JP6915618B2 - Method for producing solid catalyst component for olefin polymerization - Google Patents

Description

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

Conventionally, many solid catalyst components containing titanium atoms, magnesium atoms, halogen atoms and internal electron donors have been proposed as catalyst components for olefin polymerization.

For example, Patent Document 1 describes a solid catalyst component obtained by a method including a step of adding a suspension containing a magnesium compound and toluene to a solution containing a titanium compound and toluene.

Patent Document 2 describes a solid catalyst component obtained by a method including a step of adding a solution containing a magnesium compound and a solvent to a titanium compound.

Japanese Unexamined Patent Publication No. 2010-1420 Japanese Unexamined Patent Publication No. 2-289604

However, the method of polymerizing an olefin in the presence of a catalyst for olefin polymerization containing the solid catalyst components obtained in Patent Documents 1 and 2 is not yet satisfactory from the viewpoint of the stereoregularity of the obtained olefin polymer.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a solid catalyst component for olefin polymerization, which gives a polymer having high stereoregularity when an olefin is polymerized. Is.

The present invention provides the following.

[1] A method for producing a solid catalyst component for olefin polymerization, which comprises a titanium atom, a magnesium atom, a halogen atom and an internal electron donor.
A step (I) of contacting a titanium halide compound solution containing a titanium halide compound and a solvent with a magnesium compound to obtain a slurry containing a solid product.
In step (I), a method for producing a solid catalyst component for olefin polymerization, wherein the ratio (A / C) of A represented by the following formula (1) to C represented by the following formula (2) is 3 or less. ..
A = a / b (1)
(In the formula, a represents the volume (mL) of the titanium halide compound contained in the titanium halide compound solution, and b represents the volume (mL) of the solvent contained in the titanium halide compound solution.)
C = a / c (2)
(In the formula, a represents the volume (mL) of the titanium halide compound contained in the titanium halide compound solution, and c represents the volume (mL) of the solvent contained in the slurry containing the solid product.)
[2] The production method according to [1], wherein the magnesium compound is added to the titanium halide compound solution in the step (I).
[3] The internal electron donor is at least one compound selected from the group consisting of a monoester compound, a dicarboxylic acid ester compound, a diol diester compound, a β-alkoxy ester compound and a diether compound, [1] or [2]. ] The manufacturing method described in.
[4] The production method according to any one of [1] to [3], wherein the magnesium compound is magnesium dialkoxide.
[5] The production method according to any one of [1] to [4], further comprising a step (II) of adding an internal electron donor to a slurry containing a solid product.
[6] At least one internal electron donor selected from the group consisting of a monoester compound, an aliphatic dicarboxylic acid ester compound, a diol diester compound, a β-alkoxy ester compound and a diether compound, a titanium atom, a magnesium atom, and the like. Contains halogen atoms
A solid catalyst component for olefin polymerization that satisfies the following requirements (I) to (IV).
(I) The total pore volume measured by the mercury intrusion method according to the standard ISO15901-1: 2005 is 0.95 to 1.80 mL / g, and the specific surface area measured by the mercury intrusion method according to the standard ISO15901: 1: 2005. Is 60 to 170 m ² / g.
(II) In accordance with 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 the laser diffraction / scattering method shall be 6.5% or less.
(III) According to the standard ISO15472: 2001, among the peak components obtained by waveform-separating the peaks belonging to the 1s orbit of oxygen atoms obtained by X-ray photoelectron spectroscopy, the binding energy peaks in the range of 532 eV or more and 534 eV or less. The ratio (G / F) of the area (G) of the peak component having the peak top to the area (F) of the peak component having the peak in the range where the binding energy is 529 eV or more and less than 532 eV is 0.33 or less.
(IV) The titanium content is 1.50 to 3.40 wt%.
[7] The pores having a pore radius in the range of 30 to 700 nm with respect to the total volume (α) of the pores having a pore radius in the range of 5 to 30 nm measured by the mercury intrusion method according to the standard ISO15901-1: 2005. The solid catalyst component for olefin polymerization according to [6], wherein the ratio (β / α) of the total volume (β) is in the range of 0.45 to 3.0.
[8] The solid catalyst component for olefin polymerization according to [6] or [7], wherein the internal electron donor is a β-alkoxy ester compound.
[9] The solid catalyst component for olefin polymerization according to any one of [6] to [8], wherein the internal electron donor is ethyl 2-ethoxymethyl-3,3-dimethylbutanoate.
[10] An olefin polymerization catalyst containing the solid catalyst component for olefin polymerization according to any one of [6] to [9] and an organoaluminum compound.
[11] A method for producing an olefin polymer, which polymerizes an olefin in the presence of the catalyst for olefin polymerization according to [10].

According to the present invention, it is possible to produce a solid catalyst component for olefin polymerization that gives a polymer having high stereoregularity when the olefin is polymerized.

<Manufacturing method of solid catalyst component for olefin polymerization>
The production method of the present invention is a method for producing a solid catalyst component for olefin polymerization containing a titanium atom, a magnesium atom, a halogen atom and an internal electron donor.
A step (I) of contacting a titanium halide compound solution containing a titanium halide compound and a solvent with a magnesium compound to obtain a slurry containing a solid product.
In the step (I), the ratio (A / C) of A represented by the following formula (1) to C represented by the following formula (2) is 3 or less.
A = a / b (1)
(In the formula, a represents the volume (mL) of the titanium halide compound contained in the titanium halide compound solution, and b represents the volume (mL) of the solvent contained in the titanium halide compound solution.)
C = a / c (2)
(In the formula, a represents the volume (mL) of the titanium halide compound contained in the titanium halide compound solution, and c represents the volume (mL) of the solvent contained in the slurry containing the solid product.)

In the present specification, the "solid catalyst component for olefin polymerization" is a catalyst that exists as a solid content in at least toluene and becomes a catalyst for olefin polymerization by being combined with an auxiliary catalyst for olefin polymerization such as an organoaluminum compound. means.

The halogenated titanium compound means a compound containing a halogen atom and a titanium atom, and at least one halogen atom is bonded to the titanium atom. Specific examples include titanium tetrachloride, titanium tetrabromide, and titanium tetrahalogen such as titanium tetraiodide; methoxytitanium trichloride, ethoxytitanium trichloride, n-propoxytitanium trichloride, n-butoxytitanium trichloride. , And trihalogenated monoalkoxytitanium such as ethoxytitanium tribromid; dihalogen such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diiso-propoxytitanium dichloride, di-n-propoxytitanium dichloride, and diethoxytitanium dibromid. Dialkoxytitanium chemicals; monohalogenated trialkoxytitanium such as trimethoxytitanium chloride, triethoxytitanium chloride, triiso-propoxytitanium chloride, tri-n-propoxytitanium chloride, and tri-n-butoxytitanium chloride. .. Titanium tetrahalogenation or monoalkoxytitanium trihalogenate is preferable, titanium tetrahalogenate is more preferable, and titanium tetrachloride is more preferable. The titanium halide compounds may be used alone or in combination of two or more.

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

The magnesium compound may be a 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)
(In the equation, k is a number satisfying 0 ≦ k ≦ 2; m is a number satisfying 0 <m ≦ 2; n is a number satisfying 0 ≦ n ≦ 3; R ¹ is carbon. It is a hydrocarbyl group having 1 to 20 atoms; X is a halogen atom.)

^{Examples of R 1} in the formulas (i) to (iii) include an alkyl group, an aralkyl group, an aryl group, an alkenyl group and the like, and some or all of the hydrogen atoms contained in these groups are halogen atoms and hydrocals. It may be substituted with a viroxy group, a nitro group, a sulfonyl group, a silyl group and the like. Alkyl groups of 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 groups; branched alkyl groups such as iso-propyl, iso-butyl, tert-butyl, iso-pentyl, neopentyl, and 2-ethylhexyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Examples thereof include a group, a cycloheptyl group, a cyclic alkyl group such as a cyclooctyl group, and preferably a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. .. Examples of the aralkyl group of R ¹ include a benzyl group and a phenethyl group, and an aralkyl group having 7 to 20 carbon atoms is preferable. Examples ^{of the aryl group of R 1} include a phenyl group, a naphthyl group, a tolyl group and the like, and an aryl group having 6 to 20 carbon atoms is preferable. The alkenyl group of R ¹ is a linear alkenyl group such as a vinyl group, an allyl group, a 3-butenyl group, and a 5-hexenyl group; a branched form such as an isobutenyl group and a 4-methyl-3-pentenyl group. Alkenyl groups; cyclic alkenyl groups such as 2-cyclohexenyl groups and 3-cyclohexenyl groups are mentioned, preferably linear alkenyl groups having 2 to 20 carbon atoms and branched alkenyl groups having 3 to 20 carbon atoms. It is a group. A plurality of R ¹ 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, and a fluorine atom, and a chlorine atom is preferable. The plurality of Xs may be the same or different.

Specific examples of the magnesium compounds of the formulas (i) to (iii) include dimethyl magnesium, diethyl magnesium, diiso-propyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethyl butyl magnesium, dicyclohexyl magnesium, and butyl octyl. Dialkylmagnesiums such as magnesium; magnesium dialkoxides such as magnesium dimethoxydo, magnesium diethoxydo, magnesium dipropoxide, magnesium dibutoxide, magnesium dihexyl oxide, magnesium dioctyl oxide, and magnesium dicyclohexyl oxide; 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- Alkylmagnesium halides such as butylmagnesium iodide, hexylmagnesium iodide, iso-butylmagnesium iodide, benzylmagnesium iodide; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, and hexyloxymagnesium chloride. Alkoxymagnesium halides such as; aryloxymagnesium halides such as phenyloxymagnesium chloride; magnesium halides such as magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide.

Of these, magnesium halide or magnesium dialkoxide is preferable. 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. Do, magnesium diethoxyoxide, magnesium dipropoxide, magnesium di (iso-propoxide), or magnesium dibutoxide.

As the magnesium halide, a commercially available product may be used as it is, or a precipitate formed by dropping a commercially available solution in alcohol into a hydrocarbon liquid may be used separately from the liquid. , U.S. Pat. No. 6,825,146, WO 1998/044009, WO 2003/000754, WO 2003/000757, or WO 2003/085006 The product manufactured based on the above method or the like may be used.

As a method for producing magnesium dialkoxide, for example, a method in which metallic magnesium and an alcohol are brought into contact with each other in the presence of a catalyst (for example, JP-A-4-368391, JP-A-3-74341, JP-A-8-7338). And International Publication No. 2013/081893 Pamphlet). Alcohols include methanol, ethanol, propanol, butanol, and octanol. Catalysts include halogens such as iodine, chlorine, and bromine; magnesium iodide, and magnesium halides such as magnesium chloride, preferably iodine.

The magnesium compound may be supported on a carrier material. Carrier materials include, for example, _{porous inorganic oxides such as SiO 2} , Al ₂ O ₃ , MgO, TiO ₂ , and ZrO ₂ ; polystyrene, styrene-divinylbenzene copolymers, and styrene-ethylene glycol dimethacrylic acid. Polymers, methyl polyacrylate, ethyl polyacrylate, methyl-divinylbenzene copolymer, polymethyl methacrylate, methyl-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, poly Included are organic porous polymers such as vinyl chloride, styrene, and polypropylene. Of these, a porous inorganic oxide is preferable, and SiO ₂ is more preferable.

As the carrier substance, preferably, from the viewpoint of effectively immobilizing the magnesium compound on the carrier substance, the pores are porous and have a pore radius of 10 to 780 nm determined by a mercury intrusion method according to the standard ISO15901-1: 2005. A porous carrier substance having a total volume of 0.3 cm ³ / g or more is more preferable, and a porous carrier substance having a ^{total volume of 0.4 cm 3} / g or more is further preferable. Further, a porous carrier substance in which the total volume of pores having a pore radius of 10 to 780 nm is 25% or more with respect to the total volume of pores having a pore radius of 2 to 100 μm is preferably 30% or more. Certain porous carrier materials are more preferred.

The magnesium compounds may be used alone or in combination of two or more. The magnesium compound may be brought into contact with the halogenated titanium compound solution in the form of a magnesium compound slurry containing the magnesium compound and the solvent as long as the effects of the present invention can be obtained, but it is preferably in the form of no solvent, and the powder. It is more preferable to be a body.

Some or all of the magnesium atoms in the solid catalyst component for olefin polymerization are derived from the magnesium compound. In addition, some of the halogen atoms in the solid catalyst component for olefin polymerization can be derived from the magnesium compound.

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

The monoester compound means an organic compound having one ester bond (-CO-O-) in the molecule, and an aromatic carboxylic acid ester compound and an aliphatic carboxylic acid ester compound are preferable. 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, propyl toluate, and toluic acid. Examples thereof include butyl acid acid, p-toluic acid p-toluic acid, hexyl toluic acid and octyl toluic acid. Examples of the aliphatic carboxylic acid ester compound include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, octyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, and pentyl propionate. Hexyl propionate, octyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, pentyl butyrate, hexyl butyrate, octyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, pentyl valerate, yoshi Hexyl herbate, octyl valerate, methyl caproate, ethyl caproate, propyl caproate, butyl caproate, pentyl caproate, hexyl caproate, octyl caproate, methyl enanthate, ethyl enanthate, propyl enanthate, butyl enanthate , Pentyl enanthate, hexyl enanthate, octyl enanthate, methyl caprylate, ethyl caprylate, propyl caprylate, butyl caprylate, pentyl caprylate, hexyl caprylate, octyl caprylate, methyl pelargonate, ethyl pelargonate, pelargone Propyl acid, butyl pelargone, pentyl pelargone, hexyl pelargone, octyl pelargone, methyl caprate, ethyl caprate, propyl caprate, butyl caprate, pentyl caprate, hexyl caprate, octyl caprate, methyl laurate. , Ethyl laurate, propyl laurate, butyl laurate, pentyl laurate, hexyl laurate, octyl laurate, methyl myristate, ethyl myristate, propyl myristate, butyl myristate, pentyl myristate, hexyl myristate, myristin Octyl acid, methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate, pentyl palmitate, hexyl palmitate, octyl palmitate, methyl margarate, ethyl margarate, propyl margarate, butyl margarate, pentyl margarate , Hexyl margarate, octyl margarate, methyl stearate, ethyl stearate, propyl stearate, butyl stearate, pentyl stearate, hexyl stearate, 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 monovalent alcohol. However, aromatic dicarboxylic acid ester compounds and aliphatic dicarboxylic acid ester compounds are preferable. The aromatic dicarboxylic acid ester compound is a compound that can be synthesized from, for example, an aromatic dicarboxylic acid or an aromatic dicarboxylic acid dihalide and a monovalent alcohol, and specifically, dimethyl phthalate, diethyl phthalate, and dipropyl phthalate. , Diisopropyl phthalate, diisobutyl phthalate, dinormal butyl phthalate, ditercious butyl phthalate, dipentyl phthalate, dihexyl phthalate, dioctyl phthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, isophthalate Examples thereof include dipentyl acid, dihexyl isophthalate, dioctyl isophthalate, dimethyl terephthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dipentyl terephthalate, dihexyl terephthalate and dioctyl terephthalate. The aliphatic dicarboxylic acid ester compound is a compound that can be synthesized from, for example, an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid dihalide and a monovalent alcohol. Dipropyl Dipropyl, Dibutyl Ethanate, Dipentyl Ethanate, Dihexyl Ethanate, Dioctyl Ethanate, Dimethyl Propanate, Diethyl Propanate, Dipropyl Propanate, Dibutyl Propanate, Dipentyl Propanate, Propane Dihexyl diacid, dioctyl propanedionate, dimethyl butane diate, diethyl butane diate, dipropyl butane dipropyl, dibutyl butane diate, dipentyl butane diate, dihexyl butane diate, dioctyl butane diate, dimethyl pentanate, pentane Diethyl diate, dipropyl pentanate, dibutyl pentanate, dipentyl pentanate, dihexyl pentanate, dioctyl pentanate, dimethyl hexane diate, diethyl hexane diate, dipropyl hexane dipropyl, dibutyl hexane diate, hexane Dipentyl diate, dihexyl hexane diate, dioctyl hexane diate, dimethyl (E) -but-2-enoate, diethyl (E) -but-2-enoate, (E) -buta-2-endi Dipropyl acid, dibutyl (E) -but-2-enostate, dipentyl (E) -but-2-enostate, dihexyl (E) -but-2-enostate, (E) -porcine-2- Dioctyl enoate, dimethyl (Z) -but-2-enostate, diethyl (Z) -buta-2-enostate, dipropyl (Z) -but-2-enostate, (Z) -buta- Dibutyl 2-benzoate, dipentyl (Z) -but-2-enostate, dihexyl (Z) -buta-2-enostate, dioctyl (Z) -but-2-enoate, cyclohexane-1, Dimethyl 2-dicarboxylic acid, diethyl cyclohexane-1,2-dicarboxylic acid, dipropyl cyclohexane-1,2-dicarboxylic acid, dibutyl cyclohexane-1,2-dicarboxylic acid, dipentyl cyclohexane-1,2-dicarboxylic acid, cyclohexane-1, Dihexyl 2-dicarboxylic acid, dioctylcyclohexane-1,2-dicarboxylic acid, dimethyl 1,2-cyclohexene-1,2-dicarboxylic acid, diethyl 1,2-cyclohexene-1,2-dicarboxylic acid, 1,2-cyclohexene- Dipropyl 1,2-dicarboxylic acid, dibu 1,2-cyclohexene-1,2-dicarboxylic acid Chill, 1,2-cyclohexene-1,2-dicarboxylic acid dipentyl, 1,2-cyclohexene-1,2-dicarboxylic acid dihexyl, 1,2-cyclohexene-1,2-dicarboxylic acid dioctyl, 3-methylcyclohexane-1 , 2-Dicarboxylate dimethyl, 3-methylcyclohexane-1,2-dicarboxylic acid diethyl, 3-methylcyclohexane-1,2-dicarboxylic acid dipropyl, 3-methylcyclohexane-1,2-dicarboxylic acid dibutyl, 3-methylcyclohexane Dipentyl-1,2-dicarboxylic acid, dihexyl 3-methylcyclohexane-1,2-dicarboxylic acid, dioctyl 3-methylcyclohexane-1,2-dicarboxylic acid, dimethyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid, Dipropyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid, dipropyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid, dibutyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid, 3,6-dimethyl Examples thereof include dipentyl cyclohexane-1,2-dicarboxylic acid, dihexyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid and dioctyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid.

A diol diester compound is a compound having two ester bonds (-CO-O-) in the molecule, and each of the two hydroxyl groups of the diol has a structure in which the carboxyl group of monocarboxylic acid or dicarboxylic acid is esterified. It means a compound having 1,2-dibenzoate propane, 1,2-diacetyloxypropane, 1,2-dibenzoatebutane, 1,2-diacetyloxybutane, 1,2-dibenzoatecyclohexane. , 1,2-Diacetyloxycyclohexane, 1,3-dibenzoate propane, 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-di Examples thereof include benzoate-4-tert-butyl-6-methylbenzene and 1,3-diacetyloxy-4-tert-butyl-6-methylbenzene.

The β-alkoxy ester compound means a compound having an alkoxycarbonyl group and an alkoxy group at the β-position of the alkoxycarbonyl group, specifically, methyl 2-methoxymethyl-3,3-dimethylbutanoate, Ethyl 2-methoxymethyl-3,3-dimethylbutanoate, propyl 2-methoxymethyl-3,3-dimethylbutanoate, butyl 2-methoxymethyl-3,3-dimethylbutanoate, 2-methoxymethyl-3,3 -Pentyl dimethylbutanoate, hexyl 2-methoxymethyl-3,3-dimethylbutanoate, octyl 2-methoxymethyl-3,3-dimethylbutanoate, methyl 3-methoxy-2-phenylpropionate, 3-methoxy-2 -Ethyl phenylpropionate, propyl 3-methoxy-2-phenylpropionate, butyl 3-methoxy-2-phenylpropionate, pentyl 3-methoxy-2-phenylpropionate, hexyl 3-methoxy-2-phenylpropionate, Octyl 3-methoxy-2-phenylpropionate, methyl 2-ethoxymethyl-3,3-dimethylbutanoate, ethyl 2-ethoxymethyl-3,3-dimethylbutanoate, 2-ethoxymethyl-3,3-dimethylbutane Ppropyl acid, 2-ethoxymethyl-3,3-dimethylbutanoate butyl, 2-ethoxymethyl-3,3-dimethylbutanoate pentyl, 2-ethoxymethyl-3,3-dimethylbutanoate hexyl, 2-ethoxymethyl- Octyl 3,3-dimethylbutanoate, methyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxy-2-phenylpropionate, propyl 3-ethoxy-2-phenylpropionate, 3-ethoxy-2-phenylpropion Butyl acid, pentyl 3-ethoxy-2-phenylpropionate, hexyl 3-ethoxy-2-phenylpropionate, octyl 3-ethoxy-2-phenylpropionate, methyl 2-propyloxymethyl-3,3-dimethylbutanoate , 2-propyloxymethyl-3,3-dimethylbutanoate ethyl, 2-propyloxymethyl-3,3-dimethylbutanoate propyl, 2-propyloxymethyl-3,3-dimethylbutanoate butyl, 2-propyloxy Pentyl methyl-3,3-dimethylbutanoate, hexyl 2-propyloxymethyl-3,3-dimethylbutanoate, octyl 2-propyloxymethyl-3,3-dimethylbutanoate, 3-propyloxy-2-phenylpropio Methyl acidate, ethyl 3-propyloxy-2-phenylpropionate, propyl 3-propyloxy-2-phenylpropionate, butyl 3-propyloxy-2-phenylpropionate, 3-propyloxy-2-phenylpropionic acid Pentyl, hexyl 3-propyloxy-2-phenylpropionate, octyl 3-propyloxy-2-phenylpropionate, methyl 2-methoxybenzenecarboxylate, ethyl 2-methoxybenzenecarboxylic acid, propyl 2-methoxybenzenecarboxylic acid, Butyl 2-methoxybenzenecarboxylic acid, pentyl 2-methoxybenzenecarboxylic acid, hexyl 2-methoxybenzenecarboxylic acid, octyl 2-methoxybenzenecarboxylic acid, methyl 2-ethoxybenzenecarboxylic acid, ethyl 2-ethoxybenzenecarboxylic acid, 2- Examples thereof include propyl ethoxybenzenecarboxylic acid, butyl 2-ethoxybenzenecarboxylic acid, pentyl 2-ethoxybenzenecarboxylic acid, hexyl 2-ethoxybenzenecarboxylic acid and octyl 2-ethoxybenzenecarboxylic acid.

The diether compound means a compound having two ether bonds in the molecule, specifically 1,2-dimethoxypropane, 1,2-diethoxypropane, 1,2-dipropyloxypropane, 1,2. -Dibutoxypropane, 1,2-di-tert-butoxypropane, 1,2-diphenoxypropane, 1,2-dibenzyloxypropane, 1,2-dimethoxybutane, 1,2-diethoxybutane, 1, 2-Dipropyloxybutane, 1,2-dibutoxybutane, 1,2-di-tert-butoxybutane, 1,2-diphenoxybutane, 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-dibenzyl Oxycyclohexane, 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-Butyloxypentane, 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-dibutoxy Benzene, 1,2-di-tert-butoxybenzene, 1,2-diphenoxybenzene and 1,2- Examples thereof include dibenzyloxybenzene.

Further, the internal electron donor described in Japanese Patent Application Laid-Open No. 2011-2466699 can also be exemplified.

Of these, a dicarboxylic acid ester compound, a diol diester compound and a β-alkoxy ester compound are preferable. The internal electron donors may be used alone or in combination of two or more.

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

The solvent in step (I) is preferably inert to the solid product produced in step (I) and the solid catalyst component for olefin polymerization. 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. Hydrogen; halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene; and ether compounds such as diethyl ether, dibutyl ether, diisoamyl ether and tetrahydrofuran can be mentioned. Of these, aromatic hydrocarbons or halogenated hydrocarbons are preferable, and toluene is more preferable. The solvent may be used alone or in combination of two or more.

In the present invention, the contact between the titanium halide compound solution and the magnesium compound is usually carried out in an inert gas atmosphere such as nitrogen gas and argon gas. As a method of bringing these into contact with each other to obtain a slurry containing a solid product, a method of adding a magnesium compound to a titanium halide compound solution can be exemplified.

In the method of adding the magnesium compound to the titanium halide compound solution, the magnesium compound may be added at once or may be divided into any plurality of times. Moreover, you may add a magnesium compound continuously. Further, the magnesium compound is preferably a powder, and may be a mixture of a magnesium compound and a solvent as long as the effects of the present invention can be obtained.

As a method for bringing the components into contact with each other, known methods such as a slurry method and a mechanical pulverization method (for example, a method in which the components are brought into contact with each other while being pulverized by a ball mill) can be exemplified.

The amount of the titanium halide compound in the titanium halide compound solution is usually 0.001 to 50 mL, preferably 0.01 to 25 mL, more preferably 0.05 to 10 mL, and further, with respect to 1 mL of the solvent contained in the solution. It is preferably 0.1 to 1.0 mL.

The temperature at which the titanium halide compound solution and the magnesium compound are brought into contact with each other is usually −20 ° C. to 50 ° C., preferably −5 ° C. to 20 ° C. The contact time is usually 0.01 to 48 hours, preferably 0.1 to 36 hours, more preferably 1 to 24 hours.

In the step (I), the titanium halide compound solution and the magnesium compound so that the ratio (A / C) of A represented by the following formula (1) to C represented by the following formula (2) is 3 or less. Contact with is made. The volume of the solvent contained in the slurry containing the solid product for calculating the A / C value is contained in the slurry at the time when the contact between the total amount of the titanium halide compound solution and the total amount of the magnesium compound is completed. The volume of solvent used.
A = a / b (1)
(In the formula, a represents the volume (mL) of the titanium halide compound contained in the titanium halide compound solution, and b represents the volume (mL) of the solvent contained in the titanium halide compound solution.)
C = a / c (2)
(In the formula, a represents the volume (mL) of the titanium halide compound contained in the titanium halide compound solution, and c represents the volume (mL) of the solvent contained in the slurry containing the solid product.)

The A / C is preferably 2.5 or less, more preferably 2 or less, still more preferably 1.8 or less, and particularly preferably 1.5 or less. A / C is 1 or more.

A / C is, i.e., c / b and can be the ratio of the volume of solvent at the end of step (I) to the volume of solvent at the start of step (I). In the conventional production method, the solvent used in step (I) is used only for preparing a slurry of a magnesium compound, or is used for preparing both a titanium halide compound solution and a magnesium compound slurry, and magnesium. The amount of solvent in the compound slurry is greater than the amount of solvent in the titanium halide compound solution. On the other hand, in the production method of the present invention, the solvent used in the step (I) is more than the preparation of the titanium halide compound solution when both the titanium halide compound solution and the mixture of magnesium and the solvent are prepared. Is used, or is used only in the preparation of titanium halide compound solutions (A / C is 3 or less).

The solid product is a reaction product of a titanium halide compound and a magnesium compound. The solvent contained in the slurry may include a solvent in the titanium halide compound solution and may further include a solvent in the magnesium compound slurry and / or a solvent added alone during step (I). That is, if A / C is greater than 1, the increased solvent can be derived from the solvent in the magnesium compound slurry and / or the solvent added alone during step (I).

In the production method of the present invention, since the A / C is 3 or less, the amount of change in the solvent from the start of the reaction to the end of the reaction in step (I) is small. Therefore, in step (I), a highly uniform reaction can be realized from the start of the reaction to the end of the reaction. When an olefin polymerization catalyst containing a solid catalyst component for olefin polymerization produced under such conditions is used, the stereoregularity of the olefin polymer obtained by polymerizing the olefin can be increased (see also Examples described later). When an olefin polymerization catalyst containing a solid catalyst component for polymerization produced under such conditions is used, a particulate olefin polymer is produced by a slurry polymerization method, a solution polymerization method, a bulk polymerization method, or a vapor phase polymerization method. In some cases, polymer particles with a small amount of fine powder can be provided.

The timing of adding the internal electron donor is arbitrary. For example, it may be added to the reactor prior to step (I), may be mixed with a titanium halide compound solution, may be mixed with a magnesium compound, or may be mixed with step (I). It may be added during the above process, or it may be added to the slurry containing the solid product after the step (I), or a combination thereof may be used.

In the production method of the present invention, the amount of the internal electron donor used is usually 0.001 to 5 mol, preferably 0.01 to 0.5 mol, per 1 mol of total magnesium atoms in the magnesium compound used in step (I). Is.

In one embodiment, from the viewpoint of improving the particle properties, it is preferable to add an internal electron donor to the slurry containing the solid product after the step (I). That is, in one embodiment, the production method of the present invention preferably includes a step (II) of adding an internal electron donor to a slurry containing a solid product.

Regardless of the timing of addition of the internal electron donor, the temperature at which the solid product and the internal electron donor react with each other is usually −20 ° C. to 150 ° C., preferably −5 ° C. to 135 ° C. , More preferably 30 ° C to 120 ° C. The reaction time is usually 0.1 to 12 hours, preferably 0.5 to 10 hours. The reaction of the solid product with the internal electron donor is usually carried out in an atmosphere of an inert gas such as nitrogen gas and argon gas.

Steps (I) and (II) are each carried out with normal stirring, and the stirring is carried out so that the peripheral speed v of the stirring blade represented by the following formula (5) is usually in the range of 0.1 to 10 m / sec. It is preferably carried out under the condition of 0.5 to 5.0 m / sec, more preferably 1.0 to 3.0 m / sec.
v = n × d (5)
(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.)

After completion of the reaction, the obtained solid may be used as a solid catalyst component for olefin polymerization, or the obtained solid may be used as a precursor with one or more of a titanium halide compound, a magnesium compound and an internal electron donor. Further, the solid obtained by contact may be used as a solid catalyst component for olefin polymerization. In one embodiment, the production method of the present invention comprises the step (III) of contacting the obtained precursor with one or more of a titanium halide compound, a magnesium compound and an internal electron donor.

The solid catalyst component for olefin polymerization or the precursor is preferably washed with a solvent in order to remove unnecessary substances. The solvent is preferably inert to the precursor or solid catalyst component for olefin polymerization and as the solvent aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; aromatics such as benzene, toluene and xylene. Group hydrocarbons; alicyclic hydrocarbons such as cyclohexane and cyclopentane; and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene can be exemplified. Of these, aromatic hydrocarbons or halogenated hydrocarbons are particularly preferable. The amount of solvent used for washing can be, for example, 0.1 mL to 1000 mL per gram of solid catalyst component or precursor for olefin polymerization per step of contact. It is preferably 1 mL to 100 mL per gram. Washing is usually performed 1 to 5 times per step of contact. The washing temperature is usually −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.

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 compounds are brought into contact with each other in the step (III), the amount of the titanium halide compounds is usually 0.1 to 10 mL / mL solvent, preferably 0.1 to 1.0 mL / mL solvent. When the magnesium compounds are brought into contact with each other in the step (III), the amount of the magnesium compounds is usually 0.01 to 10 g / mL solvent, preferably 0.1 to 1.0 g / mL solvent. When the internal electron donors are brought into contact in step (III), the amount of the internal electron donors is usually 0.001 to 5 mL / mL solvent, preferably 0.005 to 0.5 mL / mL solvent, more preferably 0. It is a 0.01-0.1 mL / mL solvent.

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

The temperature of step (III) is usually −20 ° C. to 150 ° C., preferably −5 ° C. to 130 ° C., and more preferably 40 ° C. to 120 ° C. The contact time is usually 0.1-12 hours, preferably 1-8 hours. In the present invention, the contact of the precursor with one or more of the titanium halide compound, the magnesium compound and the internal electron donor is usually carried out in an inert gas atmosphere such as nitrogen gas and argon gas. Will be done. Step (III) may be performed once or may be repeated a plurality of times.

After completion of the reaction, the obtained solid can be used as a solid catalyst component for olefin polymerization. The solid catalyst component for olefin polymerization is preferably washed with a solvent in the same manner as described above. Further, it may be dried after washing (for example, drying under reduced pressure).

<Solid catalyst component for olefin polymerization>
The solid catalyst component for olefin polymerization of the present invention is, in one embodiment, the solid catalyst component for olefin polymerization obtained by the above-mentioned production method.

In another embodiment, the solid catalyst component for olefin polymerization of the present invention is the following solid catalyst component for olefin polymerization. The following solid catalyst component for olefin polymerization is obtained by the above-mentioned production method, for example.
At least one internal electron donor selected from the group consisting of monoester compounds, aliphatic dicarboxylic acid ester compounds, diol diester compounds, β-alkoxy ester compounds and diether compounds, titanium atoms, magnesium atoms and halogen atoms. Including
A solid catalyst component for olefin polymerization that satisfies the following requirements (I) to (IV).
(I) The total pore volume measured by the mercury intrusion method according to the standard ISO15901-1: 2005 is 0.95 to 1.80 mL / g, and the specific surface area measured by the mercury intrusion method according to the standard ISO15901: 1: 2005. Is 60 to 170 m ² / g.
(II) In accordance with 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 the laser diffraction / scattering method shall be 6.5% or less.
(III) In accordance with the standard ISO15472: 2001, among the peak components obtained by waveform-separating the peaks belonging to the 1s orbit of oxygen atoms 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 peak component area (G) in which the peak top binding energy is in the range of 529 eV or more and less than 532 eV to the peak component area (F) in the range is 0.33 or less.
(IV) The titanium content is 1.50 to 3.40 wt%.

The origins of the titanium atom, magnesium atom and halogen atom are the same as described above. The description of the monoester compound, the aliphatic dicarboxylic acid ester compound, the diol diester compound, the β-alkoxy ester compound and the diether compound is the same as described above. In one example, the internal electron donor is preferably a diol diester compound or a β-alkoxy ester compound, more preferably a β-alkoxy ester compound, and even more preferably ethyl 2-ethoxymethyl-3,3-dimethylbutanoate. Is.

The requirement (I) will be described below.
The total pore volume measured by the mercury intrusion method according to the standard ISO15901-1: 2005 is 0.95 to 1.80 mL / g, preferably 1.00 to 1.70 mL / g, and more preferably 1. .10 to 1.60 mL / g. When the total pore volume is 0.95 mL / g or more, the productivity of the polymer is improved. When the total pore volume is 1.80 mL / g or less, sufficient catalyst particle strength can be secured.
The specific surface area measured by the mercury intrusion method according to the standard ISO15901-1: 2005 is 60 to 170 m ² / g, preferably 80 to 150 m ² / g, and 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 obtained polymer can be reduced. When the specific surface area is 170 m ² / g or less, sufficient catalyst particle strength can be secured.

The requirement (II) will be described below.
According to the standard ISO13320: 2009, in the volume-based particle size distribution measured by the laser diffraction / scattering method, the cumulative percentage of the components having a thickness of 10 μm or less is 6.5% or less, preferably 6.2% or less. , 6.0% or less, more preferably 5.5% or less. When the cumulative percentage is 6.5% or less, fouling troubles in the polymerization process can be suppressed.

The requirement (III) will be described below.
According to the standard ISO15472: 2001, among the peak components obtained by waveform-separating the peaks belonging to the 1s orbit of the oxygen atom obtained by X-ray photoelectron spectroscopy, the binding energy has a peak top in the range of 532 eV or more and 534 eV or less. The ratio (G / F) of the area (G / F) of the peak component having the peak top in the range where the binding energy is 529 eV or more and less than 532 eV to the area (F) of the peak component is 0.33 or less, and is 0.30 or less. It is preferably 0.28 or less, and more preferably 0.28 or less. When the G / F is 0.33 or less, the formation of sticky components can be suppressed in the polymerization.

The requirement (IV) will be described below.
The titanium content is 1.50 to 3.40 wt%, preferably 1.6 to 3.0 wt%. When the titanium content is 3.40 wt% or less, the sticky component 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 solid catalyst component for olefin polymerization produced by the production method of the present invention may also satisfy at least one, at least two, or all of the requirements (I) to (III) in one embodiment.

In one example, the content of titanium atoms in the solid catalyst component for olefin polymerization is usually 1.5 to 3.4% by weight, preferably 1.8 to 3.0% by weight. The titanium atom content can be determined, for example, by the method of Examples described later.

In one example, the content of the internal electron donor in the solid catalyst component for olefin polymerization is usually 5 to 20% by weight, preferably 10 to 15% by weight. The content of the internal electron donor can be determined, for example, by the method of Examples described later.

In one example, the content of the alkoxy group in the solid catalyst component for olefin polymerization is usually 2.0% by weight or less, preferably 1.5% by weight or less. The content of the alkoxy group can be determined, for example, by the method of Examples described later.

According to the solid catalyst component for olefin polymerization of the present invention, as described later, when an olefin is polymerized using a catalyst for olefin polymerization containing the same, a polymer having high stereoregularity can be provided.

<Catalyst for olefin polymerization>
In one embodiment, a catalyst for olefin polymerization can be produced by contacting the solid catalyst component for olefin polymerization of the present invention with an organoaluminum compound by, for example, a known method. Further, in another embodiment, the catalyst for olefin polymerization can be produced by contacting the solid catalyst component for olefin polymerization of the present invention, the organoaluminum compound, and an external electron donor.

Therefore, the catalyst for olefin polymerization of the present invention contains, in one embodiment, the solid catalyst component for olefin polymerization of the present invention and the organoaluminum compound. Further, in another embodiment, the catalyst for olefin polymerization of the present invention includes the solid catalyst component for olefin polymerization of the present invention, an organoaluminum compound and an external electron donor.

The organoaluminum compound used in the present invention is a compound having one or more carbon-aluminum bonds, and specific examples thereof include the compounds described in JP-A No. 10-212319. Among them, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalmoxane is preferable, and triethylaluminum, triiso-butylaluminum, a mixture of triethylaluminum and diethylaluminum chloride or It is tetraethyldialmoxane.

Examples of the external electron donor used in the present invention 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. be able to. Of these, oxygen-containing compounds or nitrogen-containing compounds are preferable. Alkoxysilicon, ethers, esters, and ketones can be exemplified as oxygen-containing compounds. Of these, alkoxysilicon or ether is preferable.

The alkoxysilicon as an external electron donor is preferably a compound represented by any of the following formulas (iv) to (vi).
R ² _h Si (OR ³ ) _4-h ... (iv)
Si (OR ⁴ ) ₃ (NR ⁵ R ⁶ ) ・ ・ ・ (v)
Si (OR ⁴ ) ₃ (NR ⁷ ) ・ ・ ・ (vi)
[In the formula, R ² is a hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom; R ³ is a hydrocarbyl group having 1 to 20 carbon atoms; h is 0 ≦ h <4. It is an integer that satisfies. If one or both of R ² and R ³ there are a plurality, the plurality of R ² and R ³ may or may not be the same as each other. R ⁴ is a hydrocarbyl group having 1 to 6 carbon atoms; R ⁵ and R ⁶ are hydrogen atoms or a hydrocarbyl group having 1 to 12 carbon atoms; NR ⁷ is a hydrocarbyl group having 5 to 12 carbon atoms. It is a cyclic amino group of 20. ]

^{Examples of the hydrocarbyl group of R 2} and R ³ in the above formula (iv) include an alkyl group, an aralkyl group, an aryl group, an alkenyl group and the like, and examples ^{of the alkyl group of R 2} and R ³ include a methyl group and an ethyl group. Linear alkyl groups such as group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group; iso-propyl group, iso-butyl group. , Tert-butyl group, iso-pentyl group, neopentyl group, and branched alkyl group such as 2-ethylhexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group. Such a cyclic alkyl group is mentioned, and is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Examples of the aralkyl group of R ² and R ³ include a benzyl group and a phenethyl group, and an aralkyl group having 7 to 20 carbon atoms is preferable. Examples ^{of the aryl group of R 2} and R ³ include a phenyl group, a tolyl group, and a xsilyl group, and an aryl group having 6 to 20 carbon atoms is preferable. The alkenyl groups of 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, and 5-methyl-3-pentenyl group. Branched alkenyl groups such as; 2-cyclohexenyl groups, and cyclic alkenyl groups such as 3-cyclohexenyl groups, preferably alkenyl groups having 2-10 carbon atoms.

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

^{Examples of the hydroxycarbyl group of R 4 in} the above formulas (v) and (vi) include an alkyl group and an alkenyl group, and examples ^{of the alkyl group of R 4} include a methyl group, an ethyl group, an n-propyl group and n. Linear alkyl groups such as −butyl group, n-pentyl group, and n-hexyl group; branched such as iso-propyl group, iso-butyl group, tert-butyl group, iso-pentyl group, and neopentyl group. State Alkyl group: Cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group are mentioned, and a linear alkyl group having 1 to 6 carbon atoms is preferable. The alkenyl group of R ⁴ includes a linear alkenyl group such as a vinyl group, an allyl group, a 3-butenyl group, and a 5-hexenyl group; a branch such as an iso-butenyl group and a 5-methyl-3-pentenyl group. State alkenyl group; cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group are preferably linear alkenyl groups having 2 to 6 carbon atoms, and particularly preferably methyl group and ethyl. It is a group.

^{Examples of the hydrocarbyl group of R 5} and R ⁶ in the above formula (v) include an alkyl group and an alkenyl group, ^{and examples of the alkyl group of R 5} and R ⁶ include a methyl group, an ethyl group and an n-propyl group. , N-butyl group, n-pentyl group, and linear alkyl group such as n-hexyl group; such as iso-propyl group, iso-butyl group, tert-butyl group, iso-pentyl group, and neopentyl group. Bifurcated alkyl groups; cyclic alkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group are mentioned, and linear alkyl group having 1 to 6 carbon atoms is preferable. The alkenyl groups of R ⁵ and R ⁶ include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; iso-butenyl group, and 5-methyl-3-pentenyl group. Branched alkenyl groups such as; 2-cyclohexenyl groups, and cyclic alkenyl groups such as 3-cyclohexenyl groups, preferably linear alkenyl groups having 2 to 6 carbon atoms, particularly preferably. It is a methyl group and an ethyl group.

Specific examples of the alkoxysilicon represented by the above formula (v) include dimethylaminotrimethoxysilane, diethylaminotrimethoxysilane, di-n-propylaminotrimethoxysilane, dimethylaminotriethoxysilane, diethylaminotriethoxysilane, and di. -N-propylaminotriethoxysilane, methylethylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, tert-butylaminotriethoxysilane, diiso-propylaminotriethoxysilane, methyliso-propylaminotriethoxysilane Silane can be mentioned.

^{The cyclic amino group of NR 7} in the above formula (vi) includes a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, and 1,2,3,4-tetrahydroiso. Examples thereof include a quinolino group and an octamethyleneimino group.

Specific examples of the alkoxysilicon represented by the above formula (vi) include perhydroquinolinotriethoxysilane, perhydroisoquinolinotriethoxysilane, 1,2,3,4-tetrahydroquinolinotriethoxysilane, 1, Examples thereof include 2,3,4-tetrahydroisoquinolinotriethoxysilane and octamethyleneiminotriethoxysilane.

The ether of the external electron donor 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, and more preferably at least one -C-O-C-O-C in the ring structure. It is a cyclic ether compound having a − bond, and is particularly preferably 1,3-dioxolane or 1,3-dioxane.

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

The method of contacting the solid catalyst component for olefin polymerization, the organoaluminum compound, and the external electron donor is not particularly limited as long as the catalyst for olefin polymerization is produced. The contact is carried out in the presence or absence of a solvent. These contact mixtures may be supplied to the polymerization tank, each component may be separately supplied to the polymerization tank and contacted in the polymerization tank, or the contact mixture of any two components and the remaining components may be supplied. They may be separately supplied to the polymerization tank and brought into contact with each other in the polymerization tank.

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

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

According to the olefin polymerization catalyst of the present invention, as will be described later, when an olefin is polymerized using this, a polymer having high stereoregularity can be provided.

<Method for producing olefin polymer>
The method for producing an olefin polymer of the present invention polymerizes an olefin in the presence of the catalyst for olefin polymerization of the present invention.

Examples of the olefin include ethylene and α-olefin having 3 or more carbon atoms. Linear monoolefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 1-octene, and 1-decene as α-olefins; 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 of these can be exemplified. Of these, it is preferably homopolymerization of ethylene or propylene, or copolymerization of a plurality of types of olefins containing ethylene or propylene as a main component. The above-mentioned combination of a plurality of types of olefins may include a combination of two or more types of olefins, and a combination of a compound having a polyunsaturated bond such as a conjugated diene or an unconjugated diene and an olefin. It may be included.

The olefin polymer produced by the method for producing an olefin polymer of the present invention is preferably an ethylene homopolymer, a propylene homopolymer, a 1-butene homopolymer, a 1-pentene homopolymer, or a 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- It is a butene copolymer, an ethylene-propylene-1-hexene copolymer, or a polymer obtained by multi-stage polymerization of these.

In one embodiment, the method for forming the catalyst for olefin polymerization of the present invention may preferably consist of the following steps:
(I) In the presence of a solid catalyst component for olefin polymerization and an organic aluminum compound, a small amount of olefin (same or different from the olefin used in the original polymerization (usually referred to as main polymerization)) is polymerized (produced). A chain transfer agent such as hydrogen may be used to regulate the molecular weight of the olefin polymer (or an external electron donor may be used) to produce a catalyst component whose surface is covered with the polymer of the olefin. Step to make (the polymerization is usually referred to as prepolymerization, and therefore the catalyst component is usually referred to as prepolymerization catalyst component).
(Ii) A step of bringing the prepolymerization catalyst component into contact with the organoaluminum compound and the external electron donor.

The prepolymerization is preferably a slurry polymerization using an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene and toluene as a solvent.

The amount of the organoaluminum compound used in the step (i) is usually 0.5 mol to 700 mol, preferably 0.8 mol to 500 mol, particularly preferably 0.8 mol to 500 mol, per 1 mol of titanium atoms in the solid catalyst component used in the step (i). It is 1 mol to 200 mol.

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

The slurry concentration of the solid catalyst component for olefin polymerization in the slurry polymerization of the above step (i) is preferably 1 to 500 g-solid catalyst component for olefin polymerization / liter-solvent, and particularly preferably 3 to 300 g-solid catalyst component for olefin polymerization. / Lt-Solution.

The temperature of the prepolymerization is preferably −20 ° C. to 100 ° C., particularly preferably 0 ° C. to 80 ° C. The partial pressure of the olefin in the gas phase portion in the prepolymerization is preferably 0.01 MPa to 2 MPa, particularly preferably 0.1 MPa to 1 MPa, but this does not apply to olefins that are liquid at the pressure and temperature of the prepolymerization. do not have. The prepolymerization time is preferably 2 minutes to 15 hours.

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

The following methods (1) and (2) can be exemplified as a method for supplying the olefin to the polymerization tank in the prepolymerization:
(1) A method of sequentially supplying olefins to the polymerization tank so as to maintain the pressure in the polymerization tank at a predetermined pressure (2) A method of collectively supplying the entire amount of the predetermined amount of olefins to the polymerization tank.

The amount of the external electron donor used in the prepolymerization is usually 0.01 mol to 400 mol, preferably 0.02 mol to 200 mol, particularly preferably 0, with respect to 1 mol of the titanium atom contained in the solid catalyst component for olefin polymerization. It is 0.03 mol to 100 mol, and is usually 0.003 mol to 5 mol, preferably 0.005 mol to 3 mol, and particularly preferably 0.01 mol to 2 mol with respect to 1 mol of the organoaluminum compound.

The following methods (1) and (2) can be exemplified as a method for supplying an external electron donor to the polymerization tank in the prepolymerization:
(1) A method of supplying an external electron donor alone to a polymerization tank (2) A method of supplying a contact product of an external electron donor and an organoaluminum compound to a polymerization tank.

The amount of the organoaluminum compound used during the main polymerization is usually 1 mol to 1000 mol, particularly preferably 5 mol to 600 mol, per 1 mol of titanium atoms in the solid catalyst component for olefin polymerization.

When an external electron donor is used in this polymerization, the amount of the external electron donor used is usually 0.1 mol to 2000 mol, preferably 0.3 mol to 1000 mol, per 1 mol of titanium atoms contained in the solid catalyst component for olefin polymerization. It is particularly preferably 0.5 mol to 800 mol, and usually 0.001 mol to 5 mol, preferably 0.005 mol to 3 mol, and particularly preferably 0.01 mol to 1 mol per 1 mol of the organoaluminum compound.

The temperature of this polymerization is usually −30 ° C. to 300 ° C., preferably 20 ° C. to 180 ° C. The polymerization pressure is not particularly limited, and is generally about 10 MPa to 10 MPa, preferably about 200 kPa to 5 MPa from the viewpoint of being industrial and economical. The polymerization is a batch type or a continuous type, and as a polymerization method, a slurry polymerization method or a solution polymerization method using an inert hydrocarbon such as propane, butane, isobutane, pentane, hexane, heptane and octane as a solvent, or a liquid polymerization method at a polymerization temperature. A bulk polymerization method using the above-mentioned olefin as a medium and a vapor phase polymerization method can be exemplified.

Chain transfer agents (eg, hydrogen or alkyl zinc such as dimethylzinc and diethylzinc) may be used to regulate the molecular weight of the polymer obtained in this polymerization.

According to the present invention, it is possible to obtain an olefin polymerization catalyst that gives a polymer having high stereoregularity when an olefin is polymerized, and a solid catalyst component for olefin polymerization for producing the olefin polymerization catalyst. Further, by polymerizing an olefin using the olefin polymerization catalyst, an olefin polymer having high stereoregularity can be obtained. The solid catalyst component for olefin polymerization of the present invention is particularly suitable as a catalyst for an isotactic stereoregular olefin polymer.

The CXS content may be used as a measure of isotactic stereoregularity.
In one example, the CXS content is usually 2.0% by weight or less, preferably 1.5% by weight or less, and more preferably 1.0% by weight or less. The CXS content can be determined, for example, by the method of Examples described later.

Further, in one embodiment, the solid catalyst component for olefin polymerization and the catalyst for olefin polymerization of the present invention can provide polymer particles having a small amount of fine powder when a particulate olefin polymer is produced by a vapor phase polymerization method. In one example, the amount of fine powder (1 mm or less) in the olefin polymer can be preferably 4.0% by weight or less, more preferably 3.0% by weight or less.

Examples are shown below, and embodiments of the present invention will be described in more detail.

[Composition analysis of solid catalyst components]
(1) Titanium atom content After decomposing about 20 mg of a solid sample with about 30 mL of 2 specified dilute sulfuric acid, 3 mL of excess 3 wt% hydrogen peroxide solution was added thereto, and the obtained liquid sample had characteristics of 410 nm. The absorption was measured by an ultraviolet-visible spectrophotometer V-650 manufactured by JASCO Corporation in accordance with the standard JIS K0115: 2004, and the content of titanium atoms was determined based on a separately prepared calibration curve.

(2) Alkoxy group content After decomposing about 2 g of a solid sample with 100 mL of water, the amount of alcohol corresponding to the alkoxy group in the obtained liquid sample was determined by using the gas chromatography internal standard method according to the standard JIS K0114: 2012. The obtained result was converted into an alkoxy group content.

(3) Content of internal electron donor After dissolving about 300 mg of the solid catalyst component in 100 mL of N, N-dimethylacetamide, the amount of internal electron donor in the solution is determined by gas chromatography internal standard according to the standard JIS K0114: 2012. Asked by law.

(4) Pore volume The pore distribution of the solid catalyst component in the pore radius range of about 0.0018 to 100 μm was measured by the mercury intrusion method according to the standard ISO15901-1: 2005. The pore radius was calculated using Washburn's formula. As a measuring device, Autopore IV9520 manufactured by micrometrics was used. The sample was handled so as not to come into contact with air and moisture, and no pretreatment was performed. The pore volume was determined from the obtained measurement data.

(5) Central particle size (D50) of solid catalyst component and cumulative percentage of components having a particle size of 10 μm or less According to the standard ISO13320: 2009, the central particle size (D50) and the cumulative percentage of components having a particle size of 10 μm or less are measured by laser diffraction / scattering method. Was analyzed by. A laser diffraction type particle size distribution measuring device (“Mastersizer 3000” manufactured by Malvern) was used as the measuring device, and the refractive index was 1.49 for toluene and 1.53-0.1i for the solid catalyst component. A toluene solvent from which water had been removed in advance with alumina or the like was put into a dispersion device (hydro MV) whose openings were sealed with nitrogen to fill the inside of the circulatory system including the measurement cell with the solvent. The stirring speed was set to 2,000 rpm, and the particle size was measured by adding a powder sample so that the scattering intensity was 3 to 10% while circulating the solvent in the measurement cell without ultrasonic dispersion treatment. From the obtained particle size volume reference distribution map (chart), the central particle size (D50) and the cumulative percentage of the components having a particle size of 10 μm or less were determined. The sample was handled so as not to come into contact with air and moisture, and no pretreatment was performed.

(6) Binding energy The binding energy was measured by the X-ray photoelectron spectroscopy (XPS) analysis method according to the standard ISO15472: 2001. Using AXIS ULTRA DLD manufactured by Kratos Analycal as a measuring device, measurement was performed under the following measurement conditions to obtain a peak attributed to the 1s orbit of the oxygen atom. In the measurement, the energy axis was corrected so that the peak attributed to the carbon atom 1s orbital was 285.0 eV.
<Measurement conditions>
Light source: Monochromatic AlKα line (1486.6 eV)
Tube current: 10mA
Tube voltage: 15 kV, 0.1 eV step Measurement vacuum inside the device: ^10-8 to ^10-9 torr range Neutralization gun: Use

Among the peaks attributed to the 1s orbit of the obtained oxygen atom, the peak of the component having the peak top in the range of 532 eV or more and 534 eV or less of the binding energy and the component having the peak top in the range of 529 eV or more and less than 532 eV of the binding energy. For each of the peaks, waveform separation is performed using a plurality of 70% Gaussian and 30% Lorentzian linearities with the half-value width and intensity as fitting parameters, and the component having a peak top in the range of binding energy of 532 eV or more and 534 eV or less. The area (F) and the area (G) of the component having the peak top in the range where the binding energy is 529 eV or more and less than 532 eV were determined, respectively.

[Analysis of polymer]
(1) Polymerization activity The weight of the obtained polymer per unit weight of the solid catalyst component used in the polymerization reaction was defined as the polymerization activity (unit: g-polymer / g-solid catalyst component).

(2) Amount of xylene-soluble component (CXS: unit = weight%)
The amount of the xylene-soluble component at 20 ° C. (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 mixture was slowly cooled to 50 ° C., then immersed in ice water and cooled to 20 ° C. with stirring, and left at 20 ° C. for 3 hours. The precipitated polymer was filtered off, and the weight percentage of the polymer remaining in the filtrate was defined as CXS.

(3) Extreme viscosity ([η]: unit = dL / g)
The ultimate viscosity of the olefin polymer (hereinafter abbreviated as [η]) was measured as follows.
Using an Ubbelohde viscometer, the reduced viscosities of the three samples at concentrations of 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL were measured. The ultimate viscosity is calculated by the calculation method described in Reference "Polymer Solution, Polymer Experiment 11" (published by Kyoritsu Publishing Co., Ltd., 1982), that is, the reduced viscosity is plotted against the concentration, and the concentration is set to zero. It was obtained by the extrapolation method of extrapolating to. The measurement was carried out at a temperature of 135 ° C. using tetralin as a solvent.

(4) Amount of fine powder in the polymer The polymer powder was sprayed with an antistatic agent SB-8 manufactured by Showa Globe Co., Ltd. in advance. As a classifier, a vibrating sieve and a sieve having a sieve mesh opening of 1 mm were used, shaken with an amplitude of 0.35 mm, and the weight was measured every 5 minutes to obtain the weight of the subsieving component when the weight change disappeared. The weight percentage of the obtained under-sieving component with respect to the entire polymerized powder was defined as the amount of fine powder.

(Manufacturing Example 1)
(1) Synthesis of ethyl 3,3-dimethylbutanoate At room temperature, 120 g of 3,3-dimethylbutanoic acid and 78 mg of N, N-dimethylformamide were added to a 500 mL 4-neck round bottom flask substituted with nitrogen. To the mixture in the flask, 129 g of thionyl chloride was added dropwise at 55 ° C. over 4 hours, and then the reaction was carried out for 2 hours. The obtained mixture was cooled to 0 to 5 ° C., 52.2 g of ethanol was added dropwise over 3 hours, and the reaction was carried out at 0 to 10 ° C. After adding 81.6 g of heptane to the obtained reaction solution, the mixture was washed with 78 g of water, 142 g of a 45 wt% potassium carbonate aqueous solution, and 78 g of water. Concentration under reduced pressure gave 212 g of ethyl 3,3-dimethylbutanoate.
At 20 ° C., 114.6 g of diisopropylamine and 681 g of tetrahydrofuran were added to a 3.0 L 4-neck round bottom flask substituted with nitrogen. To the mixture in the flask, 363 g of a 20 wt% normal butyllithium cyclohexane solution at 5 ° C. or lower was added over 6 hours.
(2) Synthesis of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate 204 g of a normal heptane solution containing 67% by weight of ethyl 3,3-dimethylbutaneate was added dropwise over 2 hours. Next, 215 g of a normal heptane solution containing 50% by weight of chloromethyl ethyl ether was added dropwise over 8 hours. The obtained reaction solution was heated to 20 ° C. and reacted for 1 hour, and then 695 g of a 16 wt% sulfuric acid aqueous solution was added dropwise. An organic component was extracted using 251 g of normal heptane as an extraction solvent. The organic component was washed with 584 g of water, concentrated under reduced pressure, and then distilled to obtain 115.8 g of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (yield 60.5%, purity 98.3%). Got

[Example 1]
(1) Synthesis of solid catalyst component for olefin polymerization (1-1A): A 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen. 36.0 mL of toluene and 22.5 mL of titanium tetrachloride were added to the flask and stirred to obtain a toluene solution of titanium tetrachloride. After the temperature in the flask was set to 10 ° C., 0.75 g of magnesium diethoxydo (spherical, particle size 65 μm, bulk density 0.279 g / mL) was added 10 times every 6 minutes at the same temperature. Then, the slurry in the flask was stirred at 10 ° C. for 30 minutes, and 1.80 mL of dinormal butyl phthalate was put into the flask. The temperature in the flask was then raised to 110 ° C. and the mixture in the flask was stirred at the same temperature for 2 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 52.5 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): Toluene (22.5 mL) was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride was added to the slurry to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 52.5 mL of toluene at 100 ° C., and 3 times with 52.5 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. The titanium atom content of this solid catalyst component is 3.34% by weight, the ethoxy group content is 0.66% by weight, and the internal electron donor content is 13.78% by weight, as determined by XPS analysis. The amount of the peak component derived from the oxygen atom 1s orbit and having the peak top in the range of 532 to 534 eV is 80.6 area%, and the amount of the peak component having the peak top in the range of the binding energy of 529 to 532 eV. Was 19.4 area%. The total pore volume by the mercury intrusion method is 0.95 mL / g, the total volume of the pores in the pore radius range of 5 to 30 nm is 0.115 mL / g, and the fine pores in the pore radius range of 30 to 700 nm. The total volume of the pores was 0.071 mL / g and the specific surface area was 83.49 m ² / g. The central particle size by the laser diffraction / scattering method was 55.8 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 6.2%. The analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.

(2) Polymerization of propylene After the autoclave with an internal volume of 3 L was sufficiently dried, the inside was evacuated. 2.63 mmol of triethylaluminum (organoaluminium 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) were added to the autoclave. Then 780 g of propylene and 0.2 MPa of hydrogen were added to the autoclave. The temperature of the autoclave was raised to 80 ° C. and propylene was polymerized at 80 ° C. for 1 hour. After completion of the polymerization reaction, the unreacted monomer was purged to obtain a propylene polymer. The amount of polymer produced (polymerization activity) per unit amount of catalyst was 78,600 g-polymer / g-solid catalyst component. The CXS of this polymer was 1.35 wt%, [η] was 1.13 dL / g, and the amount of fine powder in the polymer was 2.5% by weight. The analysis results of the obtained polymer are shown in Table 4.

[Comparative Example 1]
(1) Synthesis of solid catalyst component for olefin polymerization (1-1A): A 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen. 1.0 mL of toluene and 22.5 mL of titanium tetrachloride were added to the flask and stirred to obtain a toluene solution of titanium tetrachloride. Next, a suspension prepared from 7.5 g of magnesium diethoxydo (spherical, particle size 65 μm, bulk density 0.279 g / mL) and 35 mL of toluene was divided into 10 times every 6 minutes, and a solution at 10 ° C. It was added to the solution kept at warm temperature. Then, the slurry in the flask was stirred at 10 ° C. for 30 minutes, and 1.80 mL of dinormal butyl phthalate was put into the flask. The temperature in the flask was then raised to 110 ° C. and the mixture in the flask was stirred at the same temperature for 2 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 52.5 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): Toluene (52.5 mL) was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride was added to the slurry to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 52.5 mL of toluene at 100 ° C., and 3 times with 52.5 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. The titanium atom content of this solid catalyst component is 3.45% by weight, the ethoxy group content is 0.69% by weight, the internal electron donor content is 12.98% by weight, and oxygen by XPS analysis. The amount of the peak component derived from the atomic 1s orbit and having the peak top in the range of 532 to 534 eV is 74.9 area%, and the amount of the peak component having the peak top in the range of the binding energy of 529 to 532 eV is It was 25.1 area%. The total pore volume by the mercury intrusion method is 0.92 mL / g, the total volume of the pores in the pore radius range of 5 to 30 nm is 0.106 mL / g, and the fine pores in the pore radius range of 30 to 700 nm. The total volume of the pores was 0.073 mL / g and the specific surface area was 77.53 m ² / g. The central particle size by the laser diffraction / scattering method was 54.0 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 6.6%. The analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.

(2) Polymerization of propylene The formation and polymerization of the polymerization catalyst were carried out in the same manner as in Example 1. The amount of polymer produced (polymerization activity) per unit amount of catalyst was 77,700 g-polymer / g-solid catalyst component. The CXS of this polymer was 1.57 wt%, [η] was 1.12 dL / g, and the amount of fine powder in the polymer was 4.4% by weight. The analysis results of the obtained polymer are shown in Table 4.

[Example 2]
(1) Synthesis of solid catalyst component for olefin polymerization (1-1A): A 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen. 36.0 mL of toluene and 22.5 mL of titanium tetrachloride were added to the flask and stirred to obtain a toluene solution of titanium tetrachloride. After the temperature in the flask was set to 0 ° C., 0.75 g of magnesium diethoxydo (spherical, central particle size 37 μm, bulk density 0.260 g / mL) was added 10 times every 6 minutes at the same temperature. Then, the slurry in the flask was stirred at 0 ° C. for 90 minutes, and 0.60 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was charged into the flask. Then, the temperature was raised to 10 ° C., and the mixture was stirred at the same temperature for 2 hours, and then the temperature was started. At 60 ° C., 4.80 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was placed in a flask and the temperature was raised to 110 ° C. The mixture in the flask was stirred at the same temperature for 2 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 56.3 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): Toluene (45.0 mL) was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride was added to the slurry to form a mixture, and the temperature was raised to 70 ° C. After adding 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate to the flask at the same temperature, the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 56.3 mL of toluene at 100 ° C., and 3 times with 56.3 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. The titanium atom content of this solid catalyst component was 1.86% by weight, the central particle size by the laser diffraction / scattering method was 33.0 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 3.9%. .. The analysis results of the solid catalyst component for olefin polymerization are shown in Table 2.

[Comparative Example 2]
(1) Synthesis of solid catalyst component for olefin polymerization (1-1A): After replacing a 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer with nitrogen, 1.0 mL of toluene and tetrachloride are added to the flask. 22.5 mL of titanium was added and stirred to obtain a toluene solution of titanium tetrachloride. Next, a suspension prepared from 7.5 g of magnesium diethoxydo (spherical, particle size 37 μm, bulk density 0.260 g / mL) and 35 mL of toluene was divided into 10 times every 6 minutes, and a solution at 0 ° C. It was added to the mixed solution kept at warm temperature. Then, the slurry in the flask was stirred at 0 ° C. for 90 minutes, and 0.60 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was charged into the flask. Then, the temperature was raised to 10 ° C., and the mixture was stirred at the same temperature for 2 hours, and then the temperature was started. At 60 ° C., 4.80 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was placed in a flask and the temperature was raised to 110 ° C. The mixture in the flask was stirred at the same temperature for 2 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 56.3 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): Toluene (45.0 mL) was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride was added to the slurry to form a mixture, and the temperature was raised to 70 ° C. After adding 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate to the flask at the same temperature, the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 56.3 mL of toluene at 100 ° C., and 3 times with 56.3 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. The titanium atom content of this solid catalyst component was 1.89% by weight, the central particle size by the laser diffraction / scattering method was 33.0 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 4.4%. .. The analysis results of the solid catalyst component for olefin polymerization are shown in Table 2.

[Example 3]
(1) Synthesis of solid catalyst component for olefin polymerization (1-1A): After replacing a 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer with nitrogen, 36.0 mL of toluene and tetrachloride are added to the flask. 22.5 mL of titanium was added and stirred to obtain a toluene solution of titanium tetrachloride. After the temperature in the flask was set to 10 ° C., 0.75 g of magnesium diethoxydo was added 10 times every 6 minutes at the same temperature. Then, the slurry in the flask was stirred at 10 ° C. for 30 minutes. Then, the temperature in the flask was raised, and at 60 ° C., 3.45 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was put into the flask, and the temperature was raised to 110 ° C. Then, the mixture in the flask was stirred at the same temperature for 2 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 52.5 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): Toluene (22.5 mL) was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to the slurry to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 52.5 mL of toluene at 100 ° C., and 3 times with 52.5 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. The titanium atom content of this solid catalyst component is 2.03% by weight, the ethoxy group content is 0.33% by weight, the internal electron donor content is 14.38% by weight, and oxygen by XPS analysis. The amount of the peak component derived from the atomic 1s orbit and having the peak top in the range of 532 to 534 eV is 91.9 area%, and the amount of the peak component having the peak top in the range of the binding energy of 529 to 532 eV is It was 8.1 area%. The central particle size by the laser diffraction / scattering method was 63.9 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 5.2%. The analysis results of the solid catalyst component for olefin polymerization are shown in Table 2.

(2) Polymerization of propylene The formation and polymerization of the polymerization catalyst were carried out in the same manner as in Example 1. The amount of polymer produced (polymerization activity) per unit amount of catalyst was 47,500 g-polymer / g-solid catalyst component. The CXS of this polymer was 0.72 wt%, and [η] was 1.18 dL / g. The analysis results of the obtained polymer are shown in Table 4.

[Example 4]
(1) Synthesis of solid catalyst component for olefin polymerization (1-1A): A 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen. 36.0 mL of toluene and 22.5 mL of titanium tetrachloride were added to the flask and stirred to obtain a toluene solution of titanium tetrachloride. After the temperature in the flask was set to 0 ° C., 0.75 g of magnesium diethoxydo was added 10 times every 6 minutes at the same temperature. Then, the temperature in the flask was raised, and at 60 ° C., 3.45 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was put into the flask, and the temperature was raised to 110 ° C. Then, the mixture in the flask was stirred at the same temperature for 2 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 52.5 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): Toluene (22.5 mL) was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to the slurry to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 52.5 mL of toluene at 100 ° C., and 3 times with 52.5 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. The titanium atom content of this solid catalyst component is 2.04% by weight, the ethoxy group content is 0.35% by weight, the internal electron donor content is 14.5% by weight, and oxygen by XPS analysis. The amount of peak component derived from the atom 1s orbit and having a peak position in the range of 532 to 534 eV for binding energy is 95.0 area%, and the amount of peak component having a peak position in the range of 529 to 532 eV for the binding energy is It was 5.0 area%. The central particle size by the laser diffraction / scattering method was 65.6 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 4.6%. The analysis results of the solid catalyst component for olefin polymerization are shown in Table 2.

(2) Polymerization of propylene The formation and polymerization of the polymerization catalyst were carried out in the same manner as in Example 1. The amount of polymer produced (polymerization activity) per unit amount of catalyst was 54,500 g-polymer / g-solid catalyst component. The CXS of this polymer was 0.79 wt%, and [η] was 1.20 dL / g. The analysis results of the obtained polymer are shown in Table 4.

[Example 5]
(1) Synthesis of solid catalyst component for olefin polymerization (1-1A): After replacing a 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer with nitrogen, 36.0 mL of toluene and tetrachloride are added to the flask. 22.5 mL of titanium was added and stirred to obtain a toluene solution of titanium tetrachloride. After setting the temperature in the flask to 0 ° C., 1.88 g of magnesium diethoxydo was added 4 times every 30 minutes at the same temperature, and then the mixture was stirred at 0 ° C. for 1.5 hours. Then, 0.60 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was put into the flask, and then the temperature inside the flask was raised to 10 ° C. Then, the mixture was stirred at the same temperature for 2 hours, and 9.8 mL of toluene was added. Next, the temperature in the flask was raised, and at 60 ° C., 3.15 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was added into the flask, and the temperature was raised to 110 ° C. The mixture in the flask was stirred at the same temperature for 3 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 56.3 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): 38.3 mL of toluene was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to the slurry to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 56.3 mL of toluene at 60 ° C., and 3 times with 56.3 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. For this solid catalyst component, the titanium atom content is 2.53% by weight, the ethoxy group content is 0.44% by weight, and the internal electron donor content is 13.7% by weight, as determined by XPS analysis. The amount of peak component derived from the oxygen atom 1s orbit and having a peak position in the range of 532 to 534 eV for the binding energy is 85.0 area%, and the amount of the peak component having the peak position in the range of 529 to 532 eV for the binding energy. Was 15.0 area%. The total pore volume by the mercury intrusion method is 1.43 mL / g, the total volume of the pores in the pore radius range of 5 to 30 nm is 0.160 mL / g, and the fine pores in the pore radius range of 30 to 700 nm. The total volume of the pores was 0.317 mL / g and the specific surface area was 107.44 m ² / g. The central particle size by the laser diffraction / scattering method was 59.5 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 5.3%. The analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.

(2) Polymerization of propylene The formation and polymerization of the polymerization catalyst were carried out in the same manner as in Example 1. The amount of polymer produced (polymerization activity) per unit amount of catalyst was 61,700 g-polymer / g-solid catalyst component. The CXS of this polymer was 0.63 wt%, and [η] was 1.20 dL / g. The analysis results of the obtained polymer are shown in Table 4.

[Example 6]
(1) Synthesis of solid catalyst component for olefin polymerization (1-1A): A 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen. 36.0 mL of toluene and 22.5 mL of titanium tetrachloride were added to the flask and stirred to obtain a toluene solution of titanium tetrachloride. After setting the temperature in the flask to 0 ° C., 1.88 g of magnesium diethoxydo was added 4 times every 30 minutes at the same temperature, and then the mixture was stirred at 0 ° C. for 1.5 hours. Then, 0.60 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was put into the flask, and then the temperature inside the flask was raised to 10 ° C. Then, the mixture was stirred at the same temperature for 2 hours, and 9.8 mL of toluene was added. Next, the temperature in the flask was raised, and at 60 ° C., 3.15 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was added into the flask, and the temperature was raised to 110 ° C. The mixture in the flask was stirred at the same temperature for 3 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 52.5 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): 29.1 mL of toluene was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to the slurry to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 29.1 mL of toluene at 100 ° C., further washed 3 times with 52.5 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. The titanium atom content of this solid catalyst component is 2.56% by weight, the ethoxy group content is 0.46% by weight, the internal electron donor content is 14.11% by weight, and oxygen by XPS analysis. The amount of the peak component derived from the atomic 1s orbit and having the peak top in the range of 532 to 534 eV is 87.8 area%, and the amount of the peak component having the peak top in the range of the binding energy of 529 to 532 eV is It was 12.2 area%. The total pore volume by the mercury intrusion method is 1.35 mL / g, the total volume of the pores in the pore radius range of 5 to 30 nm is 0.134 mL / g, and the fine pores in the pore radius range of 30 to 700 nm. The total volume of the pores was 0.298 mL / g and the specific surface area was 93.82 m ² / g. The central particle size by the laser diffraction / scattering method was 56.5 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 5.2%. The analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.

(2) Polymerization of propylene The formation and polymerization of the polymerization catalyst were carried out in the same manner as in Example 1. The amount of polymer produced (polymerization activity) per unit amount of catalyst was 71,200 g-polymer / g-solid catalyst component. The CXS of this polymer was 0.75 wt% and [η] was 1.22 dL / g. The analysis results of the obtained polymer are shown in Table 4.

[Example 7]
(1) Synthesis of solid catalyst component for olefin polymerization (1-1A): A 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen. Toluene (43.3 mL) and titanium tetrachloride (15.2 mL) were placed in the flask and stirred to obtain a toluene solution of titanium tetrachloride. After setting the temperature in the flask to 0 ° C., 1.88 g of magnesium diethoxydo was added 4 times every 30 minutes at the same temperature, and then the mixture was stirred at 0 ° C. for 1.5 hours. Then, 0.60 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was put into the flask, and then the temperature inside the flask was raised to 10 ° C. Then, the mixture was stirred at the same temperature for 2 hours, and 7.4 mL of toluene was added. Next, the temperature inside the flask was raised, and at 60 ° C., 3.00 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was added into the flask, and the temperature was raised to 110 ° C. The mixture in the flask was stirred at the same temperature for 3 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 52.5 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): 29.1 mL of toluene was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to the slurry to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 52.5 mL of toluene at 100 ° C., and 3 times with 52.5 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. The titanium atom content of this solid catalyst component is 2.17% by weight, the ethoxy group content is 0.53% by weight, the internal electron donor content is 12.11% by weight, and oxygen by XPS analysis. The amount of the peak component derived from the atomic 1s orbit and having the peak top in the range of 532 to 534 eV is 83.3 area%, and the amount of the peak component having the peak top in the range of the binding energy of 529 to 532 eV is It was 16.7 area%. The total pore volume by the mercury intrusion method is 1.39 mL / g, the total volume of the pores in the pore radius range of 5 to 30 nm is 0.150 mL / g, and the fine pores in the pore radius range of 30 to 700 nm. The total volume of the pores was 0.298 mL / g and the specific surface area was 97.24 m ² / g. The central particle size by the laser diffraction / scattering method was 61.6 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 5.3%. The analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.

(2) Polymerization of propylene The formation and polymerization of the polymerization catalyst were carried out in the same manner as in Example 1. The amount of polymer produced (polymerization activity) per unit amount of catalyst was 63,600 g-polymer / g-solid catalyst component. The CXS of this polymer was 0.67 wt%, and [η] was 1.19 dL / g. The analysis results of the obtained polymer are shown in Table 4.

[Example 8]
(1) Synthesis of solid catalyst component for olefin polymerization (1-1A): A 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer was replaced with nitrogen. Toluene (43.3 mL) and titanium tetrachloride (15.2 mL) were placed in the flask and stirred to obtain a toluene solution of titanium tetrachloride. After setting the temperature in the flask to 0 ° C., 1.88 g of magnesium diethoxydo was added 4 times every 30 minutes at the same temperature, and then the mixture was stirred at 0 ° C. for 1.5 hours. Next, the temperature inside the flask was raised to 10 ° C. Then, the mixture was stirred at the same temperature for 2 hours, and 7.4 mL of toluene was added. Next, the temperature inside the flask was raised, and at 60 ° C., 3.00 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was added into the flask, and the temperature was raised to 110 ° C. The mixture in the flask was stirred at the same temperature for 3 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 52.5 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): 29.1 mL of toluene was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride was added to the slurry to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 52.5 mL of toluene at 100 ° C., and 3 times with 52.5 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. The titanium atom content of this solid catalyst component is 2.74% by weight, the ethoxy group content is 0.52% by weight, the internal electron donor content is 11.35% by weight, and oxygen by XPS analysis is used. The amount of the peak component derived from the atomic 1s orbit and having the peak top in the range of 532 to 534 eV is 88.1 area%, and the amount of the peak component having the peak top in the range of the binding energy of 529 to 532 eV is It was 11.9 area%. The total pore volume by the mercury intrusion method is 1.48 mL / g, the total volume of the pores in the pore radius range of 5 to 30 nm is 0.139 mL / g, and the fine pores in the pore radius range of 30 to 700 nm. The total volume of the pores was 0.368 mL / g and the specific surface area was 96.06 m ² / g. The central particle size by the laser diffraction / scattering method was 57.8 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 4.5%. The analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.

(2) Polymerization of propylene The formation and polymerization of the polymerization catalyst were carried out in the same manner as in Example 1. The amount of polymer produced (polymerization activity) per unit amount of catalyst was 71,800 g-polymer / g-solid catalyst component. The CXS of this polymer was 0.78 wt% and [η] was 1.17 dL / g. The analysis results of the obtained polymer are shown in Table 4.

[Example 9]
(1) Synthesis step of solid catalyst component for olefin polymerization (1-1A): After replacing a 100 mL flask equipped with a stirrer, a dropping funnel and a thermometer with nitrogen, 43.3 mL of toluene and tetrachloride are added to the flask. 15.2 mL of titanium was added and stirred to obtain a toluene solution of titanium tetrachloride. After setting the temperature in the flask to 0 ° C., 1.88 g of magnesium diethoxydo was added 4 times every 30 minutes at the same temperature, and then the mixture was stirred at 0 ° C. for 1.5 hours. Then, 0.60 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was put into the flask, and then the temperature inside the flask was raised to 10 ° C. Then, the mixture was stirred at the same temperature for 2 hours, and 7.4 mL of toluene was added. Next, the temperature in the flask was raised, and at 60 ° C., 2.53 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate was added into the flask, and the temperature was raised to 110 ° C. The mixture in the flask was stirred at the same temperature for 3 hours. The obtained mixture was solid-liquid separated to obtain a solid. The solid was washed 3 times with 52.5 mL of toluene at 100 ° C. Table 1 shows the results of the step of obtaining a slurry containing a solid product.
Step (1-1B): 29.1 mL of toluene was added to the washed solid to form a slurry. 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to the slurry to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour. Then, the stirred mixture is solid-liquid separated, the solid is washed 3 times with 52.5 mL of toluene at 100 ° C., and 3 times with 52.5 mL of hexane at room temperature, and the washed solid is dried under reduced pressure. Obtained a solid catalyst component for olefin polymerization. The titanium atom content of this solid catalyst component is 2.30% by weight, the ethoxy group content is 0.44% by weight, the internal electron donor content is 12.56% by weight, and oxygen by XPS analysis. The amount of the peak component derived from the atomic 1s orbit and having the peak top in the range of 532 to 534 eV is 92.2 area%, and the amount of the peak component having the peak top in the range of the binding energy of 529 to 532 eV is It was 7.8 area%. The total pore volume by the mercury intrusion method is 1.43 mL / g, the total volume of the pores in the pore radius range of 5 to 30 nm is 0.165 mL / g, and the fine pores in the pore radius range of 30 to 700 nm. The total volume of the pores was 0.328 mL / g and the specific surface area was 94.27 m ² / g. The central particle size by the laser diffraction / scattering method was 54.9 μm, and the cumulative percentage of the components having a particle size of 10 μm or less was 5.4%. The analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.

(2) Polymerization of propylene The formation and polymerization of the polymerization catalyst were carried out in the same manner as in Example 1. The amount of polymer produced (polymerization activity) per unit amount of catalyst was 61,100 g-polymer / g-solid catalyst component. The CXS of this polymer was 0.69 wt%, and [η] was 1.21 dL / g. The analysis results of the obtained polymer are shown in Table 4.

In the type column of the internal electron donor in Table 1 below, "C" means dinormal butyl phthalate and "D" means ethyl 2-ethoxymethyl-3,3-dimethylbutanoate.

The present invention can be used in the production of olefin polymers.

Claims (10)

A method for producing a solid catalyst component for olefin polymerization containing a titanium atom, a magnesium atom, a halogen atom and a β-alkoxy ester compound.
A step (I) of contacting a titanium halide compound solution containing a titanium halide compound and a solvent with a magnesium compound to obtain a slurry containing a solid product.
In step (I), a method for producing a solid catalyst component for olefin polymerization, wherein the ratio (A / C) of A represented by the following formula (1) to C represented by the following formula (2) is 3 or less. ..
A = a / b (1)
(In the formula, a represents the volume (mL) of the titanium halide compound contained in the titanium halide compound solution, and b represents the volume (mL) of the solvent contained in the titanium halide compound solution.)
C = a / c (2)
(In the formula, a represents the volume (mL) of the titanium halide compound contained in the titanium halide compound solution, and c represents the volume (mL) of the solvent contained in the slurry containing the solid product.) The production method according to claim 1, wherein in the step (I), the ratio (A / C) of A represented by the formula (1) to C represented by the formula (2) is 2 or less. The production method according to claim 1 or 2 , wherein the magnesium compound is added to the titanium halide compound solution in the step (I). The production method according to any one of claims 1 to 3, wherein the magnesium compound is magnesium dialkoxide. The production method according to any one of claims 1 to 4, further comprising a step (II) of adding an internal electron donor to a slurry containing a solid product. It contains a β-alkoxy ester compound, a titanium atom, a magnesium atom, and a halogen atom.
A solid catalyst component for olefin polymerization that satisfies the following requirements (I) to (IV).
(I) The total pore volume measured by the mercury intrusion method according to the standard ISO15901-1: 2005 is 0.95 to 1.80 mL / g, and the specific surface area measured by the mercury intrusion method according to the standard ISO15901: 1: 2005. Is 60 to 170 m ² / g.
(II) In accordance with 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 the laser diffraction / scattering method shall be 6.5% or less.
(III) According to the standard ISO15472: 2001, among the peak components obtained by waveform-separating the peaks belonging to the 1s orbit of oxygen atoms obtained by X-ray photoelectron spectroscopy, the binding energy peaks in the range of 532 eV or more and 534 eV or less. The ratio (G / F) of the area (G) of the peak component having the peak top to the area (F) of the peak component having the peak in the range where the binding energy is 529 eV or more and less than 532 eV is 0.33 or less.
(IV) The titanium content is 1.50 to 3.40 wt%. The total volume of pores having a pore radius of 30 to 700 nm (α) with respect to the total volume (α) of pores having a pore radius of 5 to 30 nm measured by the mercury intrusion method according to the standard ISO15901-1: 2005. The solid catalyst component for olefin polymerization according to claim 6, wherein the ratio (β / α) of β) is in the range of 0.45 to 3.0. The solid catalyst component for olefin polymerization according to claim 6 or 7 , wherein the β-alkoxy ester compound is ethyl 2-ethoxymethyl-3,3-dimethylbutanoate. A catalyst for olefin polymerization, which comprises the solid catalyst component for olefin polymerization according to any one of claims 6 to 8 and an organoaluminum compound. A method for producing an olefin polymer, which polymerizes an olefin in the presence of the catalyst for olefin polymerization according to claim 9.