JPH06279531A - Solid titanium catalyst component for olefin polymerization, olefin polymerization catalyst, and method of olefin polymerization using the same - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] To produce olefin (co) polymers with excellent stereoregularity with high polymerization activity. [Structure] A solid titanium catalyst component for polymerization comprises (a) a magnesium-containing solution formed by the reaction of an organic magnesium compound and carbon dioxide, (b) a titanium compound in a liquid state, and (d) a cyclic ether compound. , (E) a compound having two or more ether bonds existing through a plurality of atoms,
Preferably, in formula (c) R _m SiR ′ _4-m (0 ≦ m ≦ 4
And R is H or an organic group such as a C _1-10 alkyl group, and R ′ is OR or a halogen atom. And a compound having two or more ether bonds which are present through titanium, magnesium and a plurality of atoms. [I] above
Formed from solid titanium catalyst component for olefin polymerization, [II] organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table, and optionally [III] electron donor The olefin is polymerized in the presence of the polymerization catalyst.

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, a solid titanium catalyst component and an organometallic compound catalyst component (co-catalyst component) have been used as olefin polymerization catalysts used in the production of olefin polymers by polymerizing or copolymerizing olefins. A catalyst formed from and is known.

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 (for example, It is known that a catalyst formed with (alkoxysilane) 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 a higher polymerization activity. A solid titanium catalyst component prepared by contacting a liquid state titanium compound, an organosilicon compound, a cyclic ether compound, and a compound having two or more ether bonds existing with a plurality of atoms interposed therebetween. The inventors have found that the olefin polymerization catalyst containing OH can polymerize olefin with excellent polymerization activity and can produce an olefin polymer having excellent stereoregularity, and thus completed the present invention.

[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 A solid titanium catalyst component for olefin polymerization according to the present invention comprises (a) a magnesium-containing solution formed by the reaction of an organomagnesium compound and carbon dioxide, and (b) a titanium compound in a liquid state, (c) Formula R _m SiR ′ _4-m (wherein 0 ≦ m ≦ 4, R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a haloalkyl group, an aryl group, or 1 to 1 carbon atoms). 8 is a haloalkylsilyl group, and R ′ is OR or a halogen atom.), (D) a cyclic ether compound, and (e) two or more existing through a plurality of atoms. Obtained by contacting with a compound having an ether bond of
It is characterized by containing titanium, magnesium, halogen and a compound having two or more ether bonds existing through a plurality of atoms.

The compound (e) having two or more ether bonds existing through a plurality of atoms 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 (a) a magnesium-containing solution formed by the reaction of an organomagnesium compound and carbon dioxide, and (b) a titanium compound in a liquid state. (C) Formula R _m SiR ′ _4-m (wherein 0 ≦ m ≦ 4, R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a haloalkyl group, an aryl group, or 1 carbon atom). ~ 8 is a haloalkylsilyl group, and R'is OR or a halogen atom.), (D) a cyclic ether compound, and (e) two existing through a plurality of atoms. Obtained by contacting with a compound having the above ether bond,
It contains titanium, magnesium, halogen, and a compound having two or more ether bonds existing through a plurality of atoms.

First, each component used for preparing the solid titanium catalyst component [I] will be described. (a) Magnesium-Containing Solution The (a) magnesium-containing solution used in the present invention is specifically a solvent as described below, preferably in the presence of an alcohol, and an organic magnesium compound and carbon dioxide (C
It is obtained by reacting with O ₂ ).

At this time, for example, it is preferable to use alkoxy magnesium (magnesium alcoholate) as the organic magnesium compound. Specific examples of the alkoxy magnesium as described above include the following compounds.

As such an alkoxy magnesium
Specifically, Mg (OCH₃)₂, Mg (OC₂H_Five)
₂, Mg (OC₃H₇)₂, Mg (OC_FourH₉)₂, Mg
(OC₆H₁₃)₂, Mg (OC₈H₁₇)₂, Mg (OC₉
H₁₉)₂, Mg (OC₁₂H_{twenty five})₂, Mg (OC₁₆H₃₃)
₂, Mg (OC₁₈H₃₇)₂, Mg (OC₂₀H₄₁)₂, M
g (OCH₃) (OC₂H_Five), Mg (OCH₃) (OC₆
H₁₃), Mg (OC₂H_Five) (OC₈H₁₇), Mg (OC₆
H₁₃) (OC₂₀H₄₁), Mg (OC₁₆H₃₃) (OC₁₈H
₃₇) Etc. dialkoxy magnesium, Mg (OC
_FourH₉) (OC₂H_Five), Mg (OC₃H₇) (OC_FourH₉),
Mg (OC ₂H_Five) (OC₈H₁₇) Alkoxy mugs
Nesium, Mg (OC₆H_Five)₂, Mg (OC
_TenH₇)₂, Mg (OC₁₂H₉)₂Diaryloxima such as
Gnesium, Mg (OC₃H₇) (OC_TenH₇) Etc.
Lucoxy allyloxy magnesium, Mg (OC₂H_FourC
l)₂And so on.

These may be used alone or in combination. In the present invention, in addition to these alkoxy magnesium, if necessary, other alkaline earth metal alkoxides, alkali metal alkoxides, small amounts of other metal salts such as lanthanum or lanthanide metal alkoxides or magnesium halides, hydroxy halides. , Carboxylic acid salts and the like can also be used.

Further, when the reaction between the organomagnesium compound and carbon dioxide is carried out in the presence of alcohol,
Alkoxyalkyl magnesium can also be used as the magnesium compound.

In addition, (a) when preparing a magnesium-containing solution
Then, as the organomagnesium compound, specifically, the following formula
It is also possible to use an organomagnesium compound represented by
It RMgQ In the formula, Q is a hydrogen atom, a halogen atom or 1 to 2 carbon atoms.
0 is a hydrocarbon group, and R is a hydrocarbon having 1 to 20 carbon atoms.
It is a base. As such an organomagnesium compound
Specifically, Mg (CH₃)₂, Mg (C₂H_Five)₂, M
g (C₃H₈)₂, Mg (C_FourH₉)₂, Mg (C_FiveH₁₁)₂,
Mg (C₆H_Five)₂, Mg (C₆H₁₃)₂, Mg (C₉H₁₉)
₂, Mg (C_TenH₇)₂, Mg (C_TenH_{twenty one})₂, Mg (C₁₂
H₉)₂, Mg (C₁₂H_{twenty five})₂, (C₁₆H₃₃)₂, Mg (C
₂₀H₄₁)₂, Mg (CH₃) (C₂H_Five), Mg (CH₃)
(C₆H₁₃), Mg (C₂H_Five) (C_FourH₉), Mg (C₂H
_Five) (C₈H₁₇), Mg (C_FourH₉) (C₈H₁₇), Mg
(C₆H₁₃) (C₂₀H₄₁), Mg (C₃H₇) (C
_TenH ₇), Mg (C₂H_FourCl)₂, Mg (C₁₆H₃₃) (C
₁₈H₃₇), MgH (C₂H_Five), Mg (C₂H_Five) Cl, M
g (C₃H₈) Cl, Mg (C_FourH₉) Cl, Mg (C₆H
₁₃) Cl, Mg (C_FiveH₁₁) Cl, Mg (C₂H_Five) Br
And so on.

Of these, the organomagnesium compound represented by the formula MgR ₂ and the organomagnesium halide compound represented by the formula MgR'Q 'are preferable. (R'in the formula
Is an aryl group having 6 to 12 carbon atoms and an alkyl group having 7 to 12 carbon atoms, and Q ′ is chlorine or bromine. ) (A) The magnesium-containing solution used in the present invention can be prepared by specifically suspending the above-mentioned magnesium compound in a solvent and adding carbon dioxide to the suspension to react. The reaction is preferably carried out in the presence of alcohol as described above. In the presence of alcohol, the reaction product formed in the solvent (eg magnesium hydrocarbon carbonate or carboxylic acid hydrocarbon magnesium salt) is easily solvated to form the (a) magnesium-containing solution.

As such alcohol, specifically, an alcohol having 1 to 18 carbon atoms is used. Specifically, methanol, ethanol, propanol, butanol, ethylene glycol, methylcarbitol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol, tetradecyl alcohol. , Aliphatic alcohols such as undecenol, oleyl alcohol, stearyl alcohol, cyclohexanol, alicyclic alcohols such as methylcyclohexanol, benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, α-methylbenzyl alcohol, α,
Examples thereof include aromatic alcohols such as α-dimethylbenzyl alcohol, n-butyl cellosolve, aliphatic alcohols having an alkoxy group such as 1-butoxy-2-propanol, and halogen-containing alcohols such as trichloromethanol, trichloroethanol and trichlorohexanol.

Of these, 2-ethyl-1-hexanol is particularly preferred. (b) Titanium Compound in Liquid State Specific examples of the (b) titanium compound in a liquid state used in the present invention include a tetravalent titanium compound represented by the following formula.

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 titanium compounds may be used alone or in combination. Further, it may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

(C) Organosilicon Compound The organosilicon compound used in the present invention is represented by the following formula. R _m SiR ′ _{4-m wherein} 0 ≦ m ≦ 4, and R is a hydrogen atom or a carbon number 1
-10 alkyl group, alkoxy group, haloalkyl group,
It is an aryl group, a halosilyl group or a haloalkylsilyl group having 1 to 8 carbon atoms, and R'is OR or a halogen atom.

Of these, R is preferably 1 to 1 carbon atoms.
8 is an alkyl group or a chloroalkyl group further containing 1 to 4 chlorine, and R ′ is chlorine or a —OR group having 1 to 4 carbon atoms. The R'groups may be different.

Of these organosilicon compounds, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, tetraethoxysilane, and the like are preferable.

These may be used in combination. (d) Cyclic ether compound As the (d) cyclic ether compound used in the present invention,
Specifically, tetrahydrofuran, tetrahydropyran,
2-Methyltetrahydrofuran, 2,2,5,5-tetrahydrofuran, tetrahydropyran-2-methanol and the like can be mentioned.

Of these, tetrahydrofuran is preferred. With the cyclic ether compound as described above,
You may use together cyclohexene oxide, cyclohexanone, ethyl acetate, phenyl acetate, etc.

(E) Polyether compound used in the present invention (e) existing through a plurality of atoms 2
In a compound having at least one ether bond (hereinafter sometimes referred to as a polyether compound), the atom existing between these ether bonds is one selected from the group consisting of carbon, silicon, oxygen, sulfur, phosphorus and boron. Is over,
The number of atoms is 2 or more. Of 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, Preferably, a substituent having a branched or cyclic structure is bonded.
Further, a compound in which a plurality of carbon atoms, preferably 3 to 20, more preferably 3 to 10 and particularly preferably 3 to 7 carbon atoms are contained in an atom existing between two or more ether bonds is preferable.

Examples of the polyether compound (e) include compounds represented by the following formula.

[0034]

[Chemical 3]

However, 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 above (e) polyether compound 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-dimethoxy Propane, 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, 1,3- 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 (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, diphenyl Bis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-
Butylbis (methoxymethyl) silane, cyclohexyl
-t-butylbis (methoxymethyl) silane, i-propyl-
Examples thereof include t-butylbis (methoxymethyl) silane.

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 [I], the following electron donor may be used in combination with the above-mentioned (e) polyether compound. Such other electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids,
Examples thereof include organic acid halides, organic acid or inorganic acid esters, ethers, acid amides, acid anhydrides, ammonia, amines, nitriles, and isocyanates.

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, anisole, diphenyl ether, acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-
Acid amides such as dimethylamide, trimethylamine,
Amines such as triethylamine, tributylamine, tribenzylamine, tetramethylethylenediamine,
Examples thereof include nitriles such as acetonitrile, benzonitrile and trinitrile, and acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride.

Further, as the organic acid ester, a polyvalent carboxylic acid ester can be mentioned as a particularly preferable example. As such a polyvalent carboxylic acid ester,
Examples thereof include compounds having a skeleton represented by the following general formula.

[0041]

[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 and isopropyl malon. 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. Further, the above-mentioned (e) polyether compound, electron donor, etc. 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 each component (a) magnesium-containing solution as described above, (b) a titanium compound in a liquid state, (c) an organosilicon compound, (d) a cyclic ether compound and (e) a polyether compound, If any of them contains halogen, or none of these (a), (b), (c), (d) or (e) contains halogen, use a halogen-containing compound. For example, it is preferable to finally obtain the solid titanium catalyst component [I] containing halogen together with titanium, magnesium and a 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).

As the halogen-containing silicon compound, more specifically, 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.

Further, examples of the halogen-containing compound include halogen-containing alcohols. 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. Preparation of Solid Titanium Catalyst Component The solid titanium catalyst component [I] according to the present invention comprises (a) a magnesium-containing solution, (b) a liquid titanium compound, (c) an organosilicon compound, and (d) as described above. ) It is obtained by contacting a cyclic ether compound and (e) a polyether compound.

[I] In obtaining the solid titanium catalyst component, (a) a magnesium-containing solution, (b) a liquid titanium compound, (c) an organosilicon compound, (d) a cyclic ether compound and (e) a polyether. The amount of the compound used varies depending on its type, contact conditions, contact sequence, etc.
(a) 1 mol of magnesium in the magnesium-containing solution, (b) 0.05 mol to 1 mol of the titanium compound in a liquid state.
000 mol, preferably 0.05 mol to 500 mol, particularly preferably 0.1 mol to 200 mol, and the (c) organosilicon compound is 0.01 to 50 mol, preferably 0.
In an amount of 1 to 20 moles, the (d) cyclic ether compound is 0.1.
In an amount of 01 to 50 mol, preferably 0.1 to 50 mol,
(e) The polyether compound is 0.01 to 5 mol, 0.1
Used in an amount of ~ 1 mol.

The contact of these compounds is usually from -70 ° C to 2 ° C.
It is carried out under a temperature condition of 00 ° C, preferably -50 ° C to 150 ° C. The contact of these components (a), (b), (c), (d) and (e) is preferably carried out specifically as follows.

In the present invention, first, (a) a magnesium-containing solution, (b) a liquid titanium compound and (c) an organosilicon compound are brought into contact with each other to precipitate a solid substance. The solid material is then dissolved with (d) cyclic ether and then reprecipitated.

This reprecipitated solid material and further (b)
The titanium compound and the (e) polyether compound in the liquid state are brought into contact with each other. The contact as described above is preferably performed in the presence of a solvent.

The boiling point of the solvent used in the present invention is (a) a magnesium-containing solution, (b) a liquid titanium compound,
(c) an organosilicon compound, (d) a cyclic ether compound and
(e) The temperature is preferably such that the reaction of the polyether compound can be sufficiently promoted and the catalytic performance of the solid titanium catalyst component [I] is not deteriorated.

Specific examples of such a solvent include halogenated aromatic hydrocarbons such as toluene and chlorobenzene, and a mixture of chlorobenzene and dichloroethane. Further, an aliphatic hydrocarbon such as kerosene or Isopar G (trade name) (boiling point: 156 to 176 ° C., isoparaffin hydrocarbon having an average carbon number of 10) can also be used.

In the present invention, the solvent contains 8 to 1 carbon atoms.
A small amount of 0 aromatic hydrocarbons may be included. Specific examples of the aromatic hydrocarbon having 8 to 10 carbon atoms include o-xylene, m-xylene, p-xylene, mixed xylene, ethylbenzene, naphthalene, cumene, pseudocumene, methylethylbenzene, tetrahydronaphthalene and diethylbenzene, and these. A mixture of Of these, ethylbenzene, o-xylene, m-xylene, P-xylene, naphthalene are preferable,
Naphthalene is most preferred.

The aromatic hydrocarbon having 8 to 10 carbon atoms is 0.1 to 2% by weight, preferably 0.2 to 1% by weight, and more preferably 0.4 to 1% by weight, based on the above solvent such as toluene. It is used in an amount of 0.8% by weight (0.4 to 1% by weight when only aromatic hydrocarbons having 8 carbon atoms are added).

The aromatic hydrocarbon having 8 to 10 carbon atoms may be initially contained in the solvent (eg, toluene) used for preparing the (a) magnesium-containing solution as described above. It may also be added when the solid substance is precipitated by contacting the (a) magnesium-containing solution, (b) liquid titanium compound and (c) organosilicon compound, or reprecipitation of the solid substance with cyclic ether. It may be added during the process.

In the present invention, the aromatic hydrocarbon having 8 to 10 carbon atoms is used in the precipitation of a solid substance from (a) a magnesium-containing solution, (b) a liquid titanium compound and (c) an organosilicon compound. It is preferably added to the solvent used.

When the above-mentioned contact is carried out in the presence of an aromatic hydrocarbon having 8 to 10 carbon atoms, the solid titanium catalyst component [I] finally has a narrow particle size distribution and an appropriate particle size. Obtained as uniform particles, which is preferable.

Further, in the present invention, together with the above solvent, an aliphatic hydrocarbon such as hexane, heptane, octane, decane, dodecane, undecane, an alicyclic hydrocarbon such as cyclohexane, methylcyclopentane, ethylcyclohexane, benzene, etc. Aromatic hydrocarbons such as propylbenzene and trimethylbenzene, halogenated aromatic hydrocarbons such as chlorobenzene, benzyl chloride and o-dichlorobenzene, propyl chloride, butyl chloride, butyl bromide, propyl iodide, 1,2- It is also possible to use halogenated hydrocarbons such as dichloroethane, trichloroethylene, dichloropropane, 1,1,2-trichloroethane, carbon tetrachloride, chloroform, methylene chloride and ethylene chloride.

These may be used in combination of two or more kinds. The contact method as described above will be described more specifically. For example, (a) a magnesium-containing solution (for example, a toluene solution) formed by the reaction of an organomagnesium compound with carbon dioxide in the presence of an alcohol as described above, (b) a titanium compound in a liquid state, and (c) an organosilicon compound. And are added to precipitate a solid substance. in this way
(c) When the solid substance is precipitated in the presence of the organosilicon compound, the solid titanium catalyst component [I] is finally obtained as particles having a uniform particle size, and the generation of fine powder particles is reduced, which is preferable.

The solid material is then completely dissolved in cyclic ether and heated to 40-110 ° C. for reprecipitation. Such reprecipitated solid material has a uniform particle size.

In the present invention, in addition to the solid substance reprecipitated as described above, (b) a titanium compound in a liquid state and
(e) A polyether compound, preferably an electron donor, is contacted. The contact between the solid substance and the titanium compound (b) in the liquid state and the polyether compound (e) is preferably carried out in two steps. Specifically, a solid substance is brought into contact with (b) a liquid state titanium compound, and then (b) a liquid state titanium compound is brought into contact with (e) a polyether compound. At this time, after the solid substance is brought into contact with the liquid titanium compound (b), the solid substance may be once separated from the liquid titanium compound-containing solution in the liquid state (b) After adding the titanium compound in the state, the polyether compound (e) may be added thereto.

In the present invention, the solid titanium catalyst component [I] is used.
Is usually obtained as uniform particles having a particle size of 10 to 30 μm. Further, the product obtained by such contact may be washed with an inert liquid hydrocarbon solvent such as n-heptane, if necessary. That is, it is desirable to remove unreacted substances and the like from the solid titanium catalyst component [I] obtained as described above. If an unreacted substance remains in the solid titanium catalyst component [I], the performance of the catalyst component may be deteriorated. Such an unreacted substance is a solid titanium catalyst component [I] separated from the solvent.
Are removed by washing with a suitable solvent such as liquid hydrocarbon or liquid chlorinated carbon.

Further, the solid titanium catalyst component [I] according to the present invention can be brought into contact with at least one liquid Lewis acid, if necessary, before use. The Lewis acid used in the present invention is liquid at the processing temperature and is sufficiently high to remove impurities such as unreacted starting materials and compounds that are not completely attached to the surface of the solid titanium catalyst component [I]. It preferably has a Lewis acidity.
Such Lewis acids include Group III to Group V metal halides that are in a liquid state at temperatures up to about 170 ° C. Specifically, BCl ₂ , AlBr ₃ , SiCl
₄ , GeCl ₄ , SnCl ₄ , PCl ₂ and SbCl _{3 and the} like. TiCl ₄ , TiBr ₄ , of these, TiCl ₄ and SiCl ₄ are preferred. They are,
They may be used alone or in combination of two or more. Such Lewis acids may be used with diluents that are compatible with them.

The contact between the solid titanium catalyst component [I] and the Lewis acid may be carried out after washing with the above-mentioned inert hydrocarbon solvent. In this case, it is preferable that the solid titanium catalyst component [I] is washed with an inert hydrocarbon solvent, the solvent is almost removed, and then contacted with the Lewis acid.

The method for producing the solid titanium catalyst component [I] according to the present invention is not limited to these embodiments. In the production of the solid titanium catalyst component [I] as described above, the operations such as contacting the components (a), (b), (c), (d) and (e) are substantially carried out with water, oxygen and It is preferably manufactured in the absence of catalyst poisons such as carbon dioxide. Specifically, it is preferable to carry out the contact in an atmosphere of an inert gas such as nitrogen or argon or in an atmosphere of α-olefin, because the catalyst poisons as described above are removed.

The solid titanium catalyst component [I] thus obtained contains titanium, magnesium, halogen and a compound having two or more ether bonds existing through a plurality of atoms (polyether compound). ing.

In the solid titanium catalyst component [I], the magnesium / titanium (atomic ratio) is 1 to 100,
It is preferably 2 to 50, particularly preferably 4 to 50,
The halogen / titanium (atomic ratio) is 2 to 200, preferably 4 to 90, particularly preferably 10 to 50, and the polyether compound / titanium (molar ratio) is 0.01 to 100,
Preferably 0.05 to 50, particularly preferably 0.1 to 3
It is preferably 0.

The solid titanium catalyst component [I] according to the present invention as described above may be supported on a solid carrier.
Examples of such carrier compounds include Al ₂ O ₃ and Si.
O ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO,
Resins such as Zn ₂ O, SnO ₂ , BaO, ThO, and styrene-divinylbenzene copolymer are used. Of these, Al ₂ O ₃ , SiO ₂ , and styrene-divinylbenzene copolymer are preferable.

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 and z are positive numbers, and z ≧ 2x. ] Alkenyl aluminum such as isoprenyl aluminum, trialkenyl aluminum such as triisopropenyl aluminum, dimethyl aluminum chloride,
Diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride,
Dialkyl aluminum halides such as dimethyl aluminum bromide, methyl aluminum sesquichloride,
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquibromide, ethyl aluminum sesquibromide, alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide, diethyl Examples thereof include dialkyl aluminum hydrides such as aluminum hydride and dibutyl aluminum hydride, and alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride.

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 , (iso -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 group II metal organometallic compound 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 (e) 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.

[0093]

[Chemical 5]

[0094]

[Chemical 6]

2,6-substituted piperidines such as

[0096]

[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.

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

[0100]

[Chemical 8]

2,6-substituted tetrahydropyrans such as

[0102]

[Chemical 9]

2,5-substituted tetrahydropyrans such as Two or more of these compounds may be used in combination. It may 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 olefin polymerization catalyst. Examples of the olefin used in the present invention include olefins having 2 to 20 carbon atoms, and 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, 7-methyl-1,6-octadiene, 1,7-octadiene, 1,9-decadiene 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. Alicyclic vinyl compounds such as vinylcyclohexane, substituted vinylcyclohexanes, vinylcycloheptane, substituted vinylcycloheptanes, 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 an amount such that 0.1 to 1000 g, preferably 0.3 to 500 g of a polymer 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 any of liquid phase polymerization methods such as solution polymerization and suspension polymerization (slurry polymerization) or gas phase polymerization methods. 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-mentioned catalyst component 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, as described above, is 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 atoms 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, and more preferably 0.01 to 30 mol, based on 1 mol of the [II] organometallic compound.
It is optionally used in a molar amount, particularly preferably 0.05 to 20 mol.

When hydrogen is used during 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 any of a homopolymer, a random copolymer and a block copolymer. 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.

[0123]

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.

[0126]

[Example 1] "Preparation of solid titanium catalyst component" (a) Generation of magnesium alkyl carbonate solution In a 2 liter round bottom flask sufficiently replaced with nitrogen gas, 153 g of magnesium ethoxide and 2-ethyl-1- A mixture of 276 ml of hexanol and 1100 ml of toluene was introduced. The mixture was stirred under 30 psig of carbon dioxide and reacted at 93 ° C for 3 hours. The resulting solution was introduced into a 2 liter reactor. (b) Generation of solid particles In a 1 liter reactor sufficiently replaced with nitrogen gas, 170 ml of toluene, 20.5 ml of tetraethoxysilane and Ti were added.
19.4 ml of Cl ₄ and 35 ml of decane were charged. The mixture was allowed to stir at 26-30 ° C for 15 minutes and then 114 ml of a solution of magnesium hydrcarbyl carbonate synthesized in (a).
Was added dropwise over 10 minutes to precipitate solid particles. (c) Reprecipitation of solid particles After stirring the mixture containing the precipitation for a further 5 minutes. THF
50 ml of (tetrahydrofuran) was added dropwise over 3 minutes, and the temperature inside the reactor was raised to 60 ° C. over 15 minutes. After reacting as it was at 60 ° C. for 1 hour, it was allowed to stand and decanted at 60 ° C. Then, it was washed twice with 100 ml of room temperature toluene. (d) Treatment with titanium compound In a 1 liter reactor sufficiently replaced with nitrogen gas, (c)
125 ml of toluene and TiCl
₄ was added to 50ml. 30 while stirring this mixture
The temperature was raised to 110 ° C. in minutes, and the reaction was performed as it was for 1 hour. After the reaction, the stirring was completed, and the supernatant was decanted at 110 ° C. After decanting, 150 ml of toluene, 50 ml of TiCl ₄ and 2.7 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (IPAMP) were added, and the mixture was stirred while stirring to 1
The reaction was carried out at 35 ° C for 90 minutes. 135 after finishing the reaction
The supernatant was removed by decanting at ℃. After that, 95 ml of toluene was added and the reaction was carried out at 90 ° C. for 30 minutes. After the reaction was completed, decantation was carried out at 90 ° C. to remove the supernatant. After that, 125 ml of TiCl ₄ was added, and the mixture was added at 90 ° C. to 1
The reaction was carried out over time. After completion of the reaction, decantation was performed at 90 ° C., and then washing with 250 ml of room temperature hexane 5 times was performed to obtain a solid catalyst component. The titanium component contained in the obtained catalyst component was 2.3% by weight. “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.

[0128]

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

[0129]

Example 3 "Polymerization" Propylene was polymerized in the same manner as in Example 1 except that IPAMP was not added during the polymerization. The results are shown in Table 1.

[0130]

Example 4 “Preparation of solid titanium catalyst component” In Example 1,
(d) A solid titanium catalyst component was prepared in the same manner as in Example 1 except that 4.0 ml of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added by the treatment with the titanium compound. "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.

[0131]

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.

[0132]

Example 6 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.

[0133]

Comparative Example 1 “Preparation of Solid Titanium Catalyst Component” In Example 1,
Diisobutyl phthalate instead of isopropyl-2-isopentyl-1,3-dimethoxypropane, and (c) 5.
A solid titanium catalyst component was prepared in the same manner as in Example 1 except that 0 g (d) was used in an amount of 0.48 g. "Polymerization" Polymerization was carried out in the same manner as in Example 1 except that the above solid titanium catalyst component was used. The results are shown in Table 1.

[0134]

[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] 1. A magnesium-containing solution formed by the reaction of an organomagnesium compound and carbon dioxide, (b) a titanium compound in a liquid state, (c) a formula R _m SiR ′ _4-m (wherein , 0 ≦ m ≦ 4, R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a haloalkyl group, an aryl group or a haloalkylsilyl group having 1 to 8 carbon atoms, and R ′ is OR or halogen. Atom)), (d) a cyclic ether compound, and (e) a compound having two or more ether bonds which are present through a plurality of atoms. A solid titanium catalyst component for olefin polymerization, comprising titanium, magnesium, halogen, and a compound having two or more ether bonds present through a plurality of atoms. 2. The solid titanium for olefin polymerization according to claim 1, wherein the compound (e) having two or more ether bonds existing through a plurality of atoms is represented by the following formula: Catalyst component: (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.