JP2005112920A - Solid titanium catalyst component for olefin polymerization, olefin polymerization catalyst, and olefin polymerization process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solid titanium catalyst component for olefin polymerization from which a catalyst is obtained that has a high catalytic activity and stereospecificity, gives olefin (co)polymers having good morphology and is manufactured using a special electron donor, and an olefin polymerization catalyst and an olefin polymerization process using the catalyst. <P>SOLUTION: The solid titanium catalyst component for olefin polymerization contains titanium, magnesium, a halogen and an electron donor and has an average particle size d of 25-100 μm and a particle strength N (MPa) which satisfies the relation: N>8,000×d<SP>-2</SP>. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a solid catalyst component, a catalyst, and a polymerization method for producing a homopolymer of ethylene or α-olefin or a copolymer thereof.

  Conventionally, as a catalyst used for producing an olefin polymer such as ethylene, α-olefin homopolymer or ethylene / α-olefin copolymer, a titanium compound supported on an active magnesium halide is included. Catalysts are known.

  As such an olefin polymerization catalyst (hereinafter, the polymerization catalyst may be used including a copolymerization catalyst), a solid titanium catalyst component comprising magnesium, titanium, halogen and an electron donor and an organic metal are used. Catalysts comprising compounds are known.

  This catalyst has high activity in the polymerization or copolymerization of α-olefins such as propylene and butene-1 as well as the polymerization of ethylene (hereinafter, polymerization may be used to include copolymerization). In addition, the stereospecificity of a polymer (hereinafter, the polymer may be used including a copolymer) is also high.

  Among these catalysts, in particular, a solid titanium catalyst component on which an electron donor selected from carboxylic acid esters, typically phthalate esters, is supported, an aluminum-alkyl compound as a co-catalyst component, and at least It is known that excellent performance is exhibited when a silicon compound having one Si-OR (wherein R is a hydrocarbon group) is used.

  In addition, increasing the particle size of such an olefin polymerization catalyst is effective for increasing the amount of rubber component when producing a block copolymer. However, when the particle size is increased, particle collapse occurs and the bulk density tends to decrease and the amount of fine polymer increases.

  The present inventor has conducted research for the purpose of obtaining a good morphological polymer that is a catalyst for olefin polymerization that is further excellent in polymerization activity and stereoregularity and that has no particle collapse. As a result, magnesium, halogen, titanium and electrons Catalyst comprising solid titanium catalyst component comprising donor and organometallic compound, and catalyst comprising solid titanium catalyst component comprising magnesium, titanium, halogen and electron donor, organometallic compound and organosilicon compound However, it has been found that the object of the present invention is achieved.

  The present invention has been made in view of such a current situation, and can produce an olefin (co) polymer having high catalytic activity, high stereospecificity and good morphology, and is produced using a special electron donor. It is an object of the present invention to provide a solid titanium catalyst component for olefin polymerization for obtaining a catalyst, an olefin polymerization catalyst using the same, and an olefin polymerization method.

The solid titanium catalyst component for olefin polymerization of the present invention contains titanium, magnesium, halogen and an electron donor,
i) The average particle diameter d is 25-100 μm, and
ii) Particle strength N (MPa) is expressed by the formula N> 8000 × d ⁻²
It is characterized by satisfying.

  Such a solid titanium catalyst component for olefin polymerization of the present invention comprises a solid adduct obtained by bringing a magnesium compound suspended in an inert hydrocarbon solvent into contact with an electron donor (a), and a liquid state. The titanium compound is preferably obtained by contacting the electron donor (b).

  Further, in such a solid titanium catalyst component for olefin polymerization of the present invention, the electron donor (b) preferably contains at least two kinds of electron donors, and the electron donor (b) comprises a plurality of carbons. It is also preferable to include one or more compounds having two or more ether bonds present via an atom and one or more carboxylic acid ester compounds.

  Furthermore, in such a solid titanium catalyst component for olefin polymerization of the present invention, the carboxylic acid ester compound is preferably a polyvalent carboxylic acid ester represented by the following formula;

(In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or a substituted or unsubstituted hydrocarbon group. And R ³ and R ⁴ may be linked to each other, and the substituent when R ^{1 to} R ⁶ are substituted may contain a heteroatom).

  Furthermore, in such a solid titanium catalyst component for olefin polymerization of the present invention, it is also preferable that the compound having two or more ether bonds present via the plurality of carbon atoms is represented by the following formula:

(In the above formula, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are each independently selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. It represents an atom or group having one kind of element, and any R ^{1 to} R ²⁶ may jointly form a ring other than a benzene ring, or an atom other than carbon may be contained in the main chain. Good.)

The catalyst for olefin polymerization of the present invention includes the solid titanium catalyst component for olefin polymerization of the present invention and an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table. It is characterized by.

  The olefin polymerization method of the present invention is characterized in that at least one olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms is polymerized using the olefin polymerization catalyst of the present invention.

  When the solid titanium catalyst component for olefin polymerization according to the present invention is used, the obtained polymer has high catalytic activity and high stereospecificity even without using an electron donor during polymerization. In addition, by using a compound having two or more ether bonds and other electron donors during polymerization, a polymer having higher catalytic activity, good morphology and high stereospecificity can be obtained. The resulting olefin polymerization catalyst can be produced.

  Moreover, according to the catalyst for olefin polymerization and the olefin polymerization method according to the present invention, a polymer having high catalytic activity and high steric specificity can be obtained in addition to being able to efficiently perform an olefin polymerization reaction.

  Hereinafter, the solid titanium catalyst component for olefin polymerization, the olefin polymerization catalyst, and the olefin polymerization method according to the present invention will be specifically described.

Solid titanium catalyst component for olefin polymerization (I)
The solid titanium catalyst component (I) for olefin polymerization of the present invention contains titanium, magnesium, halogen and an electron donor. Such a solid titanium catalyst component (I) for olefin polymerization of the present invention is preferably a solid adduct comprising a magnesium compound and an electron donor (a), a titanium compound in a liquid state, and an electron donor ( and b) can be obtained.

<Solid adduct>
The solid adduct preferably used in preparing the solid titanium catalyst component (I) for olefin polymerization of the present invention is composed of a magnesium compound and an electron donor (a), and is suspended in an inert hydrocarbon solvent. It is obtained by contacting the compound with the electron donor (a).

(Magnesium compound)
The solid adduct preferably used in preparing the solid titanium catalyst component (I) for olefin polymerization of the present invention is formed from a magnesium compound and an electron donor (a).

Specific examples of such a magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride;
Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride;
Alkoxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride;
Alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium;
Allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium;
Examples thereof include magnesium carboxylates such as magnesium laurate and magnesium stearate.

  These magnesium compounds may be used alone or in combination of two or more. These magnesium compounds may be complex compounds with other metals, double compounds, or mixtures with other metal compounds.

  Of these, magnesium halide is preferred, and magnesium chloride is particularly preferred. The magnesium compound may be derived from other substances.

(Electron donor (a))
As the electron donor (a) constituting the solid adduct, a compound having a magnesium compound solubilizing ability is used. As such a compound having a magnesium compound solubilizing ability, for example, alcohols, aldehydes, amines, carboxylic acids and mixtures thereof are preferably used.

Specific examples of alcohols having solubilizing ability of magnesium compounds include methanol, ethanol, propanol, butanol, ethylene glycol, methyl carbitol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol, aliphatic alcohols such as stearyl alcohol, cycloaliphatic alcohols such as cyclohexanol, methylcyclohexanol, benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl Alcohols, aromatic alcohols such as α-methylbenzyl alcohol, α, α-dimethylbenzyl alcohol, alcohols such as n-butylcellosolve, 1-butoxy-2-propanol , And the like aliphatic alcohols containing shea group.

  Examples of the carboxylic acid include organic carboxylic acids having 7 or more carbon atoms such as caprylic acid, 2-ethylhexanoic acid, undecylenic acid, undenoic acid, noneric acid, and octanoic acid. Examples of the aldehyde include aldehydes having 7 or more carbon atoms such as capric aldehyde, 2-ethylhexyl aldehyde, capryl aldehyde, and undecyl aldehyde.

  Examples of the amine include amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, decylamine, laurylamine, undecylamine, 2-ethylhexylamine and the like.

The solid adduct used for the preparation of the solid titanium catalyst component (I) of the present invention can be formed by bringing the magnesium compound and the electron donor (a) into contact with each other as described above.

  When the solid adduct is produced, the amount of the magnesium compound and the electron donor (a) used varies depending on the type and contact conditions, but the magnesium compound is added to the liquid electron donor (a). It is used in an amount of 0.1 to 20 mol / liter, preferably 0.5 to 10 mol / liter.

Such a solid adduct is preferably prepared by contacting a magnesium compound and an electron donor (a) in an inert hydrocarbon solvent. For example, the magnesium compound is suspended in an inert hydrocarbon solvent. By making it turbid and adding the electron donor (a) to this and stirring, the magnesium compound and the electron donor (a) can be contacted.

Specific examples of the inert hydrocarbon solvent that can be used for the preparation of the solid adduct include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane , Cyclohexane, methylcyclopentane, and other alicyclic hydrocarbons; benzene, toluene, xylene, and other aromatic hydrocarbons; ethylene chloride, chlorobenzene, and other halogenated hydrocarbons, and mixtures thereof. Is preferably used.

<Titanium compound>
Examples of the titanium compound in a liquid state preferably used in preparing the solid titanium catalyst component (I) for olefin polymerization of the present invention include, for example, a general formula,
Ti (OR) _g X _4-g
(Wherein, R represents a hydrocarbon group, X represents a halogen atom, and 0 ≦ g ≦ 4). More specifically,
Titanium tetrahalides such as TiCl ₄ , TiBr ₄ , TiI ₄ ;
Ti (OCH ₃ ) Cl ₃ ,
Ti (OC ₂ H ₅ ) Cl ₃ ,
Ti (O—n—C ₄ H ₉ ) Cl ₃ ,
Ti (OC ₂ H ₅ ) Br ₃ ,
Trihalogenated alkoxytitanium such as Ti (O-iso-C ₄ H ₉ ) Br ₃ ;
Ti (OCH ₃ ) ₂ Cl ₂ ,
Ti (OC ₂ H ₅ ) ₂ Cl ₂ ,
Ti (O—n—C ₄ H ₉ ) ₂ Cl ₂ ,
Dihalogenated alkoxytitanium such as Ti (OC ₂ H ₅ ) ₂ Br ₂ ;
Ti (OCH ₃ ) ₃ Cl,
Ti (OC ₂ H ₅ ) ₃ Cl,
Ti (O—n—C ₄ H ₉ ) ₃ Cl,
Monohalogenated alkoxytitanium such as Ti (OC ₂ H ₅ ) ₃ Br;
Ti (OCH ₃ ) ₄ ,
Ti (OC ₂ H ₅ ) ₄ ,
Ti (O-n-C ₄ H ₉ ) ₄ ,
Ti (O-iso-C ₄ H ₉ ) ₄ ,
Examples thereof include tetraalkoxy titanium such as Ti (O-2-ethylhexyl) ₄ .

  Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in the form of a mixture. These titanium compounds may be diluted with hydrocarbons or halogenated hydrocarbons.

<Electron Donor (b)>
The solid titanium catalyst component (I) for olefin polymerization of the present invention is preferably prepared by contacting the solid adduct, the liquid titanium compound, and the electron donor (b). As the electron donor (b), only one kind may be used, but at least two kinds of electron donors are preferably used, and more preferably, the electron donor (b) contains a plurality of carbon atoms. It is preferable that the compound (b1) which has 2 or more ether bonds which exist via this, and an electron donor (b2) other than this are included.

(Electron donor (b1))
The electron donor (b1) is a compound having two or more ether bonds that exist via a plurality of carbon atoms that acts as an electron donor. That is, the electron donor (g1) has a plurality of atoms between at least two ether bonds (C—O—C) (between C—O—C and C—O—C). A compound. Specifically, at least two ether bonds (C—O—C) are connected via a plurality of atoms, and the plurality of atoms are carbon, silicon, oxygen, sulfur, phosphorus, boron. Or two or more compounds selected from these.

  Further, the atoms connecting these ether bonds can have a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. Among these, a compound in which a relatively bulky substituent is bonded to an atom existing between ether bonds and a plurality of carbon atoms are included in the atoms connecting the ether bonds is preferable.

  Examples of the compound having two or more ether bonds include compounds represented by the following formulae.

(In the above formula, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are each independently selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. Represents an atom or group having one kind of element, and any R ^{1 to} R ²⁶ , preferably R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, other than carbon in the main chain May be included.)
As a compound having two or more ether bonds as described above,
2- (2-ethylhexyl) -1,3-dimethoxypropane,
2-isopropyl-1,3-dimethoxypropane,
2-butyl-1,3-dimethoxypropane,
2-s-butyl-1,3-dimethoxypropane,
2-cyclohexyl-1,3-dimethoxypropane,
2-phenyl-1,3-dimethoxypropane,
2-cumyl-1,3-dimethoxypropane,
2- (2-phenylethyl) -1,3-dimethoxypropane,
2- (2-cyclohexylethyl) -1,3-dimethoxypropane,
2- (p-chlorophenyl) -1,3-dimethoxypropane,
2- (diphenylmethyl) -1,3-dimethoxypropane,
2- (1-naphthyl) -1,3-dimethoxypropane,
2- (2-fluorophenyl) -1,3-dimethoxypropane,
2- (1-decahydronaphthyl) -1,3-dimethoxypropane,
2- (pt-butylphenyl) -1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane,
2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane,
2,2-dibutyl-1,3-dimethoxypropane,
2-methyl-2-propyl-1,3-dimethoxypropane,
2-methyl-2-benzyl-1,3-dimethoxypropane,
2-methyl-2-ethyl-1,3-dimethoxypropane,
2-methyl-2-isopropyl-1,3-dimethoxypropane,
2-methyl-2-phenyl-1,3-dimethoxypropane,
2-methyl-2-cyclohexyl-1,3-dimethoxypropane,
2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane,
2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane,
2-methyl-2-isobutyl-1,3-dimethoxypropane,
2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxypropane,
2,2-diphenyl-1,3-dimethoxypropane,
2,2-dibenzyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane,
2,2-diisobutyl-1,3-diethoxypropane,
2,2-diisobutyl-1,3-dibutoxypropane,
2-isobutyl-2-isopropyl-1,3-dimethoxypropane,
2,2-di-s-butyl-1,3-dimethoxypropane,
2,2-di-t-butyl-1,3-dimethoxypropane,
2,2-dineopentyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane,
2-phenyl-2-benzyl-1,3-dimethoxypropane,
2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane,
2,3-diphenyl-1,4-diethoxybutane,
2,3-dicyclohexyl-1,4-diethoxybutane,
2,2-dibenzyl-1,4-diethoxybutane,
2,3-dicyclohexyl-1,4-diethoxybutane,
2,3-diisopropyl-1,4-diethoxybutane,
2,2-bis (p-methylphenyl) -1,4-dimethoxybutane,
2,3-bis (p-chlorophenyl) -1,4-dimethoxybutane,
2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane,
2,4-diphenyl-1,5-dimethoxypentane,
2,5-diphenyl-1,5-dimethoxyhexane,
2,4-diisopropyl-1,5-dimethoxypentane,
2,4-diisobutyl-1,5-dimethoxypentane,
2,4-diisoamyl-1,5-dimethoxypentane,
3-methoxymethyltetrahydrofuran,
3-methoxymethyldioxane,
1,2-diisobutoxypropane,
1,2-diisobutoxyethane,
1,3-diisoamyloxyethane,
1,3-diisoamyloxypropane,
1,3-diisoneopentyloxyethane,
1,3-dineopentyroxypropane,
2,2-tetramethylene-1,3-dimethoxypropane,
2,2-pentamethylene-1,3-dimethoxypropane,
2,2-hexamethylene-1,3-dimethoxypropane,
1,2-bis (methoxymethyl) cyclohexane,
2,8-dioxaspiro [5,5] undecane,
3,7-dioxabicyclo [3,3,1] nonane,
3,7-dioxabicyclo [3,3,0] octane,
3,3-diisobutyl-1,5-oxononane,
6,6-diisobutyldioxyheptane,
1,1-dimethoxymethylcyclopentane,
1,1-bis (dimethoxymethyl) cyclohexane,
1,1-bis (methoxymethyl) bicyclo [2,2,1] heptane,
1,1-dimethoxymethylcyclopentane,
2-methyl-2-methoxymethyl-1,3-dimethoxypropane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane,
2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxycyclohexane,
2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane,
2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane,
2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,
2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane,
2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,
2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane,
2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,
Tris (p-methoxyphenyl) phosphine,
Methylphenylbis (methoxymethyl) silane,
Diphenylbis (methoxymethyl) silane,
Methylcyclohexylbis (methoxymethyl) silane,
Di-t-butylbis (methoxymethyl) silane,
Cyclohexyl-t-butylbis (methoxymethyl) silane,
An example is i-propyl-t-butylbis (methoxymethyl) silane.

  Of these, 1,3-diethers are preferred, and in particular, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl- 1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane are preferred.

  These electron donors (b1) may be used alone or in combination of two or more.

(Electron donor (b2))
The solid titanium catalyst component (I) of the present invention may be prepared using the electron donor (b2), and is prepared using the electron donor (b2) together with the electron donor (b1). Is more preferable. The electron donor (b2) is an electron donor other than the electron donor (b1).

Examples of such an electron donor (b2) include organic acid esters, organic acid halides, organic acid anhydrides, ethers, ketones, aldehydes, tertiary amines, phosphites, phosphate esters, phosphate amides, and carboxylic acids. Amides, nitriles and the like can be exemplified, and specifically, ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, cyclohexanone, benzoquinone; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, Aldehydes having 2 to 15 carbon atoms such as tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, valerate Chill, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate Benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate C2-18 organic acid esters such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, etc .; acid halides such as acetic anhydride, phthalic anhydride, maleic anhydride , Anhydrous Benzo Acid anhydrides such as trimellitic anhydride and tetrahydrophthalic anhydride; ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acetic acid N, Acid amides such as N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide; tertiary amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine; acetonitrile, Nitriles such as benzonitrile and trinitrile can be exemplified. Of these, aromatic carboxylic acid esters are preferred.

  Two or more of these compounds can be used in combination.

  Furthermore, as an organic acid ester, mono- or polyvalent carboxylic acid ester is preferable, and polyvalent carboxylic acid ester can be mentioned as a particularly preferable example. Examples of such a polyvalent carboxylic acid ester include compounds having a skeleton represented by the following general formula.

In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or a substituted or unsubstituted hydrocarbon group. , R ³ and R ⁴ may be linked to each other, and when R ^{1 to} R ⁶ are substituted, the substituent may contain a hetero atom. Here, preferably, at least one of R ³ and R ⁴ is a substituted or unsubstituted hydrocarbon group, R ³ and R ⁴ may be linked to each other, and the hydrocarbon groups R ^{1 to} R ⁶ are substituted. Substituents when present include heteroatoms such as N, O, S, such as C—O—C, COOR, COOH, OH, SO ₃ H, —C—N—C—, NH _2, etc. Has a group.

Specific examples of such polyvalent carboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate, diethyl isopropylmalonate. , Diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate , Aliphatic polycarboxylic acid esters such as diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconic acid; diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclohexane Alicyclic polycarboxylic acid esters such as diisobutyl rubonate, diethyl tetrahydrophthalate, diethyl nadic acid; monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, Di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-phthalate
Aromatic poly, such as ethylhexyl, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitic acid, dibutyl trimellitic acid Preferred examples include carboxylic acid esters; heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

Other examples of polyvalent carboxylic acid esters include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. And esters of chain dicarboxylic acids.

  Among these electron donors (b2), mono- or polyvalent carboxylic acid esters are preferably used, polyvalent carboxylic acid esters are more preferably used, and phthalic acid esters are preferably used. It is preferable to use an acid diester.

Further, when preparing the solid titanium catalyst component, the electron donor (b1) and the electron donor (b2) may be mixed and used as the electron donor (b).

<Preparation of solid titanium catalyst component (I) for olefin polymerization>
The solid titanium catalyst component (I) for olefin polymerization of the present invention is preferably prepared by bringing the above-mentioned solid adduct, the liquid titanium compound, and the electron donor (b) into contact with each other.

Although it does not restrict | limit especially as a preparation method of such solid titanium catalyst component (I) for olefin polymerization, For example, the following methods (1)-(4) are mentioned.
(1) A liquid titanium compound is contacted with a compound obtained by contacting the solid adduct and the electron donor (b) to obtain a solid titanium composite.
(2) The solid donor complex is obtained by bringing the electron donor (b) into contact with the compound obtained by bringing the solid adduct into contact with the liquid titanium compound.
(3) A solid titanium composite is obtained by bringing the titanium compound in a liquid state into contact with the compound obtained by contacting the solid adduct, the electron donor (b) with a halogen-containing compound and / or an organometallic compound. obtain.
(4) The compound obtained by contacting the solid adduct with the liquid titanium compound, the electron donor, (b) the compound having two or more ether bonds, a halogen-containing compound, and / or an organic compound. A metal compound is contacted to obtain a solid titanium composite.

  Here, it is preferable to use two or more kinds of electron donors as the electron donor (b). However, two or more kinds of electron donors may be used in combination, or may be used at the same time. May be used.

When the solid titanium catalyst component (I) is produced by such a method, the use amount of the solid adduct, the liquid titanium compound and the electron donor (b) is the type, contact conditions, and contact order. Depending on the number of contacts, etc., the total amount of the electron donor (b) relative to 1 mol of magnesium in the solid adduct composed of the magnesium compound and the electron donor (a) is 0.0.
1 mol-5 mol, preferably 0.1 mol-2.0 mol, more preferably 0.1 mol-
Used in an amount of 1.5 moles. The titanium compound in the liquid state is used in an amount of 0.1 mol to 1000 mol, particularly preferably 1 mol to 200 mol, relative to 1 mol of magnesium in the solid adduct. In the preparation, the titanium compound in a liquid state may be added all at once or may be added in divided portions.

  When preparing the solid titanium catalyst component (I) for olefin polymerization of the present invention, the solid adduct is preferably used in a state suspended in a hydrocarbon solvent, and usually its concentration (solid adduct) / Hydrocarbon solvent) is 1-1000 grams / liter, preferably 100-500 grams / liter.

  As a hydrocarbon solvent used here, the solvent used at the time of the preliminary polymerization mentioned later, for example can be used. Among these, aliphatic hydrocarbons such as heptane, octane, and decane are preferable.

  The temperature at the time of contacting these compounds is usually −70 ° C. to 200 ° C., preferably −25 ° C. to 150 ° C. The solid titanium catalyst component precursor thus obtained contains titanium, magnesium and halogen, and an electron donor (b).

In the solid titanium catalyst component (I), the halogen / titanium (atomic ratio) is 2 to 100, preferably 4 to 90, and the electron donor (b) / titanium (molar ratio) is 0.01 to 1
00, preferably 0.2 to 10, and magnesium / titanium (atomic ratio) is 2 to 100
Preferably, it is 4 to 50.

  The catalyst particle size (average particle size d (μm)) of the solid titanium catalyst component is 25 to 100 μm, preferably 25 to 80 μm.

Further, the solid titanium catalyst component according to the present invention has a sufficient particle strength N (MPa), and the formula N> 8000 × d ^−2.
And preferably the formula N> 12000 × d ⁻²
Meet.

Here, the particle strength is defined by using a test force (P) and a particle diameter (d) when a load is applied to the particle to cause fracture (crush). For the measurement of the particle strength N, a micro compression tester MCT-W series manufactured by Shimadzu Corporation is used. The test conditions are such that the test force is fixed at 45 mN, the load speed is set to 4.46 mN / sec, and the particle diameter is measured using an attached microscope. The calculation formula for obtaining the particle strength is (particle strength N) = 2.8P / (π × d (particle diameter) × d (particle diameter))
It is represented by

Olefin Polymerization Catalyst The olefin polymerization catalyst of the present invention includes a solid titanium catalyst component according to the above-described invention and an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table. .

<Organometallic compound catalyst component (II)>
As the organometallic compound catalyst component (II) constituting the olefin polymerization catalyst of the present invention, for example, an organoaluminum compound, a complex alkylated product of a Group I metal and aluminum, an organometallic compound of a Group II metal, or the like is used. be able to.

As the organoaluminum compound, for example, in R ^a _n AlX _3-n (wherein, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, n represents is 1-3 ) Can be exemplified. In this formula, R ^a includes, for example, an alkyl group, a cycloalkyl group, or an aryl group. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, Hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

  As such an organoaluminum compound, specifically, the following compounds are used.

Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, Dialkylaluminum halides such as diisobutylaluminum chloride and dimethylaluminium bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminium sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; methyl It is diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride; Rumi um dichloride, ethylaluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide.

As the organoaluminum ^{_{compound, R a n AlY 3-n}} ( wherein R ^a is as defined above,
Y is -OR ^b group, -OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -SiR ^f ₃ group or -N (Rg) AlR ^h ₂ group, and n is 1 to 2 , R ^b , R ^c , R ^d and R ^h are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ^e is hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group Or a trimethylsilyl group, and R ^f and R ^g are a methyl group, an ethyl group, etc.).

As such an organoaluminum compound, specifically, the following compounds are used.
(I) R ^a _n Al (OR ^b ) _3-n
For example, dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide and the like.
_{^{(Ii) R a n Al (}} OSiR c 3) 3-n
For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiMe ₃ )
(iso-Bu) ₂ Al (OSiEt ₃ ) and the like.
_{^{(Iii) R a n Al (}} OAlR d 2) 3-n
For example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) _{2 and the} like.
_{^{(Iv) R a n Al (}} NR e 2) 3-n
For example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHEt, Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN (Me ₃ Si) _{2 and the} like.
_{^{(V) R a n Al (}} SiR f 3) 3-n
For example, (iso-Bu) ₂ AlSiMe ₃ etc.
_{^{(Vi) R a n Al (}} N (R g) AlR h 2) 3-n
For example, Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

In the above examples, Et represents an ethyl group, iso-Bu represents an isobutyl group, and Me represents a methyl group.

Organoaluminum compounds mentioned _{^{above, R a 3 Al, R a}} n Al (OR b) 3-n, R a n
A preferred example is an organoaluminum compound represented by Al (OAlR ^d ₂ ) _3-n .

As the complex alkylated product of Group I metal and aluminum, the general formula M ¹ AlR ^j ₄ (however,
M ¹ is Li, Na, K, and R ^j is a hydrocarbon group having 1 to 15 carbon atoms), specifically, LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) _{4 and the} like can be mentioned.

The organometallic compounds of Group II metals include those of the general formula R ^k R ^l M ²
(However, R ^k and R ¹ are each a hydrocarbon group having 1 to 15 carbon atoms or a halogen, which may be the same or different from each other, except that they are both halogens. M ² is Mg, Zn.
, Cd), and specific examples include diethyl zinc, diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, and the like.

  These compounds can also be used as a mixture of two or more.

<Organic silicon compound (electron donor (c))>
In the preparation of the catalyst for olefin polymerization of the present invention, together with such an organometallic compound catalyst component (II), the above compound having two or more ether bonds or an organosilicon compound may be contacted as necessary.

  Examples of such an organosilicon compound include those represented by the following general formula.

R _n Si (OR ') _4-n
(In the formula, R and R ′ are hydrocarbon groups, and 0 <n <4)
Specific examples of the organosilicon compound represented by the above general formula include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t -Butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis o-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, Bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxy Silane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxy Silane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane , Ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxy Silane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, allyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane; Cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane; dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethyl) Cyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysila , Dicyclopentyl ethyl silane, hexenyl trimethoxy silane, dicyclopentyl methylethoxy silane, cyclopentyl dimethyl silane, cyclopentyl diethyl silane, is cyclopentyl dimethylethoxysilane used.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis p-tolyldimethoxy Silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane Silane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferably used. These organosilicon compounds can be used in combination of two or more.

Olefin Polymerization Method In the olefin polymerization method according to the present invention, olefin polymerization is performed using the olefin polymerization catalyst according to the present invention described above.

<Preliminary polymerization>
In the olefin polymerization method according to the present invention, an α-olefin can be prepolymerized in an olefin polymerization catalyst. This prepolymerization is performed by prepolymerizing α-olefin in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g, per 1 g of the olefin polymerization catalyst.

  In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used.

  The concentration of the solid titanium catalyst component (I) in the prepolymerization is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, and particularly preferably about 0.1 to 50 mmol in terms of titanium atom per liter of the liquid medium. A range of 1 to 20 mmol is desirable.

The amount of the organometallic compound catalyst component (II) is 0.1 to 0.1 g per 1 g of the solid titanium catalyst component (I).
The amount may be such that 1000 g, preferably 0.3 to 500 g of polymer is formed, and is usually about 0.1 to 300 mol, preferably about 0.1 to 300 mol, preferably 1 mol per titanium atom in the solid titanium catalyst component (I). The amount is preferably about 0.5 to 100 mol, particularly preferably 1 to 50 mol.

In the prepolymerization, an electron donor (b1) or an electron donor (c) organosilicon compound can be used as necessary, and these components are composed of titanium atoms in the solid titanium catalyst component (I). It is used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol per mol.

  The prepolymerization can be performed under mild conditions by adding an olefin and the above catalyst components to an inert hydrocarbon medium.

In this case, specific examples of the inert hydrocarbon medium used include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene;
Cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Examples thereof include halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof.

  Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Thus, when using an inert hydrocarbon medium, it is preferable to perform prepolymerization by a batch type.

  On the other hand, the prepolymerization can be carried out using the olefin itself as a solvent, or the prepolymerization can be carried out in a substantially solvent-free state. In this case, it is preferable to perform preliminary polymerization continuously.

  The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later. Specifically, propylene is preferable.

  The reaction temperature in the prepolymerization is usually about -20 to + 100 ° C, preferably about -20 to + 80 ° C, more preferably 0 to + 40 ° C.

  In the prepolymerization, a molecular weight regulator such as hydrogen can be used.

As described above, the prepolymerization is performed at about 0.1 to 1000 per gram of the solid titanium catalyst component (I).
g, preferably about 0.3 to 500 g, particularly preferably 1 to 200 g of polymer. If the amount of prepolymerization is too large, the production efficiency of the olefin polymer may decrease.

  Such prepolymerization can be carried out batchwise or continuously.

<Polymerization>
In the polymerization method of the present invention, olefins that can be used for polymerization (main polymerization) include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1 -Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-
Examples include dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicocene.

In the polymerization method of the present invention, these olefins can be used alone or in combination. In addition, aromatic vinyl compounds such as styrene and allylbenzene;
Alicyclic vinyl compounds such as vinylcyclohexane; cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4 , 4a, 5,8,8a-Cyclic olefins such as octahydronaphthalene; 6-methyl 1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl- 1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1
, 6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1 A compound having a polyunsaturated bond such as conjugated dienes such as dienes such as 1,6-undecadiene, isoprene and butadiene, and non-conjugated dienes can be used as a polymerization raw material together with ethylene and α-olefin.

  In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.

  When the main polymerization takes the form of slurry polymerization, the above-mentioned inert hydrocarbon can be used as the reaction solvent, or a liquid olefin can be used at the reaction temperature.

In the polymerization method of the present invention, the solid titanium catalyst component (I) is generally about 0.0001 to 0.5 mmol, preferably about 0.00, in terms of titanium atoms per liter of polymerization volume.
Used in an amount of 1 to 0.1 mmol. The organometallic compound (II) is an amount such that the metal atom is usually about 1 to 2000 mol, preferably about 5 to 500 mol, per 1 mol of titanium atom in the prepolymerization catalyst component in the polymerization system. Used in

  If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted, and a polymer having a high melt flow rate can be obtained.

In the present invention, the polymerization temperature of the olefin is usually about 20 to 100 ° C., preferably about 5
The pressure is usually set to normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² at 0 to 90 ° C. In the polymerization method of the present invention, the polymerization can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

  The olefin polymer thus obtained may be any of a homopolymer, a random copolymer and a block copolymer.

  When olefin polymerization, particularly propylene polymerization, is performed using the olefin polymerization catalyst as described above, the isotactic index (II) indicated by the boiling heptane extraction residue is 70% or more, preferably 85% or more, particularly preferably. A propylene-based polymer having a ratio of 95% or more can be obtained. At this time, stereoregularity can be easily controlled by adjusting the amount of the compound having two or more ether bonds or the amount of the electron donor.

  In addition, the molecular weight distribution index Mw / Mn value measured by GPC (gel permeation chromatography) is smaller than that of the polymer obtained by the conventional method, and generally a polymer of 5 or less is obtained.

  In the present invention, the olefin polymerization catalyst may contain other components useful for olefin polymerization in addition to the above components.

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

  In the following examples, the bulk specific gravity of the polymer, the melt flow rate, the particle size of the solid titanium catalyst component, the particle strength, and the amount of fine powder were measured by the following methods.

  (1) Bulk specific gravity: Measured according to JIS K-6721.

  (2) Melt flow rate (MFR): Measured at 190 ° C. according to ASTM D1238E.

  (3) Particle size measurement of solid titanium catalyst component: analysis by centrifugal sedimentation method using CAPA-300 PARTIC ANALYZER manufactured by HORIBA.

  (4) Measurement of particle strength N: Analysis was performed using a micro compression tester MCT-W series manufactured by Shimadzu Corporation. As test conditions, the test force is fixed at 45 mN, the load speed is set to 4.46 mN / sec, and the particle diameter is measured using an attached microscope. An arithmetic expression for obtaining the particle strength is represented by (particle strength) = 2.8P / (π × d (particle diameter) × d (particle diameter)).

(5) Measurement of the amount of fine powder: The amount of fine powder of 100 μm or less was analyzed using a vibration sieve machine manufactured by Tanaka Tech.

(Preparation of solid titanium catalyst component)
A high-speed agitator (made by Tokushu Kika Kogyo Co., Ltd.) with an internal volume of 2 liters was sufficiently purged with nitrogen, and then 700 ml of purified kerosene, 10 g of commercially available magnesium chloride, 24.2 g of ethanol, and trade name EMAZOL 320 ) 3 g was added, the system was heated with stirring, and stirred at 120 ° C. and 800 rpm for 30 minutes. Using a Teflon (registered trademark) tube with an inner diameter of 5 mm under high-speed stirring, the solution was transferred to a 2 liter glass flask (with a stirrer) into which 1 liter of purified kerosene previously cooled to −10 ° C. was put. The purified solid was sufficiently washed with purified n-hexane by filtration to obtain a solid adduct in which 2.8 mol of ethanol was coordinated with respect to 1 mol of magnesium chloride.

  The above solid adduct suspended in 30 ml of decane was introduced into 200 ml of titanium tetrachloride in which 46.2 mmol in terms of magnesium atom was maintained at −20 ° C. with stirring. The mixture was heated to 80 ° C. over 5 hours, and after reaching 80 ° C., 1.6 g of diisobutyl phthalate was added, and then 1.4 g of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane was added. The temperature was raised to 120 ° C. over 40 minutes. The temperature was held at 120 ° C. with stirring for 90 minutes.

  After completion of the reaction for 90 minutes, the solid part was collected by hot filtration, and the solid part was resuspended in 200 ml of titanium tetrachloride, and then heated to 130 ° C. and stirred for 45 minutes. Hold while. After completion of the reaction for 45 minutes, the solid part was again collected by hot filtration, and the solid part was resuspended in 200 ml of titanium tetrachloride, and then heated to 130 ° C. and stirred for 45 minutes. While holding.

  After completion of the reaction, the solid part was collected again by hot filtration, and washed sufficiently with decane and hexane at 100 ° C. until no free titanium compound was detected in the washing solution.

  The solid titanium catalyst component prepared by the above operation was stored as a decanslurry, but a part of this was dried for the purpose of examining the catalyst composition.

  The composition of the solid titanium catalyst component thus obtained was as follows: titanium 2.0% by weight, magnesium 19% by weight, diisobutyl phthalate 7.0% by weight, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane 6 1% by weight.

The average particle diameter of the catalyst component is 40 μm, and the particle strength at 40 μm of this catalyst component is 12 MP.
a.

(polymerization)
After adding 500 g of propylene and 1 NL of hydrogen at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of cyclohexylmethyldimethoxysilane, and a solid titanium catalyst component were converted to 0 in terms of titanium atoms. 0.002 mmol was added, and the temperature in the polymerization vessel was quickly raised to 70 ° C. After polymerization at 70 ° C. for 1 hour, the reaction was stopped with a small amount of methanol, and propylene was purged.

  The yield of the obtained polymer was 194 g, the apparent bulk specific gravity was 0.48 g / ml, the fine powder amount was 0.2 wt%, the MFR was 6.8 dg / min, II was 97.9%, and the activity was It was 97 kg-PP / mmol Ti.

(Preparation of solid titanium catalyst component)
A solid titanium catalyst component was prepared in the same manner as in Example 1 except that 0.9 g of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane was used. The average particle size of the catalyst component was 38 μm, and the particle strength of this catalyst component at 40 μm was 11.6 MPa.

(polymerization)
Polymerization of propylene was carried out in the same manner as in Example 1 except that the obtained solid catalyst component was used and 0.004 mmol of this catalyst component was used in terms of titanium atom.

  The yield of the obtained polymer was 260 g, the apparent bulk specific gravity was 0.48 g / ml, the fine powder amount was 0.3% by weight, MFR was 6.7 dg / min, II was 98.1%, and the activity was It was 65 kg-PP / mmol Ti.

Comparative Example 1
(Preparation of solid titanium catalyst component)
The solid adduct prepared in Example 1 was fluidized and subjected to dealcoholization treatment until ethanol reached 2.2 mol per mol of magnesium chloride. This solid adduct was suspended in 30 ml of decane, and the whole amount was introduced into 200 ml of titanium tetrachloride maintained at −20 ° C. with stirring, in terms of magnesium atoms, while stirring. The mixture was heated to 80 ° C. over 5 hours, and when it reached 80 ° C., 1.6 g of diisobutyl phthalate was added, and the temperature was raised to 120 ° C. over 40 minutes. The temperature was held at 120 ° C. with stirring for 90 minutes.

  After completion of the reaction for 90 minutes, the solid part was collected by hot filtration, and the solid part was resuspended in 200 ml of titanium tetrachloride, and then heated to 130 ° C. while stirring for 45 minutes. Retained.

  After completion of the reaction, the solid part was collected again by hot filtration, and washed sufficiently with decane and hexane at 100 ° C. until no free titanium compound was detected in the washing solution.

  The solid titanium catalyst component prepared by the above operation was stored as a decanslurry, and a part of this was dried for the purpose of examining the catalyst composition.

  The composition of the solid titanium catalyst component thus obtained was 2.7% by weight of titanium, 18% by weight of magnesium, 15.6% by weight of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane and an ethanol residue. It was 0.7% by weight. The average particle diameter of the catalyst component was 36 μm, and the particle strength of this catalyst at 40 μm was 3.2 MPa.

(polymerization)
Polymerization of propylene was carried out in the same manner as in Example 2 except that the obtained solid titanium catalyst component was used.

The yield of the obtained polymer was 238 g, the apparent bulk specific gravity was 0.41 g / ml, the fine powder amount was 0.6% by weight, MFR was 12 dg / min, II was 95.8%, and the activity was 59 kg- PP
/ Mmol Ti.

Comparative Example 2
(Preparation of solid titanium catalyst component)
The total amount of the solid adduct prepared in Comparative Example 1 was introduced with stirring into 200 ml of titanium tetrachloride in which 46.2 mmol in terms of magnesium atom was maintained at -20 ° C. The mixture was heated to 80 ° C. over 5 hours, and when it reached 80 ° C., 1.6 g of diisobutyl phthalate was added, and the temperature was raised to 120 ° C. over 40 minutes. The temperature was held at 120 ° C. with stirring for 90 minutes.

  After completion of the reaction for 90 minutes, the solid part was collected by hot filtration, and the solid part was resuspended in 200 ml of titanium tetrachloride, and then heated to 130 ° C. while stirring for 45 minutes. Retained.

  After completion of the reaction, the solid part was collected again by hot filtration, and washed sufficiently with decane and hexane at 100 ° C. until no free titanium compound was detected in the washing solution. The solid titanium catalyst component prepared by the above operation was stored as a decanslurry, but a part of this was dried for the purpose of examining the catalyst composition.

  The composition of the solid titanium catalyst component thus obtained was 3.1% by weight of titanium, 17% by weight of magnesium, 13.6% by weight of DIBP and 0.6% by weight of ethanol residue. The average particle size of the catalyst component was 36 μm, and the particle strength of this catalyst component at 40 μm was 2.9 MPa.

(polymerization)
The same polymerization as in Example 2 was performed except that the obtained solid titanium catalyst component was used.

  The yield of the polymer obtained was 163 g, the apparent bulk specific gravity was 0.43 g / ml, the fine powder amount was 0.4 wt%, the MFR was 6.0 dg / min, II was 97.4%, and the activity was It was 41 kg-PP / mmol Ti.

Claims (8)

Including titanium, magnesium, halogen and electron donors,
i) The average particle diameter d is 25-100 μm, and
ii) Particle strength N (MPa) is expressed by the formula N> 8000 × d ⁻²
A solid titanium catalyst component for olefin polymerization, characterized in that:   A solid adduct obtained by contacting a magnesium compound suspended in an inert hydrocarbon solvent with an electron donor (a), a titanium compound in a liquid state, and an electron donor (b) are contacted. The solid titanium catalyst component for olefin polymerization according to claim 1, which is obtained.   The solid titanium catalyst component for olefin polymerization according to claim 2, wherein the electron donor (b) contains at least two kinds of electron donors.   The electron donor (b) comprises one or more compounds having two or more ether bonds present via a plurality of carbon atoms, and one or more carboxylic acid ester compounds. The solid titanium catalyst component for olefin polymerization as described. 5. The solid titanium catalyst component for olefin polymerization according to claim 4, wherein the carboxylic acid ester compound is a polyvalent carboxylic acid ester represented by the following formula:

(In the above formula, R ¹ represents a substituted or unsubstituted hydrocarbon group, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or a substituted or unsubstituted hydrocarbon group. And R ³ and R ⁴ may be linked to each other, and the substituent when R ^{1 to} R ⁶ are substituted may contain a heteroatom). The solid titanium catalyst component for olefin polymerization according to claim 4 or 5, wherein the compound having two or more ether bonds existing through the plurality of carbon atoms is represented by the following formula:

(In the above formula, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are each independently selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. It represents an atom or group having one kind of element, and any R ^{1 to} R ²⁶ may jointly form a ring other than a benzene ring, or an atom other than carbon may be contained in the main chain. Good.) A solid titanium catalyst component for olefin polymerization according to any one of claims 1 to 6 and an organometallic compound catalyst component containing a metal selected from Group I to Group III of the Periodic Table. A catalyst for olefin polymerization.   A method for polymerizing olefins, wherein at least one olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms is polymerized using the olefin polymerization catalyst according to claim 7.