WO2018025862A1 - Procédé de production d'un constituant catalytique solide pour la polymérisation d'oléfines - Google Patents

Procédé de production d'un constituant catalytique solide pour la polymérisation d'oléfines Download PDF

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WO2018025862A1
WO2018025862A1 PCT/JP2017/027902 JP2017027902W WO2018025862A1 WO 2018025862 A1 WO2018025862 A1 WO 2018025862A1 JP 2017027902 W JP2017027902 W JP 2017027902W WO 2018025862 A1 WO2018025862 A1 WO 2018025862A1
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compound
catalyst component
olefin polymerization
solid catalyst
solid
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PCT/JP2017/027902
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English (en)
Japanese (ja)
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幸平 糸永
直広 田中
吉田　健
真 植村
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住友化学株式会社
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Priority to JP2018531923A priority Critical patent/JP6915618B2/ja
Publication of WO2018025862A1 publication Critical patent/WO2018025862A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • 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.
  • 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.
  • JP 2010-1420 A JP-A-2-289604
  • 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 that gives a highly stereoregular polymer when olefin is polymerized. It is.
  • the present invention provides the following.
  • a method for producing a solid catalyst component for olefin polymerization comprising a titanium atom, a magnesium atom, a halogen atom and an internal electron donor, A step (I) in which a titanium halide compound solution containing a halogenated titanium compound and a solvent is contacted with a magnesium compound to obtain a slurry containing a solid product;
  • the ratio (A / C) of A represented by the following formula (1) to C represented by the following formula (2) is 3 or less, and the method for producing a solid catalyst component for olefin polymerization .
  • A a / b (1) (Wherein, 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) (Wherein, 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 a magnesium compound is added to the titanium halide compound solution in the step (I).
  • 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 ⁇ -alkoxyester compound, and a diether compound, [1] or [2 ] The manufacturing method of description.
  • 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 ⁇ -alkoxy ester compound and a diether compound, a titanium atom, a magnesium atom, Containing halogen atoms,
  • a solid catalyst component for olefin polymerization that satisfies the following requirements (I) to (IV).
  • the total pore volume measured by mercury intrusion method according to standard ISO 15901-1: 2005 is 0.95-1.80 mL / g, and the specific surface area measured by mercury intrusion method according to standard ISO 15901-1: 2005 Is 60 to 170 m 2 / g.
  • the cumulative percentage of the component having a size of 10 ⁇ m or less is 6.5% or less in the volume-based particle size distribution measured by the laser diffraction / scattering method.
  • the peak is 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 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 having the top is 0.33 or less.
  • the titanium content is 1.50 to 3.40 wt%.
  • the production method of the present invention is a method for producing a solid catalyst component for olefin polymerization comprising a titanium atom, a magnesium atom, a halogen atom and an internal electron donor, A step (I) in which a titanium halide compound solution containing a halogenated titanium compound and a solvent is contacted with a magnesium compound to obtain a slurry containing a solid product; In 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) (Wherein, 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) (Wherein, 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 “solid catalyst component for olefin polymerization” is a solid component in at least toluene, and becomes a catalyst for olefin polymerization by being combined with an olefin polymerization cocatalyst such as an organoaluminum compound. means.
  • the halogenated titanium compound means a compound containing a halogen atom and a titanium atom, wherein at least one halogen atom is bonded to the titanium atom.
  • Specific examples include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; methoxy titanium trichloride, ethoxy titanium trichloride, n-propoxy titanium trichloride, n-butoxy titanium trichloride.
  • trihalogenated monoalkoxy titaniums such as ethoxytitanium tribromide
  • dihalogens such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diiso-propoxytitanium dichloride, di-n-propoxytitanium dichloride, and diethoxytitanium dibromide
  • dihalogens such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diiso-propoxytitanium dichloride, di-n-propoxytitanium dichloride, and diethoxytitanium dibromide
  • trimethoxytitanium chloride triethoxytitanium chloride, triiso-propoxytitanium chloride, tri-n-propoxytitanium chloride, and tri-n-butoxytitanium chloride
  • Tetrahalogenated titanium or trihalogenated monoalkoxytitanium is preferable, tetrahalogenated titanium is more preferable, and titanium tetrachloride is more preferable. Titanium halide compounds may be used alone or in combination of two or more.
  • Part or all of the titanium atoms in the solid catalyst component for olefin polymerization are derived from a 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 any compound containing a magnesium atom, and specific examples include compounds represented by the following formulas (i) to (iii). MgR 1 k X 2-k (i) Mg (OR 1 ) m X 2-m (ii) MgX 2 ⁇ nR 1 OH (iii) (Wherein 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 A hydrocarbyl group having 1 to 20 atoms; X is a halogen atom.)
  • R 1 in the formulas (i) to (iii) include an alkyl group, an aralkyl group, an aryl group, an alkenyl group, etc., and some or all of the hydrogen atoms contained in these groups are halogen atoms, hydrocarbyl groups, and the like. It may be substituted with a biloxy group, a nitro group, a sulfonyl group, a silyl group, or the like.
  • alkyl group for R 1 examples 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 group, iso-butyl group, tert-butyl group, iso-pentyl group, neopentyl group, and 2-ethylhexyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl And a cyclic alkyl group such as a cycloheptyl group and a cyclooctyl group, 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 for 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 for R 1 include a phenyl group, a naphthyl group, and a tolyl group, and an aryl group having 6 to 20 carbon atoms is preferable.
  • alkenyl group for R 1 examples include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; branched groups such as isobutenyl group and 4-methyl-3-pentenyl group Alkenyl groups; cyclic alkenyl groups such as 2-cyclohexenyl group and 3-cyclohexenyl group, preferably straight-chain 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, preferably a chlorine atom.
  • a plurality of X may be the same or different.
  • magnesium compounds of formulas (i) to (iii) include dimethylmagnesium, diethylmagnesium, diiso-propylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, dicyclohexylmagnesium, and butyloctyl.
  • Dialkylmagnesium such as magnesium; magnesium dialkoxide such as magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, magnesium dibutoxide, magnesium dihexyl oxide, magnesium dioctyl oxide, and magnesium dicyclohexyl oxide; methyl magnesium chloride, ethyl magnesium 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, methylmag
  • magnesium halide or magnesium dialkoxide preferred is magnesium halide or magnesium dialkoxide.
  • 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, particularly preferably a magnesium dialkoxide.
  • magnesium halide a commercially available product may be used as it is, or a precipitate produced by dropping a solution obtained by dissolving a commercially available product in alcohol into a hydrocarbon liquid may be used separately from the liquid.
  • magnesium dialkoxide for example, metal magnesium and alcohol are brought into contact in the presence of a catalyst (for example, JP-A-4-368391, JP-A-3-74341, JP-A-8-73388, And International Publication No. 2013/058193 pamphlet).
  • Alcohols include methanol, ethanol, propanol, butanol, and octanol.
  • Catalysts include halogens such as iodine, chlorine, and bromine; magnesium iodides, and magnesium halides such as magnesium chloride, preferably iodine.
  • the magnesium compound may be supported on a carrier material.
  • the support material include porous inorganic oxides such as SiO 2 , Al 2 O 3 , MgO, TiO 2 , and ZrO 2 ; polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol dimethacrylic acid copolymer Polymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, poly Examples include organic porous polymers such as vinyl chloride, polyethylene, and polypropylene. Of these, porous inorganic oxides are preferable, and SiO 2 is more preferable.
  • the support material is porous from the viewpoint of effectively immobilizing the magnesium compound on the support material, and has a pore radius of 10 to 780 nm determined by a mercury intrusion method according to the standard ISO 15901-1: 2005.
  • a porous carrier material having a total volume of 0.3 cm 3 / g or more is more preferred, and a porous carrier material having a total volume of 0.4 cm 3 / g or more is more preferred.
  • a porous carrier material 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 ⁇ m is preferable, and 30% or more. Some porous support 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 titanium halide compound solution in the form of a magnesium compound slurry containing a magnesium compound and a solvent as long as the effects of the present invention can be obtained. More preferably, it is a body.
  • Part or all of the magnesium atoms in the solid catalyst component for olefin polymerization are derived from the magnesium compound. Moreover, a part of 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 more metal atoms contained in the solid catalyst component for olefin polymerization, and specifically includes a monoester compound and a dicarboxylic acid ester compound. Diol diester compounds, ⁇ -alkoxy ester compounds, and diether compounds.
  • 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.
  • 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, toluyl toluate Examples include butyl acid, pentyl toluate, hexyl toluate, and octyl toluate.
  • 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, 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, valeric acid Hexyl herbate, octyl valerate, methyl caproate, ethyl caproate
  • the dicarboxylic acid ester compound means a compound having two ester bonds (—CO—O—) in the molecule and having a structure in which two carboxyl groups of the dicarboxylic acid are esterified with a monovalent alcohol.
  • Aromatic dicarboxylic acid ester compounds and aliphatic dicarboxylic acid ester compounds are preferred.
  • the aromatic dicarboxylic acid ester compound is a compound that can be synthesized from, for example, an aromatic dicarboxylic acid or aromatic dicarboxylic acid dihalide and a monohydric alcohol.
  • the aliphatic dicarboxylic acid ester compound is a compound that can be synthesized from, for example, an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid dihalide and a monohydric alcohol, and specifically includes dimethyl ethanedioate, diethyl ethanedioate, ethane.
  • Dipropyl diacid Dibutyl ethanedioate, Dipentyl ethanedioate, Dihexyl ethanedioate, Dioctyl ethanedioate, Dimethyl propanedioate, Diethyl propanedioate, Dipropyl propanedioate, Dibutyl propanedioate, Dipentyl propanedioate, Propane Dihexyl diacid, dioctyl propanedioate, dimethyl butanedioate, diethyl butanedioate, dipropyl butanedioate, dibutyl butanedioate, dipentylbutanedioate, dihexyl butanedioate, dioctylbutanedioate, dimethyl pentanedioate, pentane Diethyl diacid, pentane Dipropyl acid, Dibut
  • a diol diester compound is a compound having two ester bonds (—CO—O—) in the molecule, and has a structure in which each of two hydroxyl groups of a diol is esterified with a carboxyl group of a monocarboxylic acid or a dicarboxylic acid.
  • ⁇ -alkoxyester compound means a compound having an alkoxycarbonyl group and having an alkoxy group at the ⁇ -position of the alkoxycarbonyl group, specifically, methyl 2-methoxymethyl-3,3-dimethylbutanoate, 2-methoxymethyl-3,3-dimethylbutanoate ethyl, 2-methoxymethyl-3,3-dimethylbutanoate propyl, 2-methoxymethyl-3,3-dimethylbutanoate butyl, 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, 3-methoxy-2-phenylpropionate, 3-methoxy Butyl-2-phenylprop
  • 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-diphenoxycyclohexan
  • JP2011-246699A an internal electron donor described in JP2011-246699A can also be exemplified.
  • dicarboxylic acid ester compounds preferred are dicarboxylic acid ester compounds, diol diester compounds, and ⁇ -alkoxy ester compounds.
  • the internal electron donors may be used alone or in combination of two or more.
  • the amount of the titanium halide compound used in step (I) is usually 0.01 mol to 100 mol, preferably 0.03 mol to 50 mol, more preferably per mol of the total magnesium atom in the magnesium compound used in step (I). 0.05 mol to 30 mol.
  • solvent in the step (I) is inactive with respect to the solid product generated in the 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 carbonization such as cyclohexane, cyclopentane, methylcyclohexane and decalin And hydrogen; halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene; and ether compounds such as diethyl ether, dibutyl ether, diisoamyl ether and tetrahydrofuran.
  • aromatic hydrocarbons or halogenated hydrocarbons are preferable, and toluene is more preferable.
  • a solvent may be used independently, respectively, and may be used in
  • the contact between the titanium halide compound solution and the magnesium compound is usually performed in an inert gas atmosphere such as nitrogen gas and argon gas.
  • an inert gas atmosphere such as nitrogen gas and argon gas.
  • the magnesium compound may be added at once, or may be divided into arbitrary plural times. Moreover, you may add a magnesium compound continuously.
  • 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 are obtained.
  • Examples of a method for bringing the components into contact with each other include known methods such as a slurry method and a mechanical pulverization method (for example, a method in which components are brought into contact with each other while being pulverized by a ball mill).
  • 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, more preferably 1 mL of the solvent contained in the solution.
  • the amount 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, and more preferably 1 to 24 hours.
  • step (I) a titanium halide compound solution and a magnesium compound so that a ratio (A / C) of A represented by the following formula (1) to C represented by the following formula (2) is 3 or less Contact is made.
  • the volume of the solvent contained in the slurry containing the solid product for calculating the value of A / C is included in the slurry 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 to be removed.
  • A a / b (1) (Wherein, 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) (Wherein, 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.)
  • a / C is preferably 2.5 or less, more preferably 2 or less, further preferably 1.8 or less, and particularly preferably 1.5 or less.
  • a / C is 1 or more.
  • a / C is c / b, which can be the ratio of the volume of the solvent at the end of step (I) to the volume of the solvent at the start of step (I).
  • the solvent used in step (I) is used only for preparing a magnesium compound slurry, or is used to prepare both a titanium halide compound solution and a magnesium compound slurry, and magnesium.
  • the amount of the solvent in the compound slurry is larger than the amount of the solvent in the titanium halide compound solution.
  • the solvent used in step (I) is more concentrated in 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. Or is used only for the preparation of the titanium halide compound solution (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 includes 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 the step (I). That is, when A / C is greater than 1, the increased amount of solvent can come from the solvent in the magnesium compound slurry and / or the solvent added alone during step (I).
  • step (I) since A / C is 3 or less, the amount of change in the solvent from the start of the reaction in step (I) to the end of the reaction 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.
  • the olefin polymerization catalyst containing the olefin polymerization solid catalyst component 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).
  • a particulate olefin polymer is produced by a slurry polymerization method, a solution polymerization method, a bulk polymerization method, or a gas phase polymerization method. In some cases, polymer particles with a small amount of fines 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 process, or may be added to the slurry containing the solid product after step (I), or a combination thereof.
  • 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). It is.
  • the production method of the present invention preferably has a step (II) of adding an internal electron donor to a slurry containing a solid product.
  • 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, it is 30 ° C to 120 ° C.
  • the reaction time is usually 0.1 to 12 hours, preferably 0.5 to 10 hours.
  • the reaction between the solid product and the internal electron donor is usually carried out in an inert gas atmosphere such as nitrogen gas and argon gas.
  • Step (I) and step (II) are each carried out with normal stirring, and the stirring is carried out with the peripheral speed v of the stirring blade represented by the following formula (5) usually in the range of 0.1 to 10 m / sec.
  • the reaction is preferably carried out under the condition of 0.5 to 5.0 m / second, more preferably 1.0 to 3.0 m / second.
  • v n ⁇ d (5)
  • n represents the rotation speed (rad / sec) of the stirring blade
  • d represents the blade diameter (m) of the stirring blade.
  • the obtained solid may be used as a solid catalyst component for olefin polymerization, or the obtained solid is used as a precursor, and one or more of a titanium halide compound, a magnesium compound, and an internal electron donor, and Furthermore, it is good also considering the solid obtained by making it contact as a solid catalyst component for olefin polymerization.
  • the production method of the present invention includes a step (III) of bringing the obtained precursor into contact 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 the solid catalyst component for olefin polymerization, and the solvent is an aliphatic hydrocarbon such as pentane, hexane, heptane and octane; an aromatic such as benzene, toluene and xylene. Examples include aliphatic hydrocarbons; cycloaliphatic hydrocarbons such as cyclohexane and cyclopentane; and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene.
  • the amount of the solvent used for washing can be, for example, 0.1 mL to 1000 mL per 1 g of the solid catalyst component or precursor for olefin polymerization per one stage of contact. The amount is preferably 1 mL to 100 mL per 1 g. Washing is usually performed 1 to 5 times per step.
  • 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 performed in a solvent.
  • the description of the solvent in the step (III) is the same as the description of the solvent in the step (I).
  • the amount of the titanium halide compound is usually 0.1 to 10 mL / mL solvent, preferably 0.1 to 1.0 mL / mL solvent.
  • the magnesium compound is contacted in step (III)
  • the amount of the magnesium compound is usually 0.01 to 10 g / mL solvent, preferably 0.1 to 1.0 g / mL solvent.
  • the amount of the internal electron donor is usually 0.001 to 5 mL / mL solvent, preferably 0.005 to 0.5 mL / mL solvent, more preferably 0. .01-0.1 mL / mL solvent.
  • step (III) The types of the titanium halide compound, magnesium compound and internal electron donor in step (III) may be the same as or different from those in step (I) or (II).
  • the temperature in step (III) is usually ⁇ 20 ° C. to 150 ° C., preferably ⁇ 5 ° C. to 130 ° C., more preferably 40 ° C. to 120 ° C.
  • the contact time is usually 0.1 to 12 hours, preferably 1 to 8 hours.
  • the contact between the precursor and one or more of a titanium halide compound, a magnesium compound and an internal electron donor is usually performed under an inert gas atmosphere such as nitrogen gas and argon gas. Done.
  • Step (III) may be performed once or may be repeated a plurality of times.
  • 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 as described above. Moreover, you may dry (for example, drying under reduced pressure) after washing
  • the solid catalyst component for olefin polymerization of the present invention is a solid catalyst component for olefin polymerization obtained by the above production method.
  • 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 production method in one example.
  • At least one internal electron donor selected from the group consisting of monoester compounds, aliphatic dicarboxylic acid ester compounds, diol diester compounds, ⁇ -alkoxy ester compounds and diether compounds, a titanium atom, a magnesium atom, and a halogen atom
  • the peak top binding energy is 532 eV or more and 534 eV or less.
  • the ratio (G / F) of the peak component area (G) where the binding energy of the peak top 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.
  • the titanium content is 1.50 to 3.40 wt%.
  • the origin of titanium atom, magnesium atom and halogen atom is the same as described above.
  • the description of the monoester compound, aliphatic dicarboxylic acid ester compound, diol diester compound, ⁇ -alkoxy ester compound and diether compound is the same as described above.
  • the internal electron donor is preferably a diol diester compound or a ⁇ -alkoxy ester compound, more preferably a ⁇ -alkoxy ester compound, and still more preferably ethyl 2-ethoxymethyl-3,3-dimethylbutanoate. It is.
  • the requirement (I) will be described below.
  • the total pore volume measured by the mercury intrusion method according to the standard ISO 15901-1: 2005 is 0.95-1.80 mL / g, preferably 1.00-1.70 mL / g, more preferably 1 10 to 1.60 mL / g.
  • the productivity of the polymer is improved.
  • 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 ISO 15901-1: 2005 is 60 to 170 m 2 / g, preferably 80 to 150 m 2 / g, more preferably 88 to 130 m 2 / g. If the specific surface area is 60 m 2 / g or more, sticky components contained in the resulting polymer can be reduced. When the specific surface area is 170 m 2 / g or less, sufficient catalyst particle strength can be secured.
  • the cumulative percentage of components of 10 ⁇ m or less is 6.5% or less, and preferably 6.2% or less. More preferably 6.0% or less, and even 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 peak energy is 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 a peak top in the range where the binding energy is 529 eV or more and less than 532 eV with respect to the area (F) of the peak component is 0.33 or less, It is preferable that it is 0.28 or less.
  • 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%. If the titanium content is 3.40 wt% or less, the sticky component contained in the resulting polymer can be reduced, and if 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 can satisfy at least one, at least two, or all of the requirements (I) to (III) in one embodiment.
  • 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 content of titanium atoms can be determined, for example, by the method of Examples described later.
  • 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 the examples described later.
  • 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.
  • a polymer having high stereoregularity can be obtained when an olefin is polymerized using an olefin polymerization catalyst containing the olefin polymerization catalyst.
  • the olefin polymerization catalyst can be produced by bringing the solid catalyst component for olefin polymerization of the present invention into contact with the organoaluminum compound by, for example, a known method.
  • an olefin polymerization catalyst can be produced by contacting the solid catalyst component for olefin polymerization of the present invention, an organoaluminum compound, and an external electron donor.
  • the catalyst for olefin polymerization of the present invention includes the solid catalyst component for olefin polymerization of the present invention and an organoaluminum compound.
  • the olefin polymerization catalyst of the present invention contains 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 include compounds described in JP-A-10-212319. Among them, preferred is trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane, more preferably triethylaluminum, triiso-butylaluminum, a mixture of triethylaluminum and diethylaluminum chloride or Tetraethyl dialumoxane.
  • Examples of the external electron donor used in the present invention include 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.
  • an oxygen-containing compound or a nitrogen-containing compound is preferable.
  • Examples of the oxygen-containing compound include alkoxy silicon, ether, ester, and ketone. Among them, preferred is alkoxy silicon or ether.
  • the alkoxysilicon as the external electron donor is preferably a compound represented by any one of the following formulas (iv) to (vi).
  • 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 hydrocarbyl group having a carbon number of 1 - 6
  • R 5 and R 6 is hydrocarbyl group of hydrogen or carbon atoms 1 ⁇ 12
  • NR 7 the carbon atom number of 5 to 20 cyclic amino groups
  • 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, and an alkenyl group.
  • Examples of the alkyl group of R 2 and R 3 include a methyl group, an ethyl group, and the like.
  • a linear alkyl group such as a 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 Branched alkyl groups such as tert-butyl, iso-pentyl, neopentyl, and 2-ethylhexyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl
  • a cyclic alkyl group such as this, preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • Examples of the aralkyl group for 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 xylyl group, and an aryl group having 6 to 20 carbon atoms is preferable.
  • alkenyl group for R 2 and R 3 examples 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 A branched alkenyl group such as 2-cyclohexenyl group and a cyclic alkenyl group such as 3-cyclohexenyl group, preferably an alkenyl group having 2 to 10 carbon atoms.
  • alkoxysilicon represented by the above formula (iv) include cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diiso-propyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane.
  • Examples of the hydrocarbyl group of R 4 in the above formulas (v) and (vi) include an alkyl group and an alkenyl group.
  • Examples of the alkyl group of R 4 include a methyl group, an ethyl group, an n-propyl group, n Linear alkyl groups such as -butyl, n-pentyl, and n-hexyl; branched such as iso-propyl, iso-butyl, tert-butyl, iso-pentyl, and neopentyl
  • a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, preferably a linear alkyl group having 1 to 6 carbon atoms.
  • alkenyl group for R 4 examples include linear alkenyl groups such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; branched groups such as iso-butenyl group and 5-methyl-3-pentenyl group
  • a cyclic alkenyl group such as a 2-cyclohexenyl group and a 3-cyclohexenyl group, preferably a linear alkenyl group having 2 to 6 carbon atoms, particularly preferably a methyl group and an ethyl group 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.
  • Examples of the alkyl group of R 5 and R 6 include a methyl group, an ethyl group, and an n-propyl group.
  • Linear alkyl groups such as n-butyl, n-pentyl, and n-hexyl; iso-propyl, iso-butyl, tert-butyl, iso-pentyl, and neopentyl
  • a branched alkyl group; a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and a linear alkyl group having 1 to 6 carbon atoms is preferable.
  • alkenyl group for R 5 and R 6 examples 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 A branched alkenyl group such as 2-cyclohexenyl group and a cyclic alkenyl group such as 3-cyclohexenyl group, preferably a straight-chain alkenyl group having 2 to 6 carbon atoms, particularly preferably A methyl group and an ethyl group.
  • alkoxysilicon represented by the above formula (v) include dimethylaminotrimethoxysilane, diethylaminotrimethoxysilane, di-n-propylaminotrimethoxysilane, dimethylaminotriethoxysilane, diethylaminotriethoxysilane, di -N-propylaminotriethoxysilane, methylethylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, tert-butylaminotriethoxysilane, diiso-propylaminotriethoxysilane, methyliso-propylaminotriethoxysilane Examples include silane.
  • the cyclic amino group of NR 7 in the above formula (vi) includes perhydroquinolino group, perhydroisoquinolino group, 1,2,3,4-tetrahydroquinolino group, 1,2,3,4-tetrahydroiso group.
  • a quinolino group and an octamethyleneimino group are mentioned.
  • alkoxysilicon represented by the above formula (vi) include perhydroquinolinotriethoxysilane, perhydroisoquinolinotriethoxysilane, 1,2,3,4-tetrahydroquinolinotriethoxysilane, Examples 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.
  • External electron donors may be used alone or in combination of two or more.
  • the method for bringing the solid catalyst component for olefin polymerization into contact with the organoaluminum compound and the external electron donor is not particularly limited as long as the olefin polymerization catalyst is produced.
  • Contacting is performed 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 any two-component contact mixture and the remaining components may be contacted. You may supply separately to a polymerization tank and you may make these contact in a polymerization tank.
  • the amount of the organoaluminum compound used is usually 0.01 to 1000 ⁇ mol, preferably 0.1 to 500 ⁇ mol, per 1 mg of the solid catalyst component for olefin polymerization.
  • the amount of the external electron donor to be used is usually 0.0001 to 1000 ⁇ mol, preferably 0.001 to 500 ⁇ mol, more preferably 0.01 to 150 ⁇ mol per 1 mg of the solid catalyst component for olefin polymerization.
  • a polymer having high stereoregularity can be obtained when an olefin is polymerized using the catalyst as described later.
  • ⁇ Olefin polymer production method The method for producing an olefin polymer of the present invention polymerizes an olefin in the presence of the olefin polymerization catalyst of the present invention.
  • olefins examples include ethylene and ⁇ -olefins having 3 or more carbon atoms.
  • ⁇ -olefins include linear monoolefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene; 3-methyl-1-butene, 3-
  • Illustrative examples include branched monoolefins such as methyl-1-pentene and 4-methyl-1-pentene; cyclic monoolefins such as vinylcyclohexane; and combinations of two or more thereof.
  • homopolymerization of ethylene or propylene or copolymerization of a plurality of types of olefins mainly composed of ethylene or propylene.
  • the combination of a plurality of types of olefins may include a combination of two or more types of olefins.
  • a combination of a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene with an olefin. 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 multistage polymerization thereof.
  • the method for forming the olefin polymerization catalyst of the present invention may be preferably a method comprising the following steps: (I) A small amount of olefin (same or different from the olefin used in the original polymerization (usually referred to as main polymerization)) is polymerized (generated) in the presence of the solid catalyst component for olefin polymerization and the organoaluminum compound.
  • a chain transfer agent such as hydrogen may be used, or an external electron donor may be used), and a catalyst component whose surface is covered with the olefin polymer is generated.
  • the prepolymerization is preferably slurry polymerization using an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene and toluene as a solvent.
  • 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 per mol of titanium atom in the solid catalyst component used in the step (i). 1 mol to 200 mol.
  • the amount of olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid catalyst component for olefin polymerization used in step (i).
  • the slurry concentration of the solid catalyst component for olefin polymerization in the slurry polymerization in the step (i) is preferably 1 to 500 g-solid catalyst component for olefin polymerization / liter-solvent, particularly preferably 3 to 300 g-solid catalyst component for olefin polymerization. / L-solvent.
  • the temperature for 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 in the prepolymerization is preferably 0.01 MPa to 2 MPa, particularly preferably 0.1 MPa to 1 MPa.
  • the olefin that is liquid at the prepolymerization pressure or temperature is not limited to this. Absent.
  • 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 to the polymerization tank in the prepolymerization: (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 methods for supplying olefin to the polymerization tank in the prepolymerization: (1) A method of sequentially supplying olefins to the polymerization tank so that the pressure in the polymerization tank is maintained at a predetermined pressure.
  • 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 titanium atom contained in the solid catalyst component for olefin polymerization. 0.03 mol to 100 mol, and 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 the external electron donor to the polymerization tank in the prepolymerization: (1) Method of supplying an external electron donor alone to the polymerization tank (2) Method of supplying a contact product between the external electron donor and the organoaluminum compound to the polymerization tank.
  • the amount of the organoaluminum compound used in the main polymerization is usually 1 mol to 1000 mol, particularly preferably 5 mol to 600 mol, per mol of titanium atom in the solid catalyst component for olefin polymerization.
  • the amount of the external electron donor is usually 0.1 mol to 2000 mol, preferably 0.3 mol to 1000 mol, per mol of titanium atom contained in the solid catalyst component for olefin polymerization.
  • the amount is 0.5 mol to 800 mol, and is usually 0.001 mol to 5 mol, preferably 0.005 mol to 3 mol, particularly preferably 0.01 mol to 1 mol, per mol of the organoaluminum compound.
  • the temperature of the main polymerization is usually ⁇ 30 ° C. to 300 ° C., preferably 20 ° C. to 180 ° C.
  • the polymerization pressure is not particularly limited, and is generally from atmospheric pressure to 10 MPa, preferably from about 200 kPa to 5 MPa in terms of industrial and economic efficiency.
  • the polymerization is batch or continuous, 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 at the polymerization temperature. Examples thereof include a bulk polymerization method using an olefin as a medium and a gas phase polymerization method.
  • a chain transfer agent for example, hydrogen or alkyl zinc such as dimethyl zinc and diethyl zinc
  • alkyl zinc such as dimethyl zinc and diethyl zinc
  • an olefin polymerization catalyst that gives a highly stereoregular polymer when an olefin is polymerized
  • a solid catalyst component for olefin polymerization for producing the olefin polymerization catalyst Moreover, an olefin polymer with high stereoregularity can be obtained by polymerizing an olefin using the olefin polymerization catalyst.
  • the solid catalyst component for olefin polymerization of the present invention is particularly suitable as a catalyst for an isotactic stereoregular olefin polymer.
  • CXS content may be used as a measure of isotactic stereoregularity.
  • 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 obtained, for example, by the method of Examples described later.
  • the solid catalyst component for olefin polymerization and the catalyst for olefin polymerization of the present invention can give polymer particles with a small amount of fine powder when a particulate olefin polymer is produced by a gas phase polymerization method.
  • the amount of fine powder (1 mm or less) in the olefin polymer is preferably 4.0% by weight or less, more preferably 3.0% by weight or less.
  • composition analysis of solid catalyst components (1) Content of titanium atom About 20 mg of a solid sample was decomposed with about 30 mL of 2N dilute sulfuric acid, and then 3 mL of an excess of 3 wt% hydrogen peroxide water was added thereto. Absorption was measured with a UV-visible spectrophotometer model V-650 manufactured by JASCO Corporation according to the standard JIS K0115: 2004, and the content of titanium atoms was determined based on a separately prepared calibration curve.
  • Pore volume The pore distribution of the solid catalyst component in the range of pore radius of about 0.0018 to 100 ⁇ m was measured by mercury porosimetry according to standard ISO 15901-1: 2005. The pore radius was calculated using the Washburn equation. As a measuring device, an 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.
  • Central particle size (D50) of solid catalyst component and cumulative percentage of component of particle size of 10 ⁇ m or less According to standard ISO13320: 2009, the central particle size (D50) and cumulative percentage of component of particle size of 10 ⁇ m or less are determined by laser diffraction / scattering method. Was analyzed. A laser diffraction 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 moisture had been removed in advance with alumina or the like was put into a dispersion apparatus (Hydro MV) whose opening was sealed with nitrogen, and the circulation system including the measurement cell was filled with the solvent.
  • the stirring speed was set to 2,000 rpm, and the particle size was measured by introducing 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 chart (chart), the central particle size (D50) and the cumulative percentage of components having a particle size of 10 ⁇ m or less were determined.
  • the sample was handled so as not to come into contact with air and moisture, and no pretreatment was performed.
  • Binding energy was measured by X-ray photoelectron spectroscopy (XPS) analysis according to the standard ISO15472: 2001. Using AXIS ULTRA DLD manufactured by Kratos Analytical as a measuring device, measurement was performed under the following measurement conditions to obtain a peak attributed to the 1s orbital 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.
  • XPS X-ray photoelectron spectroscopy
  • the peak of the component having a peak top in the range of 532 eV or more and 534 eV or less, and the component having the peak top in the range of the binding energy of 529 eV or more and less than 532 eV For each of the peaks, the waveform separation is performed using a plurality of 70% Gaussian and 30% Lorentzian lines, with the half width and intensity as fitting parameters, respectively, and the peak energy of the component having a peak top in the range of 532 eV to 534 eV
  • the area (F) and the area (G) of the component having a peak top in the range where the binding energy is 529 eV or more and less than 532 eV were determined.
  • CXS 20 ° C. xylene-soluble component amount
  • CXS 20 ° C. xylene-soluble component
  • the amount of the 20 ° C. xylene-soluble component (hereinafter abbreviated as CXS) of the olefin polymer was measured as follows. 1 g of the polymer was dissolved in 200 mL of boiling xylene and then slowly cooled to 50 ° C., then immersed in ice water, cooled to 20 ° C. with stirring, and allowed to stand at 20 ° C. for 3 hours. The precipitated polymer was separated by filtration, and the weight percentage of the polymer remaining in the filtrate was defined as CXS.
  • the intrinsic viscosity (hereinafter abbreviated as [ ⁇ ]) of the olefin polymer was measured as follows. Using an Ubbelohde viscometer, the reduced viscosities of three samples having concentrations of 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL were measured.
  • the intrinsic viscosity is calculated by the method described in the reference document “Polymer solution, polymer experiment 11” (published by Kyoritsu Shuppan Co., Ltd., 1982), that is, the reduced viscosity is plotted against the concentration, and the concentration is zero Was obtained by extrapolation to extrapolate to. Measurement was performed at a temperature of 135 ° C. using tetralin as a solvent.
  • a static electricity removing spray SB-8 manufactured by Showa Grove Co. was previously sprayed on the polymer powder as an antistatic agent.
  • a vibration sieve and a sieve having a sieve opening of 1 mm were used. The shaker was shaken at an amplitude of 0.35 mm, and the weight was measured every 5 minutes. The weight of the under-sieving component when the weight change disappeared was obtained. The weight percentage of the obtained sieving component with respect to the entire polymerization powder was defined as the amount of fine powder.
  • Example 1 Step of synthesizing 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. To the flask, 36.0 mL of toluene and 22.5 mL of titanium tetrachloride were added and stirred to obtain a toluene solution of titanium tetrachloride. After the temperature in the flask was 10 ° C., 0.75 g of magnesium diethoxide (spherical, particle size 65 ⁇ m, bulk density 0.279 g / mL) was added 10 times every 6 minutes at the same temperature.
  • the solid catalyst component had a titanium atom content of 3.34% by weight, an ethoxy group content of 0.66% by weight, and an internal electron donor content of 13.78% by weight, as determined by XPS analysis.
  • the peak component amount derived from the oxygen atom 1s orbital and having a peak top in the range of the binding energy of 532 to 534 eV is 80.6 area%, and the peak component amount 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 pores in the pore radius range of 5 to 30 nm is 0.115 mL / g, and the fine pore size in the range of pore radius 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 center particle size determined by the laser diffraction / scattering method was 55.8 ⁇ m, and the cumulative percentage of components having a particle size of 10 ⁇ m or less was 6.2%.
  • the analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.
  • the solid catalyst component had a titanium atom content of 3.45% by weight, an ethoxy group content of 0.69% by weight, an internal electron donor content of 12.98% by weight, and an oxygen by XPS analysis.
  • the peak component amount derived from the atomic 1s orbital and having a peak top in the range of the binding energy of 532 to 534 eV is 74.9 area%, and the peak component amount 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 mercury intrusion method is 0.92 mL / g
  • the total volume of pores in the pore radius range of 5 to 30 nm is 0.106 mL / g
  • the fine pore radius in the range of 30 to 700 nm is fine.
  • the total volume of the pores was 0.073 mL / g
  • the specific surface area was 77.53 m 2 / g.
  • the center particle size determined by the laser diffraction / scattering method was 54.0 ⁇ m, and the cumulative percentage of components having a particle size of 10 ⁇ m or less was 6.6%.
  • the analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.
  • Example 2 (1) Step of synthesizing 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. To the flask, 36.0 mL of toluene and 22.5 mL of titanium tetrachloride were added and stirred to obtain a toluene solution of titanium tetrachloride. After setting the temperature in the flask to 0 ° C., 0.75 g of magnesium diethoxide (spherical, center particle size 37 ⁇ m, bulk density 0.260 g / mL) was added 10 times every 6 minutes at the same temperature.
  • the solid catalyst component had a titanium atom content of 1.86% by weight, a center particle size of 33.0 ⁇ m by laser diffraction / scattering method, and a cumulative percentage of components having a particle size of 10 ⁇ m or less was 3.9%.
  • Table 2 shows the analysis results of the solid catalyst component for olefin polymerization.
  • a suspension prepared from 7.5 g of magnesium diethoxide (spherical, particle size of 37 ⁇ m, bulk density of 0.260 g / mL) and 35 mL of toluene was divided into 10 portions every 6 minutes to obtain a liquid at 0 ° C. It added in the said mixed solution kept at temperature. Thereafter, 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. Next, the temperature was raised to 10 ° C. and stirred at the same temperature for 2 hours, and then the temperature was raised.
  • the solid catalyst component had a titanium atom content of 1.89% by weight, a center particle size of 33.0 ⁇ m by laser diffraction / scattering method, and a cumulative percentage of components having a particle size of 10 ⁇ m or less was 4.4%. .
  • Table 2 shows the analysis results of the solid catalyst component for olefin polymerization.
  • Example 3 (1) Step of synthesizing 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 were 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 10 ° C., 0.75 g of magnesium diethoxide was added 10 times every 6 minutes at the same temperature. Thereafter, the slurry in the flask was stirred at 10 ° C. for 30 minutes.
  • the solid catalyst component had a titanium atom content of 2.03% by weight, an ethoxy group content of 0.33% by weight, an internal electron donor content of 14.38% by weight, and oxygen by XPS analysis.
  • the peak component amount derived from the atomic 1s orbital and having a peak top in the range of the binding energy of 532 to 534 eV is 91.9 area%, and the peak component amount having the peak top in the range of the binding energy of 529 to 532 eV is It was 8.1 area%.
  • the center particle size determined by the laser diffraction / scattering method was 63.9 ⁇ m, and the cumulative percentage of components having a particle size of 10 ⁇ m or less was 5.2%.
  • Table 2 shows the analysis results of the solid catalyst component for olefin polymerization.
  • Example 4 (1) Step of synthesizing 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. To the flask, 36.0 mL of toluene and 22.5 mL of titanium tetrachloride were added and stirred to obtain a toluene solution of titanium tetrachloride. After setting the temperature in the flask to 0 ° C., 0.75 g of magnesium diethoxide was added 10 times every 6 minutes at the same temperature.
  • the solid catalyst component had a titanium atom content of 2.04% by weight, an ethoxy group content of 0.35% by weight, an internal electron donor content of 14.5% by weight, and oxygen by XPS analysis.
  • the peak component amount derived from the atomic 1s orbital and having a peak position in the range of 532 to 534 eV in the bond energy is 95.0 area%, and the peak component amount having the peak position in the range of the bond energy from 529 to 532 eV is It was 5.0 area%.
  • the center particle diameter determined by the laser diffraction / scattering method was 65.6 ⁇ m, and the cumulative percentage of components having a particle diameter of 10 ⁇ m or less was 4.6%.
  • Table 2 shows the analysis results of the solid catalyst component for olefin polymerization.
  • Example 5 Step of synthesizing 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 were 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 0 ° C., 1.88 g of magnesium diethoxide was added four times every 30 minutes at the same temperature, followed by stirring at 0 ° C. for 1.5 hours.
  • 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour.
  • the titanium atom content is 2.53% by weight
  • the ethoxy group content is 0.44% by weight
  • the internal electron donor content is 13.7% by weight
  • XPS analysis The peak component amount derived from the oxygen atom 1s orbital and having a peak position in the range of 532 to 534 eV in the binding energy is 85.0 area%, and the peak component amount having the peak position in the range of 529 to 532 eV in the binding energy was 15.0 area%.
  • the total pore volume by mercury intrusion method is 1.43 mL / g
  • the total volume of pores in the pore radius range of 5-30 nm is 0.160 mL / g
  • the total volume of the pores was 0.317 mL / g and the specific surface area was 107.44 m 2 / g.
  • the center particle size determined by the laser diffraction / scattering method was 59.5 ⁇ m, and the cumulative percentage of components having a particle size of 10 ⁇ m or less was 5.3%.
  • the analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.
  • Example 6 (1) Step of synthesizing 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. To the flask, 36.0 mL of toluene and 22.5 mL of titanium tetrachloride were added and stirred to obtain a toluene solution of titanium tetrachloride. After the temperature in the flask was 0 ° C., 1.88 g of magnesium diethoxide was added four times every 30 minutes at the same temperature, followed by stirring at 0 ° C. for 1.5 hours.
  • 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour.
  • the solid catalyst component had a titanium atom content of 2.56% by weight, an ethoxy group content of 0.46% by weight, an internal electron donor content of 14.11% by weight, and oxygen by XPS analysis.
  • the peak component amount derived from the atomic 1s orbital and having a peak top in the range of the binding energy of 532 to 534 eV is 87.8 area%, and the peak component amount having the peak top in the range of the binding energy of 529 to 532 eV is 12.2 area%.
  • the total pore volume by mercury intrusion method is 1.35 mL / g, the total volume of pores in the range of pore radius 5-30 nm is 0.134 mL / g, and the fine volume in the range of pore radius 30-700 nm.
  • the total volume of the holes was 0.298 mL / g, and the specific surface area was 93.82 m 2 / g.
  • the center particle size determined by the laser diffraction / scattering method was 56.5 ⁇ m, and the cumulative percentage of components having a particle size of 10 ⁇ m or less was 5.2%.
  • the analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.
  • Example 7 (1) Step of synthesizing 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. To the flask, 43.3 mL of toluene and 15.2 mL of titanium tetrachloride were added and stirred to obtain a toluene solution of titanium tetrachloride. After the temperature in the flask was 0 ° C., 1.88 g of magnesium diethoxide was added four times every 30 minutes at the same temperature, followed by stirring at 0 ° C. for 1.5 hours.
  • 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour.
  • the solid catalyst component had a titanium atom content of 2.17 wt%, an ethoxy group content of 0.53% wt, an internal electron donor content of 12.11 wt%, and oxygen by XPS analysis.
  • the peak component amount derived from the atomic 1s orbital and having a peak top in the range of the binding energy of 532 to 534 eV is 83.3 area%, and the peak component amount 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 mercury intrusion method is 1.39 mL / g, the total volume of pores in the pore radius range of 5 to 30 nm is 0.150 mL / g, and the fine pore size in the range of pore radius 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 center particle diameter determined by the laser diffraction / scattering method was 61.6 ⁇ m, and the cumulative percentage of components having a particle diameter of 10 ⁇ m or less was 5.3%.
  • the analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.
  • Example 8 (1) Step of synthesizing 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. To the flask, 43.3 mL of toluene and 15.2 mL of titanium tetrachloride were added and stirred to obtain a toluene solution of titanium tetrachloride. After the temperature in the flask was 0 ° C., 1.88 g of magnesium diethoxide was added four times every 30 minutes at the same temperature, followed by stirring at 0 ° C. for 1.5 hours. Next, the temperature in the flask was raised to 10 ° C.
  • the solid catalyst component had a titanium atom content of 2.74% by weight, an ethoxy group content of 0.52% by weight, an internal electron donor content of 11.35% by weight, and oxygen by XPS analysis.
  • the peak component amount derived from the atomic 1s orbital and having a peak top in the range of the binding energy of 532 to 534 eV is 88.1 area%, and the peak component amount having the peak top in the range of the binding energy of 529 to 532 eV is 11.9 area%.
  • the total pore volume by mercury intrusion method is 1.48 mL / g, the total volume of pores in the range of pore radius 5-30 nm is 0.139 mL / g, and the fine volume in the range of pore radius 30-700 nm.
  • the total volume of the pores was 0.368 mL / g, and the specific surface area was 96.06 m 2 / g.
  • the center particle size determined by the laser diffraction / scattering method was 57.8 ⁇ m, and the cumulative percentage of components having a particle size of 10 ⁇ m or less was 4.5%.
  • the analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.
  • Example 9 (1) Step of synthesizing 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 were added to the flask. Titanium 15.2 mL was added and stirred to obtain a toluene solution of titanium tetrachloride. After the temperature in the flask was 0 ° C., 1.88 g of magnesium diethoxide was added four times every 30 minutes at the same temperature, followed by stirring at 0 ° C. for 1.5 hours.
  • 15.0 mL of titanium tetrachloride and 0.75 mL of ethyl 2-ethoxymethyl-3,3-dimethylbutanoate were added to form a mixture, and the mixture was stirred at 110 ° C. for 1 hour.
  • This solid catalyst component has a titanium atom content of 2.30% by weight, an ethoxy group content of 0.44% by weight, an internal electron donor content of 12.56% by weight, and oxygen content by XPS analysis.
  • the peak component amount derived from the atomic 1s orbital and having a peak top in the range of the binding energy of 532 to 534 eV is 92.2 area%, and the peak component amount 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 mercury intrusion method is 1.43 mL / g, the total volume of pores in the pore radius range of 5 to 30 nm is 0.165 mL / g, and the fine pore size in the range of pore radius of 30 to 700 nm is small.
  • the total volume of the pores was 0.328 mL / g and the specific surface area was 94.27 m 2 / g.
  • the center particle diameter determined by the laser diffraction / scattering method was 54.9 ⁇ m, and the cumulative percentage of components having a particle diameter of 10 ⁇ m or less was 5.4%.
  • the analysis results of the solid catalyst component for olefin polymerization are shown in Tables 2 and 3.
  • the present invention can be used for the production of olefin polymers.

Abstract

L'invention concerne un procédé de production d'un constituant catalytique solide pour la polymérisation d'oléfines, ledit constituant catalytique solide contenant un atome de titane, un atome de magnésium, un atome d'halogène et un donneur d'électrons interne. Ce procédé de production d'un constituant catalytique solide pour la polymérisation d'oléfines comprend une étape consistant à obtenir une suspension qui contient un produit solide par mise en contact d'un composé de magnésium avec une solution de composé d'halogénure de titane contenant un composé d'halogénure de titane et un solvant ; et le rapport de A à C (A/C) dans cette étape est inférieur ou égal à 3. A = a/b (1) a : le volume (ml) du composé d'halogénure de titane contenu dans la solution de composé d'halogénure de titane ; b : le volume (ml) du solvant contenu dans la solution de composé d'halogénure de titane ; C = a/c (2) a : le volume (ml) du composé d'halogénure de titane contenu dans la solution de composé d'halogénure de titane ; c : le volume (ml) du solvant contenu dans la suspension qui contient un produit solide.
PCT/JP2017/027902 2016-08-03 2017-08-01 Procédé de production d'un constituant catalytique solide pour la polymérisation d'oléfines WO2018025862A1 (fr)

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DE102021104360A1 (de) 2020-03-31 2021-09-30 Sumitomo Chemical Company, Limited Feste katalysatorkomponente für olefinpolymerisation
CN113710710A (zh) * 2019-04-25 2021-11-26 住友化学株式会社 丙烯聚合物的制造方法
EP4155324A2 (fr) 2021-09-22 2023-03-29 Sumitomo Chemical Company, Limited Procede de production d'un composant de catalyseur solide pour la polymérisation d'olefine, procede de production de catalyseur pour la polymérisation d'olefine, et procede de production de polymere d'olefine
EP4212557A2 (fr) 2022-01-14 2023-07-19 Sumitomo Chemical Company, Limited Matériau de polymérisation hétérophasique du propylène et polymère d'oléfine
US11713389B2 (en) 2020-11-25 2023-08-01 Sumitomo Chemical Company, Limited Propylene polymer composition and film

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US11713389B2 (en) 2020-11-25 2023-08-01 Sumitomo Chemical Company, Limited Propylene polymer composition and film
EP4155324A2 (fr) 2021-09-22 2023-03-29 Sumitomo Chemical Company, Limited Procede de production d'un composant de catalyseur solide pour la polymérisation d'olefine, procede de production de catalyseur pour la polymérisation d'olefine, et procede de production de polymere d'olefine
EP4212557A2 (fr) 2022-01-14 2023-07-19 Sumitomo Chemical Company, Limited Matériau de polymérisation hétérophasique du propylène et polymère d'oléfine

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