JPH06279526A - Solid titanium catalyst component for polymerization of olefin, catalyst for polymerization of olefin, and polymerization of olefin by using the same catalyst - Google Patents

Abstract

PURPOSE:To provide the component which can produce an olefin (co)polymer of excellent stereoregularity in high polymerization activity and the polymerization process. CONSTITUTION:The component is obtained by bringing a compound of the formula: XMg(OR) [wherein X is Br or I, and R is a hydrocarbon group], a liquid titanium compound and a compound having at least two ether bonds separated from each other by two or more atoms and comprises titanium, magnesium, the above ether compound, and bromine or iodine. The catalyst is formed from this component, an organometallic compound catalyst component, and optionally an electron donor.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization solid titanium catalyst component for producing an olefin polymer, an olefin polymerization catalyst containing the solid titanium catalyst component, and an olefin polymerization method.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a catalyst for olefin polymerization used for producing an olefin polymer by polymerizing or copolymerizing an olefin, a solid titanium catalyst component and an organometallic compound catalyst component (co-catalyst component) are used. ) And a catalyst formed from

As the solid titanium catalyst component as described above, it is known that a titanium compound is supported on magnesium halide in an active state and contains magnesium, titanium, halogen and an electron donor. According to the olefin polymerization catalyst containing the solid titanium catalyst component, olefins such as ethylene propylene and 1-butene can be polymerized or copolymerized with high polymerization activity (catalytic activity), and propylene, 1 -It is known that an olefin polymer having high stereospecificity can be obtained by polymerizing butene and the like.

Among these olefin polymerization catalysts, a solid titanium catalyst component containing an aromatic dicarboxylic acid diester as an electron donor, an organoaluminum compound as a cocatalyst component, and an organosilane compound as an electron donor. It is known that the catalyst formed from and exhibits excellent performance.

The inventors of the present invention conducted a study for the purpose of obtaining an olefin polymerization catalyst capable of producing an olefin polymer having excellent stereoregularity with higher polymerization activity, and found that a titanium compound in a liquid state was obtained. A catalyst for olefin polymerization containing a solid titanium catalyst component obtained by contacting a specific magnesium compound containing bromine or iodine and a compound having two or more ether bonds is capable of polymerizing an olefin with excellent polymerization activity. It was found that an olefin polymer having excellent stereoregularity can be produced, and the present invention has been completed.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is an olefin (co) having excellent stereoregularity.
An object of the present invention is to provide a solid titanium catalyst component for olefin polymerization capable of producing a polymer with high polymerization activity, a catalyst for olefin polymerization containing the solid titanium catalyst component, and a method for olefin polymerization.

[0007]

SUMMARY OF THE INVENTION The solid titanium catalyst component for olefin polymerization according to the present invention is (i) Formula XMg (OR) [X is Br or I, and R is a hydrocarbon group. ] Magnesium compound represented by, (ii) titanium compound in a liquid state,
(iii) Titanium, magnesium, a compound having two or more ether bonds existing through a plurality of atoms, which is obtained by contacting with a compound having two or more ether bonds existing through a plurality of atoms, and It is characterized by containing bromine or iodine.

This (iii) 2 which exists through a plurality of atoms
The compound having at least one ether bond is preferably a compound represented by the following formula.

[0009]

[Chemical 2]

(In the formula, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are at least one selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon. A substituent having an element of R ¹
R ²⁶ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon. ).

The olefin polymerization catalyst according to the present invention comprises the above-mentioned [I] olefin polymerization solid titanium catalyst component and [II] a metal selected from Group I to Group III of the periodic table. It is characterized in that it is formed from an organometallic compound catalyst component and, if necessary, a [III] electron donor.

The olefin polymerization method according to the present invention is characterized by polymerizing or copolymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst.

[0013]

DETAILED DESCRIPTION OF THE INVENTION 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 below.

In the present invention, the term "polymerization" may be used to include not only homopolymerization but also copolymerization, and the term "polymer" refers to not only homopolymer but also copolymer. It may be used in a meaning including a polymer.

The solid titanium catalyst component [I] for olefin polymerization according to the present invention comprises (i) the formula XMg (OR) [X is Br or I, and R is a hydrocarbon group. ] A magnesium compound represented by the formula (ii), a titanium compound in a liquid state, and (iii) a compound having two or more ether bonds existing through a plurality of atoms are brought into contact with each other to obtain titanium or magnesium. , A compound having two or more ether bonds existing through a plurality of atoms and bromine or iodine, preferably further halogen.

(I) Formula XMg (O used in the present invention
R) [X is Br or I, and R is a hydrocarbon group. ] As the magnesium compound represented by, specifically, methoxy magnesium bromide, ethoxy magnesium bromide, propoxy magnesium bromide, isopropoxy magnesium bromide, butoxy magnesium bromide, alkoxy magnesium bromide such as octoxy magnesium bromide, Alkoxy magnesium iodides such as methoxy magnesium iodide, magnesium ethoxy iodide, propoxy magnesium iodide, isopropoxy magnesium iodide, butoxy magnesium iodide, octoxy magnesium iodide, magnesium phenoxy bromide, and methyl phenoxy magnesium bromide. Roxymagnesium bromide, phenoxymagnesium iodide, methylphenoxymagnesium iodide and other allyloxymagnesium iodides It is below.

Of these, ethoxy magnesium bromide, butoxy magnesium bromide, ethoxy magnesium iodide and butoxy magnesium iodide are preferred. These may be used alone or in combination.

Further, in the present invention, other magnesium compounds may be used in combination with the above (i) magnesium compound. Specific examples of such other magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride, methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride. , Alkoxy magnesium halides such as octoxy magnesium chloride, phenoxy magnesium chloride, allyloxy magnesium halides such as methylphenoxy magnesium chloride, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, dioctoxy magnesium, di (2-ethylhexoxy) magnesium, etc. Dialkoxy magnesium, butoxy ethoxy magnesium, butoxy propoxy magnesium, ethoxy Alkoxy magnesium such as toxy magnesium, diphenoxy magnesium, bis (dimethylphenoxy) magnesium, phenoxymethylphenoxy magnesium and the like allyloxy magnesium, magnesium laurate, magnesium carboxylates such as magnesium stearate, magnesium carbonate, magnesium borate, Examples thereof include inorganic acid salts such as magnesium silicate.

These magnesium compounds may be complex compounds with other metals, double compounds, or mixtures with other metal compounds. Further, it may be used as a solid adduct of a magnesium compound or liquefied by using an electron donor as described below.

The above (i) magnesium compound is
It can also be derived from other compounds during the preparation of the catalyst components. For example, alkoxy magnesium bromide or phenoxy magnesium bromide can be derived using an alkyl magnesium bromide and an alcohol or phenol.

In the present invention, the liquid titanium compound (ii) used for preparing the solid titanium catalyst component [I] is, for example, a tetravalent titanium compound represented by the following formula. To be

In the formula Ti (OR) _g X _4-g , R is a hydrocarbon group, X is a halogen atom, and 0≤g≤4. Specific examples of such compounds include titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃
, Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti
Trihalogenated alkoxy titanium such as (O-iso-C ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) ₂ Cl ₂ ; Ti (OC ₂ H ₅ ) ₂ Cl ₂ ;
_{Ti (On-C 4 H 9} ) 2 Cl 2, Ti (OC 2 H 5) dihalogenated dialkoxy titanium, such as _{2 Br 2, Ti (OCH 3} ) 3 Cl, T
i (OC ₂ H ₅ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC
₂ H _{5) 3} monohalogenated trialkoxy titanium such as _{Br, Ti (OCH 3) 4} , Ti (OC 2 H 5) 4, Ti (On-C 4 H
Examples thereof include tetraalkoxytitanium such as ₉ ) ₄ , Ti (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These may be used alone or in combination of two or more. In the compound (iii) having two or more ether bonds (hereinafter sometimes referred to as a polyether compound) used in the present invention, the atoms existing between these ether bonds are
It is one or more selected from the group consisting of carbon, silicon, oxygen, sulfur, phosphorus, and boron, and has 2 or more atoms.
Among these, a relatively bulky substituent at an atom between ether bonds, specifically, a substituent having a carbon number of 2 or more, preferably 3 or more and having a linear, branched or cyclic structure,
More preferably, a substituent having a branched or cyclic structure is bonded. Further, the atom existing between two or more ether bonds has a plurality of atoms, preferably 3 to 2
Compounds containing 0, more preferably 3 to 10 and particularly preferably 3 to 7 carbon atoms are preferred.

Examples of such (iii) polyether compounds include compounds represented by the following formula.

[0025]

[Chemical 3]

In the formula, n is an integer of 2≤n≤10, R ^{1 to} R ²⁶ are carbon, hydrogen, oxygen, halogen, nitrogen,
It is a substituent having at least one element selected from sulfur, phosphorus, boron and silicon, and has any R ^{1 to} R
²⁶ , preferably R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon.

Specific examples of the (iii) polyether compound as described above include 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-dicyclopentyl-1,
3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane,
2,2-diisopropyl-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- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane,
2- (1-methylbutyl) -2-s-butyl-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-isopropyl- 1,3-dimethoxypropane, 2-phenyl-2-s-
Butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-
1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-
s-Butyl-1,3-dimethoxypropane, 2-cyclohexyl-
2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-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-di Ethoxybutane, 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, 1,3-diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxypropane , 1,
3-diisoneopentyloxyethane, 1,3-dineopentyloxypropane, 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 (methoxy Methyl) 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-ethoxy Methyl-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, i
-Propyl-t-butylbis (methoxymethyl) silane and the like.

Of these, 1,3-diethers are preferably used, and particularly 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2 -Dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3 -Dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane , 2-cyclohexyl-2-s-butyl-1,3-
Dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-
Dimethoxypropane, 2-phenyl-2-isopropyl-1,3-
Dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-
1,3-dimethoxypropane is preferably used.

In the present invention, when preparing the solid titanium catalyst component, the following electron donor may be used in combination with the above-mentioned (iii) polyether compound.
Such other electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, esters of organic or inorganic acids, ethers,
Acid amide, acid anhydride, ammonia, amine, nitrile,
Examples thereof include isocyanate.

More specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,
Alcohols having 1 to 18 carbon atoms such as cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol, halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol, phenol, cresol, xylenol, ethylphenol , Propylphenol,
C6 to C20 phenols which may have a lower alkyl group such as nonylphenol, cumylphenol and naphthol, and C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone , Acetaldehyde, propionaldehyde, octyl aldehyde,
Aldehydes having 2 to 15 carbon atoms such as benzaldehyde, tolualdehyde, naphthaldehyde, methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Benzyl acid, methyl toluate,
2 to 2 carbon atoms such as ethyl toluate, amyl toluate, ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethyl carbonate
18 organic acid esters, acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride and other acid halides having 2 to 15 carbon atoms, methyl ether,
Ethers having 2 to 20 carbon atoms such as ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethyl Acid amides such as amides, amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine, nitriles such as acetonitrile, benzonitrile, trinitrile, acids such as acetic anhydride, phthalic anhydride, benzoic anhydride Anhydrous etc. are mentioned.

In addition to these, water, anionic surfactants, cationic surfactants, and nonionic surfactants can also be used. Further, as the organic acid ester, a polyvalent carboxylic acid ester can be mentioned as a particularly preferable example, and as such a polyvalent carboxylic acid ester, compounds having a skeleton represented by the following general formula can be given.

[0032]

[Chemical 4]

In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted group. Alternatively, it is an unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. Also R ³
And R ⁴ may be connected to each other to form a cyclic structure. When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent includes a hetero atom such as N, O and S, and is, for example, C-
O-C, COOR, COOH, OH, SO 3 H, -C-
It has groups such as N—C— and NH ₂ .

Specific examples of such polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methyl glutarate, diethyl methyl malonate, diethyl ethyl malonate, isopropyl malonate. Acid diethyl, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, diethyl dibutylmalonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butylmaleate, diethyl butylmaleate, β-methylglutar Acid diisopropyl, ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, aliphatic polycarboxylic acid esters such as dioctyl citracone, diethyl 1,2-cyclohexanecarboxylate, 1,2-cyclyl Hexane carboxylic acid diisobutyl, tetrahydrophthalic acid diethyl, alicyclic polycarboxylic acid esters such as nadic diethyl, monoethyl phthalate, dimethyl phthalate, methyl phthalate, ethyl phthalate monoisobutyl, diethyl phthalate,
Ethyl isobutyl phthalate, di-n-propyl phthalate, di-isopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, di-2-phthalate
Aromatic polyenes such as ethylhexyl, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate Examples thereof include heterocyclic polycarboxylic acid esters such as carboxylic acid esters and 3,4-furandicarboxylic acid.

Other examples of the polycarboxylic acid ester include diethyl adipate, diisobutyl adipate,
Examples thereof include esters of long-chain dicarboxylic acids such as diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Among these compounds, it is preferable to use a carboxylic acid ester, and it is particularly preferable to use a polyvalent carboxylic acid ester, especially a phthalic acid ester.

Two or more of these compounds can be used in combination. In addition, (iii) a polyether compound as described above,
The electron donor may be derived from other compounds during the preparation of the catalyst component.

In the present invention, the solid titanium catalyst component [I] is used.
In the preparation of (i) a specific magnesium compound as described above, (ii) a titanium compound in a liquid state, and (iii)
If necessary, a halogen-containing compound can be used together with the polyether compound.

As such a halogen-containing compound,
For example, the general formula SiX _m R _4-m (X is a halogen atom, R is an alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms)
Is a cycloalkyl group or an aryl group having 6 to 20 carbon atoms, and m is a real number of 1 to 4. ) And a halogen-containing silicon compound represented by the formula (1).

More specifically, as the halogen-containing silicon compound, when m = 4 in the above formula, tetrachlorosilane, tetrabromosilane, tetraiodosilane, tetrafluorosilane, trichlorobromide is used. Silane, trichloroiodosilane, trichlorofluorosilane, dichlorodibromosilane, dichlorodiiodosilane, dichlorodifluorosilane, chlorotribromosilane, chlorotriiodosilane, chlorotrifluorosilane, bromotriiodosilane, bromotrifluorosilane Examples of tetrapasilanes include silane, dibromodiiodosilane, dibromodifluorosilane, tribromoiodosilane, tribromofluorosilane, iodotrifluorosilane, diiododifluorosilane, and triiodofluorosilane.

In the formula, when m = 3, methyltrichlorosilane, ethyltrichlorosilane, n-or
i-Propyltrichlorosilane, n-, i-, sec- or tert
-Butyltrichlorosilane, n- or i-amyltrichlorosilane, n-hexyltrichlorosilane, n-heptyltrichlorosilane, n-octyltrichlorosilane, n-dodecyltrichlorosilane, n-tetradecyltrichlorosilane, n-hexadecyltrichlorosilane Unsaturated alkyltrichlorosilane having an unsaturated alkyl group having 1 to 4 carbon atoms, such as alkyltrichlorosilane having a saturated alkyl group having 1 to 6 carbon atoms, such as silane, vinyltrichlorosilane, isobutenyltrichlorosilane, chloro Methyltrichlorosilane, dichloromethyltrichlorosilane,
Trichloromethyltrichlorosilane, (2-chloroethyl) trichlorosilane, (1,2-dibromoethyl) trichlorosilane, trifluoromethyltrichlorosilane,
Saturated or unsaturated cycloalkyltrichlorosilanes such as haloalkyl or unsaturated haloalkyltrichlorosilanes such as (vinyl-1-chloro) trichlorosilane, cyclopropyltrichlorosilane, cyclopentyltrichlorosilane, cyclohexenyltrichlorosilane, 3-cyclohexenyltrichlorosilane. Aryl or aralkyltrichlorosilane such as phenyltrichlorosilane, 2-, 3- or 4-tolyltrichlorosilane, benzyltrichlorosilane, methyldifluorochlorosilane,
Methylfluorodichlorosilane, ethyldifluorochlorosilane, ethylfluorodichlorosilane, n- or i-
Propyldifluorochlorosilane, n-butyldifluorochlorosilane, n-butylfluorodichlorosilane, phenyldifluorochlorosilane, methyldichlorobromosilane, ethyldichlorobromosilane, methyldichloroiodosilane, (trifluoromethyl ) Examples include alkyl- or haloalkyl-mixed trihalosilanes such as difluorobromsilane.

In the formula, when m = 2, dimethyldichlorosilane, diethyldichlorosilane, di-n-or-
i-Propyldichlorosilane, di-n-, -i-, -sec- or -t
ert-Butyldichlorosilane, di-n- or -i-amyldichlorosilane, di-n-hexyldichlorosilane, di-n-heptyldichlorosilane, di-n-octyldichlorosilane, etc. Halosilane, dicyclopentyldichlorosilane, dicyclohexyldichlorosilane, dicyclohexyldibromosilane, dicyclohexyldiiodosilane, dicycloalkyldihalosilane such as dicyclohexyldifluorosilane, diphenyldichlorosilane,
Examples thereof include diaryl or diaralkyldihalosilanes such as di-2-,-3- or -4-tolyldichlorosilane and dibenzyldichlorosilane.

In the formula, when m = 1, trimethylchlorosilane, triethylchlorosilane, tri (n- and i-propyl) chlorosilane, tri (n- and i-butyl) chlorosilane, tri (n-hexyl) ) Chlorsilane,
Tri (n-heptyl) chlorosilane, tri (n-octyl)
Trialkylhalosilanes such as chlorosilane, dimethyl (ethyl) chlorosilane, methyl (diethyl) chlorosilane, triphenylchlorosilane, tri (2-, 3- or 4-tolyl) chlorosilane, triaryl or triaryl such as tribenzylchlorosilane. Examples include aralkylhalosilane.

Among these, tetrachlorosilane, trichlorobromosilane, dichlorodibromosilane, chlorotribromosilane, and mono-, di- or trichlorosilane in which R is methyl, ethyl or phenyl are preferable.

As the halogen-containing compound, halogen-containing alcohols can be exemplified. Specific examples of the halogen-containing alcohols include 2-chloroethanol, 1-chloro-2-propanol, 3-chloro-1-propanol, 1-chloro-2-methyl-2-propanol and 4-chloro-1.
-Butanol, 5-chloro-1-pentanol, 6-chloro-1-
Hexanol, 3-chloro-1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol,
(m, o, p) -chlorobenzyl alcohol, 4-chlorocatechol, 4-chloro- (m, o) -cresol, 6-chloro- (m, o) -cresol, 4-chloro-3,5-dimethyl Phenol, chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthol, (m, o, p) -chlorophenol, p-chloro-α-methylbenzyl alcohol, 2-chloro-4-phenyl Phenol, 6-chlorothymol, 4-chlororesorcin, 2-bromoethanol, 3-bromo-1-propanol, 1
-Brom-2-propanol, 1-Brom-2-butanol, 2-
Brom-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (m, o, p) -bromophenol, 4-bromoresorcin, (m, o, p) -fluorophenol, p -Iodophenol, 2,2-dichloroethanol, 2,3-dichloro-1-
Propanol, 1,3-dichloro-2-propanol, 3-chloro-1- (α-chloromethyl-1-propanol, 2,3-dibromo-1-propanol, 1,3-dibromo-2-propanol, 2,
4-dibromophenol, 2,4-dibromo-1-naphthol,
2,2,2-trichloroethanol, 1,1,1-trichloro-2-propanol, β, β, β-trichloro-tert-butanol,
2,3,4-trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,3,5-tribromo-2-hydroxytoluene, 2,3,5-tribromo-4-hydroxytoluene, 2,2,2-
Trifluoroethanol, α, α, α-trifluoro-m-cresol, 2,4,6-triiodophenol, 2,3,4,6-tetrachlorophenol, tetrachlorohydroquinone, tetrachlorobisphenol A, tetrabromo Bisphenol A, 2,2,3,3-tetrafluoro-1-propanol, 2,
Examples include 3,5,6-tetrafluorophenol and tetrafluororesorcin.

As other halogen-containing compounds, halogen in the elemental state such as chlorine, bromine and iodine, hydrogen halide such as hydrogen chloride, hydrogen bromide and hydrogen iodide,
Carbon tetrachloride, chloroform, ethane dichloride, ethane tetrachloride, methylene chloride, trichlene, methyl chloride, ethyl chloride, haloalkanes such as -n-butyl chloride, -n-octyl chloride, sulfuryl chloride, thionyl chloride, nitrosyl chloride,
Non-metal oxyhalides such as phosphorus oxychloride and phosgene, metal halides such as phosphorus trichloride and phosphorus pentachloride, metal or ammonium halides such as aluminum chloride and ammonium chloride, ethyl magnesium chloride, propyl magnesium chloride, There can also be mentioned alkyl magnesium halides such as butyl magnesium chloride, hexyl magnesium chloride and amyl magnesium chloride.

These halogen-containing compounds may be used alone or in combination of two or more. The solid titanium catalyst component [I] according to the present invention is prepared by bringing (i) the specific magnesium compound, (ii) the liquid titanium compound, and (iii) the polyether compound into contact with each other. It

In the present invention, this contact can be carried out in the presence of a solvent. As such a solvent, specifically,
Aromatic hydrocarbons, halogenated hydrocarbons, titanic acid esters, alcohols, aldehydes, amines, carboxylic acids, esters of metal acids other than titanic acid, inert solvents, organic epoxy compounds, organic phosphoric acid compounds and the like. .

Specific examples of such aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, propylbenzene and trimethylbenzene.

Specific examples of the halogenated hydrocarbon include aromatic or aliphatic hydrocarbons which are liquid at room temperature, and examples thereof include propyl chloride, butyl chloride, butyl bromide, propyl iodide, chlorobenzene and benzyl chloride. , Dichloroethane, trichloroethylene, dichloropropane, dichlorobenzene, trichloroethane, carbon tetrachloride, chloroform, methylene chloride, ethylene chloride and the like.

Specific examples of the titanic acid ester include methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, i-propyl orthotitanate, n-butyl orthotitanate, and i-butyl orthotitanate. N-amyl orthotitanate, 2-ethylhexyl orthotitanate, n-octyl orthotitanate, orthotitanate esters such as phenyl orthotitanate and cyclohexyl orthotitanate, methyl polytitanate, ethyl polytitanate,
N-propyl polytitanate, i-propyl polytitanate, n-butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate and cyclohexyl polytitanate, etc. The polytitanate esters of are listed.

Specific examples of the alcohol include methanol, ethanol, propanol, butanol, ethylene glycol, methylcarbitol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol and 2-ethylhexanol. , Decanol, dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol, stearyl alcohol and other aliphatic alcohols, cyclohexanol, methylcyclohexanol and other alicyclic alcohols, benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, α-methylbenzyl Aliphatic alcohols containing alcohols, aromatic alcohols such as α, α-dimethylbenzyl alcohol, and alkoxy groups such as n-butyl cellosolve and 1-butoxy-2-propanol. Le and the like.

Specific examples of the carboxylic acid include caprylic acid, 2-ethylhexanoic acid, undecylenic acid,
Examples thereof include organic carboxylic acids having 7 or more carbon atoms such as undecanoic acid, nonionic acid, and octanoic acid.

Specific examples of the aldehyde include 7 carbon atoms such as capric aldehyde, 2-ethylhexyl aldehyde, capryl aldehyde and undecyl aldehyde.
The above aldehydes can be mentioned.

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

Examples of metal acid esters other than titanic acid include zirconium tetraalkoxides such as zirconium tetramethoxide, zirconium tetraethoxide, zirconium tetrabutoxide and zirconium tetrapropoxide.

Specific examples of the inert solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, and cycloaliphatic rings such as cyclopentane, cyclohexane and methylcyclopentane. Examples thereof include aromatic hydrocarbons such as group hydrocarbons, benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof.

Specific examples of the organic epoxy compound include
Examples thereof include ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, butadiene dioxide, and epoxychloropropane.

Specific examples of the organic phosphoric acid compound include trimethyl phosphoric acid, triethyl phosphoric acid, tributyl phosphoric acid and triphenyl phosphoric acid. Of these, toluene, xylene, ethylbenzene, decane, octane, heptane, propyl chloride, dichloroethane, carbon tetrachloride, chloroform and methylene chloride are preferable.

These may be used alone or in combination of two or more. In the present invention, in the preparation of the solid titanium catalyst component [I], the above-mentioned (i) magnesium compound, (ii) liquid-state titanium compound and (iii) polyether compound may be used, if necessary, in any step. Other compounds may be used in combination, such as calcium chloride (CaCl ₂ ), calcium oxide (CaO), and fatty acid calcium.

In the present invention, the above-mentioned (i) magnesium compound, (ii) liquid state titanium compound and (ii)
i) In preparing the solid titanium catalyst component [I] from the polyether compound, these (i), (ii) and (i)
Although the amount of ii) used varies depending on the type, contact conditions, contact sequence, etc., it is usually 0.05 mol to (ii) titanium compound in a liquid state per 1 mol of magnesium compound.
1000 mol, preferably 0.05 mol to 500 mol,
It is particularly preferably used in an amount of 0.1 mol to 200 mol, and (iii) the polyether compound is 0.01 mol to 5 mol, preferably 0.05 mol to 2 mol, and particularly preferably 0.1 mol to. Used in an amount of 1 mol.

The contact of these compounds is usually from -70 ° C to 2 ° C.
It is carried out at a temperature of 00 ° C, preferably -50 ° C to 150 ° C. In the present invention, the compounds (i), (ii) and
The solid titanium catalyst component [I] is prepared by contacting (iii) with each other, but the order of contacting these compounds is not particularly limited.

The preferred contact method will be described in detail below. In addition, in the following description, the organometallic compound is a [II] organometallic compound as specifically described below. (1) (i) After suspending the magnesium compound in a solvent,
(i) In the suspension of magnesium compound (ii) Titanium compound
(iii) A method of obtaining a solid titanium catalyst component by contacting with a polyether compound.

At this time, the (ii) titanium compound and the (iii) polyether compound may be added separately or simultaneously to the suspension of the (i) magnesium compound. At this time, the calcium compound may be used in any step. (2) A method in which (i) a magnesium compound and an electron donor are brought into contact with each other, then an organometallic compound and / or a halogen-containing compound is brought into contact therewith, and (ii) a titanium compound is subjected to a catalytic reaction. At this time, in any step, (iii) the polyether compound is always used once. (3) A method in which (i) a complex comprising a magnesium compound and an electron donor is brought into contact with an organometallic compound and / or a halogen-containing compound, and then (ii) a titanium compound is subjected to a catalytic reaction. At this time, in any step, (iii) the polyether compound is always used once. Further, the complex may be solid or liquid. (4) A method of reacting a complex composed of (i) a magnesium compound and (iii) a polyether compound with (ii) a titanium compound. (5) A method in which a complex composed of (i) a magnesium compound and (iii) a polyether compound is contacted with an organometallic compound and / or a halogen-containing compound, and then (ii) a titanium compound is subjected to a catalytic reaction. (6) A method in which (i) a magnesium compound and alkoxytitanium are mixed and then contacted with (ii) a titanium compound and (iii) a polyether compound. At this time, it is preferable to coexist with a halogen-containing compound such as a halogen-containing silicon compound. Further, (i) a magnesium compound and alkoxytitanium may be mixed to form a liquid. (7) (i) After reacting a magnesium compound with an organometallic compound to precipitate a solid magnesium-metal (aluminum) complex, (iii) a polyether compound and
(ii) A method of reacting with a titanium compound. (8) (i) a magnesium compound and, if necessary, a solid obtained by crushing the calcium compound, (ii)
A method of contacting with i) a polyether compound and (ii) a titanium compound. At this time, a halogen-containing compound may coexist. (9) A method of co-milling (i) a magnesium compound and (ii) a titanium compound, and then contacting with (iii) a polyether compound. (10) A method of further reacting the reaction product obtained in (1) to (9) with (ii) a titanium compound. At this time, it is preferable to carry out in the presence of an aromatic hydrocarbon and / or a halogenated hydrocarbon. (11) A method of further reacting the reaction product obtained in (1) to (9) with (iii) a polyether compound and (ii) a titanium compound. At this time, it is preferable to carry out in the presence of an aromatic hydrocarbon and / or a halogenated hydrocarbon.

In the present invention, compounds (i), (ii) and (ii)
Upon contacting i), it is preferable that the magnesium compound (i) is used by suspending it in an aromatic hydrocarbon or halogenated hydrocarbon in advance.

The (i) magnesium compound is preferably suspended in an aromatic hydrocarbon or a halogenated hydrocarbon at a temperature near room temperature. At this time, as described above, the titanium compound (ii) and the polyether compound (iii) may be added to the magnesium compound (i) (or a suspension thereof) separately or simultaneously.

The above reaction is usually carried out with stirring. The solid titanium catalyst component [I] (solid substance) thus obtained may be washed with a suitable solvent such as n-heptane.

In the present invention, when the solid titanium catalyst component [I] is prepared, a trialkoxyboron compound, alkoxyaluminum, alcohol or the like may be used in combination, if necessary.

Specific examples of such trialkoxyboron compounds include trimethoxyboron, triethoxyboron, tripropoxyboron, triisopropoxyboron, tributoxyboron and triisobutoxyboron.

Specific examples of the alkoxyaluminum include triethoxyaluminum, tripropoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, triisobutoxyaluminum and the like.

Specific examples of the alcohol include ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, isopentanol, hexanol, isohexanol, heptanol, isoheptanol, octanol and isooctanol.

These trialkoxyboron compounds, alkoxyaluminums or alcohols can be prepared, for example, in the contacting step as described above at 80 ° C. or lower after (ii) a titanium compound is added to a suspension of (i) a magnesium compound. It is preferably added. More specifically, for example
(i) After adding the titanium compound (ii) to the magnesium compound suspension, adding a trialkoxyboron compound, alkoxyaluminum or alcohol at 80 ° C or lower, and then raising the temperature to 80 ° C or higher, (iii) It is preferable to add a polyether compound and react at a temperature of 80 to 135 ° C.

Further, in the present invention, the solid titanium catalyst component [I] obtained as described above may be further contacted with the titanium compound (ii). This contacting is preferably carried out in the presence of a solvent such as an aromatic hydrocarbon or a halogenated hydrocarbon. Further, prior to this contact, it is preferable to wash the solid titanium catalyst component [I] obtained above in advance with an inert solvent, aromatic hydrocarbon, halogenated hydrocarbon or the like described later.

The contact temperature and time of the solid titanium catalyst component [I] and the titanium compound (ii) are not particularly limited, but the contact temperature is usually 80 to 135 ° C., and the contact time is usually 10 minutes. ~ 10 hours.

Solid titanium catalyst component [I] as described above
And (ii) upon contact with the titanium compound, (iii) a polyether compound, another electron donor, a solvent,
Other compounds used as necessary may coexist.

In the present invention, the solid titanium catalyst component [I] obtained as described above is further contacted with a silicon compound and an organoaluminum compound which are used in the preparation of an olefin polymerization catalyst as described below. Good.

The solid titanium catalyst component thus obtained may be washed with a suitable solvent such as n-heptane. The solid titanium catalyst component according to the present invention can be used as it is after washing, resuspended in a solvent, or dried after washing.

The solid titanium catalyst component according to the present invention obtained as described above is composed of titanium, magnesium, a compound having two or more ether bonds existing through a plurality of atoms (polyether compound) and bromine or Iodine and more preferably contains other halogen.

In the solid titanium catalyst component [I], the magnesium / titanium (atomic ratio) is 1 to 10
0, preferably 2 to 50, particularly preferably 4 to 50, and the polyether compound / titanium (molar ratio) is 0.01.
To 100, preferably 0.05 to 50, particularly preferably 0.1 to 30, and iodine or bromine / titanium (atomic ratio) is preferably 2 to 200, more preferably 4 to
90. Other halogen / titanium (atomic ratio)
It is preferably 10 or less, more preferably 5 or less, and particularly preferably 1 or less.

The solid titanium catalyst component according to the present invention may be supported on a solid carrier. Examples of such carriers include Al ₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO,
CaO, TiO ₂ , ZnO, Zn ₂ O, SnO ₂ , Ba
Resins such as O, ThO, and styrene-divinylbenzene copolymer are used. Among them, Al ₂ O ₃ and SiO ₂
A styrene-divinylbenzene copolymer is preferred.

The olefin polymerization catalyst according to the present invention is an organometallic compound containing a solid titanium catalyst component [I] as described above and a metal selected from [II] Group I to Group III of the periodic table. It comprises a catalyst component and, if necessary, a [III] electron donor.

FIG. 1 shows the steps for preparing the olefin polymerization catalyst according to the present invention. As such an organometallic compound catalyst component [II], for example, an organoaluminum compound, a complex alkylated product of a group I metal and aluminum, an organometallic compound of a group II metal, and the like can be used.

As such an organoaluminum compound, for example, an organoaluminum compound represented by the following formula can be exemplified. In the formula of R ¹ _n AlX _3-n , R ¹ is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3.

Examples of the hydrocarbon group having 1 to 15 carbon atoms include an alkyl group, a cycloalkyl group and an aryl group. Specific examples include a methyl group, an ethyl group, an n-propyl group, Examples thereof include isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trimethylaluminum, triethylaluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, trialkyl aluminum Nim and tri 2-ethylhexyl aluminum, the general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z [Where x, y, z
Is a positive number and z ≧ 2x. ] Alkenyl aluminum such as isoprenyl aluminum represented by
Trialkenyl aluminum such as triisopropenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum halide such as dimethyl aluminum bromide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, Alkyl aluminum sesquichlorides such as butyl aluminum sesquichloride, ethyl aluminum sesquibromide, alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide, diethyl aluminum hydride Dialkylaluminum hydride such as dibutyl aluminum hydride, ethyl aluminum dihydride, alkyl aluminum dihydride such as propyl aluminum dihydride and the like.

As the organoaluminum compound, compounds represented by the following formula can also be mentioned. R ¹ _n AlY _{3-n In the} formula, R ¹ is the same as the above formula, Y is a —OR ¹⁰ group,
OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR ¹³ ₂ group, -S
iR ¹⁴ ₃ group or —N (R ¹⁵ ) AlR ¹⁶ ₂ group.
R ¹⁰ , R ¹¹ , R ¹² and R ¹⁶ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ¹³ is hydrogen, a methyl group, an ethyl group,
It is an isopropyl group, a phenyl group, a trimethylsilyl group or the like, and R ¹⁴ and R ¹⁵ are a methyl group, an ethyl group or the like. n is 1-2.

Specific examples of the organoaluminum compound represented by the above formula include the following compounds. (1) Compounds represented by R ¹ _n Al (OR ¹⁰ ) _3-n , for example, dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, ethyl aluminum sesquiethoxide, butyl aluminum Sesquibutoxide and partially alkoxylated alkylaluminum having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 , ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, ethylaluminum ethoxy bromide and the like. And halogenated alkylaluminums. (2) a compound represented by R ¹ _n Al (OSi R ¹¹ ₃ ) _3-n ,
For example, Et ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Et ₃ ), etc. (3) R ¹ _n Al (OAlR ¹² ₂ ) _3- a compound represented by _n ,
For example, Et ₂ AlOAlEt ₂ (iso-Bu) ₂ AlOAl (iso-Bu) _{2 and} other compounds represented by (4) R ¹ _n Al (NR ¹³ ₂ ) _3-n , such as Me ₂ AlNEt ₂ Et ₂ AlNHMe Me ₂ AlNHET Et ₂ AlN (Si Me ₃ ) ₂ (iso-Bu) ₂ AlN (SiMe ₃ ) _{2 and} other compounds represented by (5) R ¹ _n Al (Si R ¹⁴ ₃ ) _3-n , for example, , (Iso-Bu) ₂ AlSi Me _3, etc., (6) compounds represented by R ¹ _n Al [N (R ¹³ ) AlR ¹⁶ ₂ ] _3-n , such as Et ₂ AlN (Me) AlEt ₂ , (i
so-Bu) ₂ AlN (Et) Al (iso-Bu) _{2 and the} like.

Organoaluminum used in the present invention
The compound is an organic compound component of a metal other than aluminum.
It may be contained in a small amount. Among these, R¹ ₃Al,
R¹ _nAl (OR^Ten)_3-n, R¹ _nAl (OAlR¹² ₂)
_3-nThe organoaluminum compound represented by is preferred.

Examples of complex alkylated products of Group I metal and aluminum include compounds represented by the following general formula. M ¹ AlR ^j ₄ (wherein M ¹ is Li, Na, K, and R ^j is 1 carbon atom)
~ 15 hydrocarbon groups. ) Specifically, LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H
₁₅ ) ₄ etc.

Examples of the organometallic compound of Group II metal include compounds represented by the following general formula. R ^k R ^l M ² (provided that R ^k and R ^l are a hydrocarbon group having 1 to 15 carbon atoms or a halogen atom, and they may be the same or different from each other, but they are excluded when they are halogen atoms. M
² is Mg, Zn and Cd. ) Specifically, diethyl zinc, diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, butyl magnesium chloride and the like can be mentioned.

These may be used alone or in combination. In the present invention, the [III] electron donor, which is optionally used when preparing the olefin polymerization catalyst, is specifically, when preparing the above-mentioned [I] solid titanium catalyst component. The indicated (iii) polyether compound and electron donor are used, but an organosilicon compound represented by the following general formula can also be used.

R _n Si (OR ′) _4-n (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysisilane, diisopropyldimethoxysilane,
t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane , Screw p-
Tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-
Aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethylsilane Dimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane,
Methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane Silane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, Dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane Orchid, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane.

Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Bis p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentylmethoxysilane, cyclopentyldimethylmethoxysilane, etc. It is preferably used. These may be used alone or in combination.

Further, in the present invention, as the [III] electron donor, a nitrogen-containing compound, another oxygen-containing compound, a phosphorus-containing compound or the like can be used. Specific examples of such nitrogen-containing compounds include the compounds shown below.

[0095]

[Chemical 5]

[0096]

[Chemical 6]

2,6-substituted piperidines such as

[0098]

[Chemical 7]

2,5-substituted piperidines such as N, N, N ', N'-
Substituted methylenediamines such as tetramethylmethylenediamine, N, N, N ', N'-tetraethylmethylenediamine, 1,
Substituted imidazolines such as 3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine.

Specific examples of the phosphorus-containing compound include phosphite esters shown below. Triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite,
Phosphorous acid esters such as triisobutyl phosphite, diethyl n-butyl phosphite, and diethyl phenyl phosphite.

Further, as the oxygen-containing compound, specifically,
The following compounds may be mentioned.

[0102]

[Chemical 8]

2,6-substituted tetrahydropyrans such as

[0104]

[Chemical 9]

2,5-Substituted tetrahydropyrans such as the above and the above compounds can be used in combination of two or more kinds. These compounds can also be used when preparing a solid titanium catalyst component.

In the olefin polymerization method according to the present invention, the olefin is polymerized or copolymerized in the presence of the above-mentioned olefin polymerization catalyst. Examples of the olefin used in the present invention include α-olefins having 2 to 20 carbon atoms, specifically, ethylene, propylene, 1-butene, 1-
Pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-
1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3- Ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. These may be used alone or in combination.

Further, aromatic vinyl compounds such as styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalene, substituted vinylnaphthalene, allylnaphthalene and substituted allylnaphthalene, vinylcyclopentane, substituted vinylcyclopentanes. , Vinylcyclohexane, substituted vinylcyclohexanes, vinylcycloheptane, substituted vinylcycloheptanes, alicyclic vinyl compounds such as allyl norbornane, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1 -Hexene, 8-trimethylsilyl-1-octene, 10-trimethylsilyl-1-
Silane unsaturated compounds such as decene, cyclopentene,
Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene Such as cyclic olefins, 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- Conjugate or non-conjugate of dienes such as ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, isoprene and butadiene. A conjugated diene or the like can also be used.

Of these, ethylene, propylene, 1-
Butene, 4-methyl-1-pentene, 3-methyl-1-butene, 7-
Methyl-1,6-octadiene, 1,7-octadiene, 1,9-decadiene, allyltrimethylsilane and the like are preferably used.

In the olefin polymerization method according to the present invention,
The olefin can be preliminarily polymerized with the olefin polymerization catalyst prior to the polymerization (main polymerization). This prepolymerization is 0.1 to 1000 per 1 g of the olefin polymerization catalyst.
g preferably 0.3 to 500 g, particularly preferably 1 to 2
It is carried out by prepolymerizing an olefin as described above in an amount of 00 g.

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 10
It is 0 mmol, particularly preferably 0.1 to 50 mmol.

The organometallic compound catalyst component [II] is used in such an amount that a polymer of 0.1 to 1000 g, preferably 0.3 to 500 g, is produced per 1 g of the solid titanium catalyst component [I]. It is generally used in an amount of about 0.1 to 300 mol, preferably about 0.5 to 100 mol, and particularly preferably 1 to 50 mol, per mol of titanium atom in the titanium catalyst component [I].

When the electron donor [III] is used, it is 0.01 to 100 mol, preferably 0.05 to 100 mol, per 1 mol of titanium atom in the solid titanium catalyst component [I].
It is used in an amount of 80 mol, more preferably 0.1 to 50 mol.

The prepolymerization of olefin can be carried out by either liquid phase polymerization method such as solution polymerization, suspension polymerization (slurry polymerization) or gas phase polymerization method. The prepolymerization can be carried out batchwise or continuously.

In the present invention, this prepolymerization can be carried out in the presence of an inert hydrocarbon medium, and the olefin and the above catalyst components are added to the inert hydrocarbon medium and the prepolymerization is carried out under relatively mild conditions. It is preferable. As the inert hydrocarbon medium used in this case, specifically, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and combinations thereof. Of these inert hydrocarbon media, it is particularly preferred to use aliphatic hydrocarbons.

On the other hand, the olefin itself can be used as a solvent to carry out the prepolymerization, or the olefin itself can be prepolymerized in a substantially solvent-free state. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization, and specifically, propylene is preferable.

The reaction temperature in the prepolymerization is usually about -20.
It is desirable that the temperature is from about + 100 ° C, preferably about -20 to + 80 ° C, more preferably 0 to + 40 ° C. In the prepolymerization, a molecular weight modifier such as hydrogen can be used.

The prepolymerization is, as described above, about 0.1 to 1000 g, preferably about 0.3 to 500 g, particularly preferably 1 to 200 g per 1 g of the solid titanium catalyst component [I].
It is desirable to carry out so that a polymer of If the prepolymerization amount is too large, the production efficiency of the olefin polymer may decrease.

In the olefin polymerization method according to the present invention, the main 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 reaction form of slurry polymerization, the above-mentioned inert hydrocarbon may be used as the reaction solvent, or a liquid olefin at the reaction temperature may be used.

In the polymerization method of the present invention, the solid titanium catalyst component [I] is generally about 0.001 to 1 mmol, preferably about 0.005 in terms of Ti atom per liter of polymerization volume. Used in an amount of 0.5 mmol. The organometallic compound [II] is used in an amount such that the metal atom is usually about 1 to 2000 mol, preferably about 5 to 500 mol, based on 1 mol of the titanium atom in the polymerization system. The [III] electron donor is 100 mol or less, preferably 0.005 to 50 mol, more preferably 0.01 to 30 mol, and particularly preferably 0.05 to 100 mol, relative to 1 mol of the [II] organometallic compound. It is optionally used in an amount of 20 moles.

When hydrogen is used in the main polymerization, a polymer having a high melt flow rate can be obtained, and the molecular weight of the obtained polymer can be adjusted by the amount of hydrogen added.
In the present invention, the olefin polymerization is carried out at a temperature of usually about 20 to 200 ° C., preferably about 50 to 150 ° C., and a pressure of usually atmospheric pressure to 100 kg / cm ² , preferably about 2 to 50 ° C.
It is performed under the condition of Kg / cm ² .

In the polymerization method of the present invention, such polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The olefin polymer thus obtained may be a homopolymer, a random copolymer, a block copolymer or the like. When olefin polymerization, especially propylene polymerization, is carried out using the above olefin polymerization catalyst, the isotactic index (II) represented by the boiling heptane extraction residue is 70% or more, preferably 85% or more, more preferably 90%. Above all, particularly preferably 95% or more of a propylene polymer is obtained.

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

[0124]

EFFECTS OF THE INVENTION The solid titanium catalyst component for olefin polymerization according to the present invention has a high catalytic activity during polymerization and is capable of producing an olefin polymer excellent in stereospecificity in a high yield. Form a catalyst for use.

In the olefin polymerization method according to the present invention, olefin is polymerized by using the olefin polymerization catalyst according to the present invention, and the catalyst activity is high and the polymerization reaction can be performed efficiently and the stereospecificity is high. A polymer can be obtained.

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

[0127]

[Example 1] "Preparation of solid titanium catalyst component" In a 200 ml round bottom flask equipped with a stirrer, which was sufficiently replaced with nitrogen gas, 28 g of magnesium ethoxyiodide and 80 ml of toluene were added.
It was taken and fully suspended. The suspension is then charged with TiCl
20 ml of ₄ was added, and the temperature was raised to 90 ° C., and 2-isopentyl-2-
Isopropyl-1,3-dimethoxypropane (IPAMP)
2.5 ml was added, the temperature was further raised to 115 ° C., and the reaction was carried out while stirring for 2 hours. After completion of the reaction, the product was washed twice with 100 ml of toluene at 90 ° C., and 20 ml of TiCl ₄ was newly added.
Then, 80 ml of toluene was added and the reaction was carried out while stirring at 115 ° C. for 2 hours. After completion of the reaction, decantation was performed at 115 ° C, and then the reaction product was washed 10 times with 200 ml of 40 ° C n-heptane. The catalyst component thus obtained contained 2.8% by weight of titanium component. “Polymerization” 750 ml of purified n-hexane was inserted into an autoclave with an internal volume of 2 liters, and 0.75 mmol of triethylaluminum and 0.075 of cyclohexylmethyldimethoxysilane (CMMS) in a propylene atmosphere at 60 ° C.
And 0.0075 mmol Ti in terms of titanium atom based on the solid titanium catalyst component obtained as described above.
Charged.

150 ml of hydrogen was introduced, the temperature was raised to 70 ° C., and this was held for 2 hours to carry out propylene polymerization. The pressure during the polymerization was kept at 7 kg / cm ² G. The polymerization results are shown in Table 1.

[0129]

Example 2 “Polymerization” In Example 1, instead of CMMS, IP
Example 1 except that 0.075 mmol of AMP was used.
Polymerization of propylene was carried out in the same manner as in. The results are shown in Table 1.

[0130]

[Example 3] "Polymerization" Polymerization of propylene was carried out in the same manner as in Example 1 except that IPAMP was not added during the polymerization. The results are shown in Table 1.

[0131]

[Example 4] "Preparation of solid titanium catalyst component"
Except that 3.8 ml of isopentyl-2-isopropyl-1,3-dimethoxypropane was added instead of 2.5 ml.
A solid titanium catalyst component was prepared in the same manner as in Example 1. "Polymerization" In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component was changed to the above-mentioned one. The results are shown in Table 1.

[0132]

Example 5 A solid titanium catalyst component was prepared in the same manner as in Example 4, and propylene was polymerized in the same manner as in Example 2. The results are shown in Table 1.

[0133]

Example 6 “Preparation of solid titanium catalyst component” A solid titanium catalyst component was prepared in the same manner as in Example 4, and propylene was polymerized in the same manner as in Example 3. The results are shown in Table 1.

[0134]

Comparative Example 1 “Preparation of Solid Titanium Catalyst Component” In Example 1,
A solid titanium catalyst component was prepared in the same manner as in Example 1 except that 2.7 ml of diisobutyl phthalate was used instead of isopentyl-2-isopropyl-1,3-dimethoxypropane. The obtained solid titanium catalyst component,
It contained 2.7% by weight of titanium. "Polymerization" Other than using the solid titanium catalyst component described above,
Polymerization was carried out in the same manner as in Example 1. The results are shown in Table 1.

[0135]

[Table 1]

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (4)

[Claims] (I) Formula XMg (OR) [X is Br or I, and R is a hydrocarbon group. ] A magnesium compound represented by: (ii) a titanium compound in a liquid state, and (iii) a compound having two or more ether bonds existing through a plurality of atoms are brought into contact with each other to obtain titanium, magnesium , Existing through multiple atoms 2
A solid titanium catalyst component for olefin polymerization, which comprises a compound having at least one ether bond and bromine or iodine. 2. The (iii) 2 which exists through a plurality of atoms
The solid titanium catalyst component for olefin polymerization according to claim 1, wherein the compound having at least one ether bond is represented by the following formula: (In the formula, n is an integer of 2 ≦ n ≦ 10, and R ¹ to
R ²⁶ is a substituent having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any R ^{1 to} R ²⁶ are jointly other than a benzene ring. May form a ring, and the main chain may contain atoms other than carbon. ). 3. [I] The solid titanium catalyst component for olefin polymerization according to claim 1, and [II] Group I to II of the periodic table.
An olefin polymerization catalyst, which is formed from an organometallic compound catalyst component containing a metal selected from Group I and, if necessary, a [III] electron donor. 4. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 3.