manufactured by Tsutsui Rikagaku Kiki).

[Example 11]
-Synthesis of Solid Catalyst Component 11 for Olefin Polymerization The gas in a reactor equipped with a stirrer was replaced with nitrogen gas. Next, toluene (120 mL) and magnesium diethoxide (33 g) were added into the reactor and stirred to obtain a suspension. Then, silicon tetrachloride (10 mL) was added into the reaction vessel over 5 seconds while stirring the temperature inside the reaction vessel at 40°C. Thereafter, the temperature in the reaction vessel was maintained at 40° C. and stirred for 3 hours (first chlorination step, exothermic reaction). Toluene (100 mL) was added to the obtained reaction mixture while maintaining the temperature at 40° C., and the mixture was stirred for 5 minutes and then solid-liquid separated.
Toluene (129 mL) was added into the reaction vessel containing the resulting solid. Then, the temperature in the reaction vessel was adjusted to 45° C., and titanium tetrachloride (25 mL) was added. After completion of dropping, the temperature was maintained at 45° C. and stirred for 20 minutes (first titanium supply step, exothermic reaction). Feed rate of titanium tetrachloride in the step of supplying titanium tetrachloride, feed amount of titanium tetrachloride, internal temperature of reactor at the time of heat generation, maximum temperature difference (ΔT = internal temperature of reactor - temperature of jacket refrigerant), heat generation The times and total heat release are shown in Table 3 below. After that, the temperature inside the reaction vessel was set to 110° C. and the mixture was stirred for 30 minutes. After the resulting reaction mixture was subjected to solid-liquid separation at 110°C, the obtained solid was washed with toluene (129 mL) at 110°C four times.
After that, toluene (129 mL) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 50° C., and tetrahydrofuran (12 mL) was added. Next, the temperature of the jacket was set to 50° C. and the mixture was stirred for 1 hour. After solid-liquid separation of the obtained reaction mixture at 50° C., the obtained 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).

-Synthesis of ethylene-butene copolymer 11 After sufficiently drying an autoclave with an internal volume of 3 L and equipped with a stirrer, the interior was evacuated. 0.12 MPa of hydrogen, 100 g of butene and 652 g of butane were then added to the autoclave. The temperature of the autoclave is raised to 70° C., 0.6 MPa of ethylene, 3 mmol of triisobutylaluminum (organoaluminum compound) and about 60 mg of the solid catalyst component for olefin polymerization 11 are added to the autoclave, and then the pressure in the system becomes constant. After supplying ethylene as above, ethylene and butene were copolymerized at 70° C. for 2 hours. After completion of the polymerization reaction, unreacted monomers were purged to obtain an ethylene-butene copolymer 11. Then, 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.

[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 into the reactor and stirred to obtain a suspension. Then, silicon tetrachloride (10 mL) was added into the reaction vessel over 5 seconds while stirring the temperature inside the reaction vessel at 40°C. Thereafter, the temperature in the reaction vessel was maintained at 40° C. and stirred for 3 hours (first chlorination step, exothermic reaction). The resulting reaction mixture was maintained at 40° C., toluene (100 mL) was added, and the mixture was stirred for 5 minutes, followed by solid-liquid separation.
Toluene (129 mL) was added into the reaction vessel containing the resulting solid. Then, the temperature in the reaction vessel was adjusted to 45° C., titanium tetrachloride (10 mL) was added, and after the dropwise addition was completed, the temperature was maintained at 45° C. and stirred for 20 minutes (first titanium supply step, exothermic reaction). Feed rate of titanium tetrachloride in the step of supplying titanium tetrachloride, feed amount of titanium tetrachloride, internal temperature of reactor at the time of heat generation, maximum temperature difference (ΔT = internal temperature of reactor - temperature of jacket refrigerant), heat generation The times and total heat release are shown in Table 3 below. After that, the temperature inside the reaction vessel was set to 110° C. and the mixture was stirred for 30 minutes. After the resulting reaction mixture was subjected to solid-liquid separation at 110°C, the obtained solid was washed once with toluene (129 mL) at 110°C.
Then, toluene (129 mL) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 40° C., and titanium tetrachloride (15 mL, 90 mL/min) was added (second titanium supply step, ΔT = 0, no fever). After that, the temperature in the reaction vessel was set to 110° C. and the mixture was stirred for 60 minutes. After the resulting reaction mixture was subjected to solid-liquid separation at 110°C, the obtained solid was washed with toluene (129 mL) at 110°C four times.
After that, toluene (129 mL) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 50° C., and tetrahydrofuran (12 mL) was added. Next, the temperature of the jacket was set to 50° C. and the mixture was stirred for 1 hour. After solid-liquid separation of the obtained reaction mixture at 50° C., the obtained solid was washed once with toluene (129 mL) at 50° C., then washed twice with hexane (129 mL), and then vacuum-dried. to obtain solid catalyst component 12 (39 g) for olefin polymerization.

-Synthesis of ethylene-butene copolymer 12 After thoroughly drying an autoclave with an internal volume of 3 L and equipped with a stirrer, the interior was evacuated. 0.12 MPa of hydrogen, 100 g of butene and 652 g of butane were then added to the autoclave. The temperature of the autoclave was raised to 70° C., and 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (organoaluminum compound) and about 20 mg of solid catalyst component for olefin polymerization 12 were added to the autoclave. Then, after supplying ethylene so that the pressure in the system was kept constant, ethylene and butene were copolymerized at 70° C. for 2 hours. After completion of the polymerization reaction, unreacted monomers were purged to obtain an ethylene-butene copolymer 12. Then, 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.

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

-Synthesis of ethylene-butene copolymer 13 After thoroughly drying an autoclave with an internal volume of 3 L and equipped with a stirrer, the interior was evacuated. 0.12 MPa of hydrogen, 100 g of butene and 652 g of butane were then added to the autoclave. The temperature of the autoclave was raised to 70° C., and 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (organoaluminum compound) and about 20 mg of the solid catalyst component for olefin polymerization 13 were added to the autoclave. Then, after supplying ethylene so that the pressure in the system was kept constant, ethylene and butene were copolymerized at 70° C. for 2 hours. After completion of the polymerization reaction, unreacted monomers were purged to obtain an ethylene-butene copolymer 13. Then, 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.

[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 into the reactor and stirred to obtain a suspension. Then, silicon tetrachloride (10 mL) was added into the reaction vessel over 5 seconds while stirring the temperature inside the reaction vessel at 40°C. Thereafter, the temperature in the reaction vessel was maintained at 40° C. and stirred for 3 hours (first chlorination step, exothermic reaction).
Thereafter, while maintaining the temperature in the reaction vessel at 40° C., titanium tetrachloride (10 mL) was added and stirred for 10 minutes (primary titanium supply step, exothermic reaction). Feed rate of titanium tetrachloride in the step of supplying titanium tetrachloride, feed amount of titanium tetrachloride, internal temperature of reactor at the time of heat generation, maximum temperature difference (ΔT = internal temperature of reactor - temperature of jacket refrigerant), heat generation The times and total heat release are shown in Table 3 below. After that, the temperature in the reaction vessel was set to 105° C. and the mixture was stirred for 60 minutes. After the resulting reaction mixture was subjected to solid-liquid separation at 105°C, the obtained solid was washed once with toluene (129 mL) at 105°C.
After that, toluene (129 mL) was added into the reaction vessel, the temperature inside the reaction vessel was set to 40° C., and titanium tetrachloride (10 mL, 60 mL/min) was added (second titanium supply step, ΔT = 0, no fever). After that, the temperature inside the reaction vessel was set to 110° C. and the mixture was stirred for 120 minutes. After the resulting reaction mixture was subjected to solid-liquid separation at 110°C, the resulting solid was washed with toluene (129 mL) at 110°C three times.
After that, toluene (129 mL) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 50° C., and tetrahydrofuran (6 mL) was added. Next, the temperature of the jacket was set to 50° C. and stirred for 30 minutes, and then set to 70° C. and stirred for 30 minutes. After solid-liquid separation of the obtained reaction mixture at 70° C., the obtained solid was washed twice with toluene (129 mL) at 70° C., then washed twice with hexane (129 mL), and then vacuum-dried. to obtain solid catalyst component 14 (36 g) for olefin polymerization.

-Synthesis of ethylene-butene copolymer 14 After thoroughly drying an autoclave with an internal volume of 3 L and equipped with a stirrer, the interior was evacuated. 0.12 MPa of hydrogen, 100 g of butene and 652 g of butane were then added to the autoclave. The temperature of the autoclave is raised to 70° C., 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (organoaluminum compound) and about 20 mg of the solid catalyst component for olefin polymerization 14 are added to the autoclave, and then the pressure in the system becomes constant. After supplying ethylene as above, ethylene and butene were copolymerized at 70° C. for 2 hours. After completion of the polymerization reaction, unreacted monomers were purged to obtain an ethylene-butene copolymer 14. Then, 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.

[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 into the reactor and stirred to obtain a suspension. Then, silicon tetrachloride (14 mL) was added into the reaction vessel over 5 seconds while stirring the temperature in the reaction vessel at 30°C. Thereafter, the temperature in the reaction vessel was maintained at 30° C. and stirred for 2 hours (first chlorination step, exothermic reaction). After that, the temperature in the reaction vessel was set to 105° C. and the mixture was stirred for 60 minutes. After the resulting reaction mixture was maintained at 105° C. and the supernatant was removed, the resulting solid was washed once with toluene (216 mL) at 105° C. (washing off the supernatant).
After that, the temperature in the reaction vessel was adjusted to 35° C., and titanium tetrachloride (15 mL) was added (first titanium supply step, exothermic reaction). Feed rate of titanium tetrachloride in the step of supplying titanium tetrachloride, feed amount of titanium tetrachloride, internal temperature of reactor at the time of heat generation, maximum temperature difference (ΔT = internal temperature of reactor - temperature of jacket refrigerant), heat generation The times and total heat release are shown in Table 3 below. After that, the temperature inside the reaction vessel was set to 110° C. and the mixture was stirred for 120 minutes. After solid-liquid separation of the obtained reaction mixture at 110°C, the obtained solid was washed with toluene (129 mL) at 110°C four times and then with hexane (129 mL) at 30°C twice.
Thereafter, hexane (129 mL) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 30° C., and tetrahydrofuran (12 mL) was added. After that, the temperature in the reaction vessel was set to 30° C. and the mixture was stirred for 30 minutes. After solid-liquid separation of the obtained reaction mixture was carried out at 30° C., the obtained solid was washed twice with hexane (129 mL) and then vacuum-dried to obtain a solid catalyst component for olefin polymerization C11 (40 g).

-Synthesis of ethylene-butene copolymer C11 After thoroughly drying an autoclave with an internal volume of 3 L and equipped with a stirrer, the interior was evacuated. 0.12 MPa of hydrogen, 100 g of butene and 652 g of butane were then added to the autoclave. The temperature of the autoclave was raised to 70° C., 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (organoaluminum compound), and about 20 mg of solid catalyst component C11 for olefin polymerization were added to the autoclave, and then the pressure in the system became constant. After supplying ethylene as above, ethylene and butene were copolymerized at 70° C. for 2 hours. After completion of the polymerization reaction, unreacted monomers were purged to obtain ethylene-butene copolymer C11. Then, 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.

[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 into the reactor and stirred to obtain a suspension. Then, silicon tetrachloride (14 mL) was added into the reaction vessel over 5 seconds while stirring the temperature in the reaction vessel at 30°C. After that, the temperature in the reaction vessel was set to 30° C. and the mixture was stirred for 3 hours (first chlorination step, exothermic reaction). After that, the temperature in the reaction vessel was set to 105° C. and the mixture was stirred for 60 minutes. Toluene (216 mL) was added to the resulting reaction mixture, which was maintained at 105° C., stirred, and the supernatant was removed. After that, the obtained solid was washed once with toluene (126 mL) at 105° C. (washing removal of the supernatant).
After that, the temperature in the reaction vessel was adjusted to 35° C., and titanium tetrachloride (20 mL) was added (primary titanium supply step, exothermic reaction). Feed rate of titanium tetrachloride in the step of supplying titanium tetrachloride, feed amount of titanium tetrachloride, internal temperature of reactor at the time of heat generation, maximum temperature difference (ΔT = internal temperature of reactor - temperature of jacket refrigerant), heat generation The times and total heat release are shown in Table 3 below. After that, the temperature inside the reaction vessel was set to 110° C. and the mixture was stirred for 120 minutes. After solid-liquid separation of the obtained reaction mixture at 110°C, the obtained solid was washed with toluene (129 mL) at 110°C four times and then with hexane (129 mL) at 30°C twice.
Thereafter, hexane (129 mL) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 30° C., and tetrahydrofuran (12 mL) was added. After that, the temperature in the reaction vessel was set to 30° C. and the mixture was stirred for 30 minutes. After solid-liquid separation of the obtained reaction mixture was carried out at 30° C., the obtained solid was washed twice with hexane (129 mL) and then vacuum-dried to obtain a solid catalyst component for olefin polymerization C12 (41 g).

-Synthesis of ethylene-butene copolymer C12 After thoroughly drying an autoclave with an internal volume of 3 L and equipped with a stirrer, the interior was evacuated. 0.12 MPa of hydrogen, 100 g of butene and 652 g of butane were then added to the autoclave. The temperature of the autoclave is raised to 70° C., 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (organoaluminum compound) and about 20 mg of solid catalyst component C12 for olefin polymerization are added to the autoclave, and then the pressure in the system becomes constant. After supplying ethylene as above, ethylene and butene were copolymerized at 70° C. for 2 hours. After completion of the polymerization reaction, unreacted monomers were purged to obtain ethylene-butene copolymer C12. Then, 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.

[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 into the reactor and stirred to obtain a suspension. Then, silicon tetrachloride (10 mL) was added into the reaction vessel over 5 seconds while stirring the temperature inside the reaction vessel at 40°C. After that, the temperature in the reaction vessel was raised to 40° C. and the mixture was stirred for 3 hours (first chlorination step, exothermic reaction). After that, the temperature in the reaction vessel was set to 105° C. and the mixture was stirred for 60 minutes. Toluene (216 mL) was added while the resulting reaction mixture was maintained at 105° C., stirred, and the supernatant was removed. After that, the obtained solid was washed once with toluene (126 mL) at 105° C. (washing removal of the supernatant).
After that, the temperature in the reaction vessel was adjusted to 35° C., and titanium tetrachloride (15 mL) was added (first titanium supply step, exothermic reaction). Feed rate of titanium tetrachloride in the step of supplying titanium tetrachloride, amount of titanium tetrachloride fed, internal temperature of reactor during heat generation, maximum temperature difference (ΔT = internal temperature of reactor - coolant temperature of jacket), heat generation time and total calorific value are shown in Table 3 below. After that, the temperature inside the reaction vessel was set to 110° C. and the mixture was stirred for 120 minutes. After solid-liquid separation of the obtained reaction mixture at 110°C, the obtained solid was washed with toluene (129 mL) at 110°C four times and then with hexane (129 mL) at 30°C twice.
Thereafter, hexane (129 mL) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 30° C., and tetrahydrofuran (6 mL) was added. After that, the temperature in the reaction vessel was set to 30° C. and the mixture was stirred for 30 minutes. After the obtained reaction mixture was subjected to solid-liquid separation at 30° C., the obtained solid was washed twice with hexane (129 mL) and then vacuum-dried to obtain a solid catalyst component for olefin polymerization C13 (36 g).

-Synthesis of ethylene-butene copolymer C13 After thoroughly drying an autoclave with an internal volume of 3 L and equipped with a stirrer, the interior was evacuated. 0.12 MPa of hydrogen, 100 g of butene and 652 g of butane were then added to the autoclave. The temperature of the autoclave is raised to 70° C., 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (organoaluminum compound) and about 20 mg of solid catalyst component C13 for olefin polymerization are added to the autoclave, and then the pressure in the system becomes constant. After supplying ethylene as above, ethylene and butene were copolymerized at 70° C. for 2 hours. After completion of the polymerization reaction, unreacted monomers were purged to obtain ethylene-butene copolymer C13. Then, 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.

[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 into the reactor and stirred to obtain a suspension. Then, silicon tetrachloride (14 mL) was added into the reaction vessel over 5 seconds while stirring the temperature in the reaction vessel at 30°C. After that, the temperature in the reaction vessel was set to 30° C. and the mixture was stirred for 3 hours (first chlorination step, exothermic reaction). After that, the temperature in the reaction vessel was set to 105° C. and the mixture was stirred for 60 minutes. Toluene (216 mL) was added to the resulting reaction mixture, which was maintained at 105° C., stirred, and the supernatant was removed. After that, the obtained solid was washed once with toluene (126 mL) at 105° C. (washing removal of the supernatant).
After that, the temperature in the reaction vessel was adjusted to 35° C., and titanium tetrachloride (20 mL) was added (primary titanium supply step, exothermic reaction). Feed rate of titanium tetrachloride in the step of supplying titanium tetrachloride, feed amount of titanium tetrachloride, internal temperature of reactor at the time of heat generation, maximum temperature difference (ΔT = internal temperature of reactor - temperature of jacket refrigerant), heat generation The times and total heat release are shown in Table 3 below. After that, the temperature inside the reaction vessel was set to 110° C. and the mixture was stirred for 120 minutes. After solid-liquid separation of the obtained reaction mixture at 110°C, the obtained solid was washed with toluene (129 mL) at 110°C four times and then with hexane (129 mL) at 30°C twice.
Then, toluene (129 mL) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 40° C., and titanium tetrachloride (15 mL, 3 mL/min) was added (second titanium supply step, ΔT = 0, no fever). After that, the temperature in the reaction vessel was set to 110° C. and the mixture was stirred for 60 minutes. After the resulting reaction mixture was subjected to solid-liquid separation at 110°C, the obtained solid was washed with toluene (129 mL) at 110°C four times.
After that, toluene (129 mL) was added into the reaction vessel, the temperature inside the reaction vessel was adjusted to 30° C., and tetrahydrofuran (12 mL) was added. After that, the temperature in the reaction vessel was set to 30° C. and the mixture was stirred for 30 minutes. The obtained reaction mixture was subjected to solid-liquid separation at 30° C., and the obtained solid was washed once with toluene (129 mL) and then twice with hexane (129 mL), and dried in vacuo to obtain a solid for olefin polymerization. Catalyst component C14 (41 g) was obtained.

-Synthesis of ethylene-butene copolymer C14 After thoroughly drying an autoclave with an internal volume of 3 L and equipped with a stirrer, the interior was evacuated. 0.12 MPa of hydrogen, 100 g of butene and 652 g of butane were then added to the autoclave. The temperature of the autoclave is raised to 70° C., 0.6 MPa of ethylene, 1 mmol of triisobutylaluminum (organoaluminum compound) and about 20 mg of solid catalyst component C14 for olefin polymerization are added to the autoclave, and then the pressure in the system becomes constant. After supplying ethylene as above, ethylene and butene were copolymerized at 70° C. for 2 hours. After completion of the polymerization reaction, unreacted monomers were purged to obtain ethylene-butene copolymer C14. Then, 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.

<Summary>
From Tables 3 and 4, it can be seen that each example with a high total calorific value has a lower rate of decrease in polymerization activity than each comparative example. That is, as in the second invention, by providing a step of reacting the magnesium compound and the halogenated titanium compound so that the total calorific value per 1 mol of the titanium compound falls within a predetermined range, the solid catalyst component for olefin polymerization is heated. It is possible to suppress the decrease in polymerization activity due to the addition of. In addition, from Tables 3 and 4, it can be seen that in each example, the bulk density of the olefin polymer is 0.300 g/mL or more, and the rate of decrease in bulk density is small. That is, as in the second invention, by providing a step of reacting the magnesium compound and the halogenated titanium compound so that the total calorific value per 1 mol of the titanium compound falls within a predetermined range, the solid catalyst component for olefin polymerization is heated. is added, the decrease in bulk density of the resulting olefin polymer can be suppressed.

Claims (17)

A method for producing a solid catalyst component for olefin polymerization, comprising reacting a magnesium compound and a titanium halide compound to produce a solid catalyst component for olefin polymerization, comprising:
A step of reacting the magnesium compound and the titanium halide compound so that the maximum heat generation rate per 1 mol of the magnesium compound is 18 W or less,
A method for producing a solid catalyst component for olefin polymerization. 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 step (I) comprises a step of maintaining the supply rate of the titanium halide compound to 1 mol of the magnesium compound at 0.01 mol/min or less until at least 1 mol of the titanium halide compound is supplied to 1 mol of the magnesium compound.
The method for producing the solid catalyst component for olefin polymerization according to claim 1. The step (I) further comprises supplying at least 1 mol of the titanium halide compound to 1 mol of the magnesium compound, and then increasing the supply rate of the titanium halide compound to 1 mol of the magnesium compound to exceed 0.01 mol/min. ,
The method for producing the solid catalyst component for olefin polymerization according to claim 2. A step (II) of supplying an internal electron donor to the slurry obtained in the step (I);
4. The method for producing the solid catalyst component for olefin polymerization according to claim 2 or 3. the magnesium compound is a magnesium dialkoxide,
A method for producing the solid catalyst component for olefin polymerization according to any one of claims 1 to 4. the titanium halide compound is a titanium tetrahalide;
A method for producing the solid catalyst component for olefin polymerization according to any one of claims 1 to 5. A mixing step of mixing a 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 6 and an organoaluminum compound,
A method for producing an olefin polymerization catalyst. polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 7;
A method for producing an olefin polymer. A method for producing a solid catalyst component for olefin polymerization, comprising reacting a magnesium compound and a titanium halide compound to produce a solid catalyst component for olefin polymerization, comprising:
A method for producing a solid catalyst component for olefin polymerization, comprising a step of reacting a magnesium compound with a titanium halide compound such 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 mixture containing a magnesium compound and a solvent to obtain a slurry containing a solid product;
In step (XI), the supply rate of the titanium halide compound to 1 mol of the magnesium compound is 0.005 mol/min to 3.8 mol/min until at least 0.5 mol of the titanium halide compound is supplied to 1 mol of the magnesium compound. 10. The method for producing a solid catalyst component for olefin polymerization according to claim 9, comprising a step of maintaining at In the step (XI), after supplying at least 0.5 mol of the titanium halide compound to 1 mol of the magnesium compound, the supply rate of the titanium halide compound to 1 mol of the magnesium compound is set to 1.0 mol/min to 5.0 mol/min. 11. The method for producing a solid catalyst component for olefin polymerization according to claim 10, comprising a step of maintaining. 12. The method for producing a solid catalyst component for olefin polymerization according to claim 10 or 11, comprising step (XII) of supplying an internal electron donor to the slurry obtained in step (XI). 13. The method for producing a solid catalyst component for olefin polymerization according to claim 12, wherein the internal electron donor is tetrahydrofuran. 14. The method for producing a solid catalyst component for olefin polymerization according to any one of claims 9 to 13, wherein the magnesium compound is a compound obtained by reacting a magnesium dialkoxide and a silicon halide compound. The method for producing a solid catalyst component for olefin polymerization according to any one of claims 9 to 14, wherein the titanium halide compound is titanium tetrahalide. An olefin polymerization catalyst comprising a mixing step of mixing a 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 9 to 15 and an organoaluminum compound. Production method. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 16 .