JPH07133307A - Catalyst component for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain a polyolefin in a high yield using a small amount of a modified organoaluminum compound by using a catalyst component obtained from an organic compound of Zr, etc., an organic compound of a metal of Group I, II, or III, a specific cyclic organic compound, and a sulfide through contacting. CONSTITUTION:A catalyst component is produced from two compounds (A) and (B) respectively represented by formulae I and II R<1> to R<4> each is a 1-24C hydrocarbon group; X is a halogen; Me<1> is Zr, Ti, or Hf; Me<2> is an element of Group I, II, or III of the Periodic Table; 0<=p<=4 and 0<=q<=4, provided that 0<=(p+q)<=4; z is the valence of Me<2>; and 0<=m<=z and 0<=n<=z, provided that 0<=(m+n)<=z), a cyclic organic compound having two or more conjugated double bonds, and a sulfide through contacting. An olefin is (co) polymerized in the presence of a modified organoaluminum compound containing an Al-O-Al bond and obtained by the reaction of the catalyst component with an organoaluminum compound (especially preferably trimethylaluminum) and water. Me<1> is preferably Zr. Examples of A include tetrabutoxyzirconium. Examples of B include trihexylaluminum.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is used for polymerizing or copolymerizing olefins, and has a high catalytic efficiency, a small amount of a modified organoaluminum compound used, a polymer having a high molecular weight and a molecular weight distribution. Olefin which gives a olefin polymer having a relatively wide range and having a narrow composition distribution in the case of a copolymer, and moreover, it is easy to control the molecular weight and the molecular weight distribution and has excellent oxidation resistance. The present invention relates to a catalyst component for polymerization. The present invention also relates to a catalyst using this catalyst component and a method for producing an olefin polymer by the catalyst. Here, the olefin polymer is a generic term for a homopolymer and a copolymer of olefins.

[0002]

2. Description of the Related Art Recently, a catalyst comprising a zirconium compound and an aluminoxane has been proposed as a means for obtaining an ethylene polymer having a narrow molecular weight distribution and a narrow composition distribution in an ethylene polymer or an ethylene / α-olefin copolymer ( JP-A-58-19309). By such a method, an ethylene-based copolymer can be obtained in a high yield, and its physical properties have a narrow molecular weight distribution, and a copolymer having a narrow composition distribution can be obtained. Another drawback is that the amount of aluminoxane used is large.

JP-A-63-234005 proposes that the molecular weight of a polymer obtained by using a transition metal compound having a 2,3- and 4-substituted cyclopentadienyl group can be improved. Further, JP-A-2-22307 proposes to improve the molecular weight of a polymer by using a hafnium compound having a ligand bonded to at least two bridged conjugated cycloalkadienyl groups. However, the use of hafnium as the transition metal also has the disadvantage that the yield of the obtained polymer is low.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have found that the olefin polymer or the olefin polymer of high yield can be obtained in a high yield under the condition that the amount of the modified organoaluminum compound such as methylaluminoxane is extremely low and the molecular weight distribution is relatively wide. As a result of studying a catalyst and a method for producing a copolymer, a new catalyst component was found, the intended purpose was achieved, and the present invention was achieved.

[0005]

That is, the present invention is as follows.
(1) General formula ^{_{Me 1 R 1 p (OR 2}} ) q X 1 4-p-q
A compound represented by the formula (wherein R ¹ and R ² are independently carbon atoms 1
~ 24 hydrocarbon groups, X ¹ is a halogen atom, Me ¹ is Z
r, Ti or Hf, where p and q are 0 ≦ p
≦ 4, 0 ≦ q ≦ 4, 0 ≦ p + q ≦ 4), (2) a compound represented by the general formula Me ² R ³ _m (OR ⁴ ) _n X ² _z-m-n (in the formula, R ³ , R ⁴ are individually a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom, Me ² is an element of Group I to III of the periodic table, z is the valence of Me ² , and m and n
Are 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m +
n ≦ z), (3) a cyclic, organic compound having two or more conjugated double bonds, and (4) a sulfide, which are obtained by bringing them into contact with each other.

The present invention also relates to Al-obtained by reacting the catalyst component and the organoaluminum compound with water.
The present invention relates to a catalyst for olefin polymerization, which comprises a modified organoaluminum compound containing an O—Al bond. The present invention also relates to a method for producing an olefin polymer or copolymer, which comprises polymerizing or copolymerizing olefins in the presence of the catalyst.

The olefin polymerization catalyst of the present invention has a high catalytic efficiency, uses a small amount of a modified organoaluminum compound such as aluminoxane, and produces a polymer having a high molecular weight.
It is possible to produce a polymer having a relatively wide molecular weight distribution, a narrow composition distribution in the case of a copolymer, and excellent oxidation resistance. Further, when molding a polymer produced using the olefins polymerization catalyst of the present invention, particularly in film molding,
There is no stickiness in both the inflation method and the T-die method, high-speed molding is possible, and the moldability is extremely good. Further, the formed film is excellent in transparency, anti-blocking property and strength both in the inflation method and in the T-die method, and particularly excellent in the mouth opening property in the inflation method. Also in pipe molding and blow molding, the moldability is good, the appearance is good, and the molded product is not roughened.

The present invention will be described in detail below. First, the general formula Me ¹ R ¹ _p (OR ² ) _{q of the} component (1) is obtained.
The compound represented by X ¹ _4-pq will be described. In the formula, R ¹ and R ² represent a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms. Examples of the hydrocarbon group include methyl group and ethyl group. Group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tert-butyl group, cyclobutyl group, pentyl group, isopentyl group,
Neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, alkyl group such as octyl group, vinyl group, alkenyl group such as allyl group, phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, Examples thereof include an aryl group such as a naphthyl group, a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, a phenylpropyl group, and an aralkyl group such as a neofil group. These may have branches. X ¹ is a halogen atom of fluorine, iodine, chlorine and bromine, Me ¹ is Zr, T
i or Hf is shown, and Zr is preferable. p and q
Are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ p + q ≦ 4, and preferably 0 <p + q ≦ 4.

The compounds represented by these general formulas are as follows:
Specifically, tetramethyl zirconium, tetraethyl zirconium, tetrapropyl zirconium, tetra n
-Butyl zirconium, tetrapentyl zirconium,
Tetraphenylzirconium, tetratolylzirconium, tetrabenzylzirconium, tetraallylzirconium, tetraneophyllzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrapentyloxyzirconium, tetraphenoxyzirconium, tetratolyloxyzirconium ,
Tetrabenzyloxyzirconium, tetraallyloxyzirconium, tetraneophylloxyzirconium, trimethyl monochloro zirconium, triethyl monochloro zirconium, tripropyl monochloro zirconium, tri-n-butyl monochloro zirconium, tripentyl monochloro zirconium, triphenyl monochloro zirconium, tritolyl monochloro zirconium , Tribenzyl monochloro zirconium, triallyl monochloro zirconium, trineophyl monochloro zirconium, dimethyldichloro zirconium, diethyl dichloro zirconium, dipropyl dichloro zirconium, di n-butyl dichloro zirconium, dipentyl dichloro zirconium, diphenyl dichloro zirconium, ditolyl dichloro di Conium, dibenzyldichlorozirconium, diallyldichlorozirconium, dineofildichlorozirconium, monomethyltrichlorozirconium, monoethyltrichlorozirconium, monopropyltrichlorozirconium, mono-n-butyltrichlorozirconium, monopentyltrichlorozirconium, monophenyltrichlorozirconium, monotolyl Trichlorozirconium, monobenzyltrichlorozirconium, monoallyltrichlorozirconium, mononeophyltrichlorozirconium, tetrachlorozirconium, trimethoxymonochlorozirconium,

Dimethoxydichlorozirconium, monomethoxytrichlorozirconium, triethoxymonochlorozirconium, diethoxydichlorozirconium, monoethoxytrichlorozirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, monopropoxytrichlorozirconium, tri-n.
-Butoxymonochlorozirconium, di-n-butoxydichlorozirconium, mono-n-butoxytrichlorozirconium, tripentyloxymonochlorozirconium, dipentyloxydichlorozirconium, monopentyloxytrichlorozirconium, triphenoxymonochlorozirconium, diphenoxydichlorozirconium, monophenoxytrichlorozirconium , Tritolyloxymonochlorozirconium, ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium, tribenzyloxymonochlorozirconium, dibenzyloxydichlorozirconium, monobenzyloxytrichlorozirconium, triallyloxymonochlorozirconium, diallyloxydichlorozirconium, monoallyl Carboxymethyl trichloro zirconium,
Trineophylloxy monochlorozirconium, Dineofiloxy dichlorozirconium, Mononeophylloxy trichlorozirconium,

Tetrabromozirconium, trimethylmonobromozirconium, triethylmonobromozirconium, tripropylmonobromozirconium, tri-n-
Butylmonobromozirconium, tripentylmonobromozirconium, triphenylmonobromozirconium, tritolylmonobromozirconium, tribenzylmonobromozirconium, triallylmonobromozirconium, trineophile monobromozirconium, dimethyldibromozirconium, diethyldibromozirconium, di Propyldibromozirconium, di-n-butyldibromozirconium, dipentyldibromozirconium, diphenyldibromozirconium, ditolyldibromozirconium, dibenzyldibromozirconium, diallyldibromozirconium, dineofildibromozirconium, monomethyltribromozirconium, monoethyltribromozirconium, Monopropyltribromozirconium, n-butyltribromozirconium, monopentyltribromozirconium, monophenyltribromozirconium, monotolyltribromozirconium, monobenzyltribromozirconium, monoallyltribromozirconium, mononeophyltribromozirconium, tetrabromozirconium, trimethoxy Monobromozirconium, dimethoxydibromozirconium, monomethoxytribromozirconium, triethoxymonobromozirconium, diethoxydibromozirconium, monoethoxytribromozirconium, tripropoxymonobromozirconium, dipropoxydibromozirconium, monopropoxytribromozirconium, tri-n -Butoxymonobromozirconium, di-n-butoxydibromozirconium , Mono-n-butoxytribromozirconium, tripentyloxymonobromozirconium, dipentyloxydibromozirconium, monopentyloxytribromozirconium, triphenoxymonobromozirconium, diphenoxydibromozirconium, monophenoxytribromozirconium, tritolyloxymonobromo Zirconium, ditolyloxydibromozirconium, monotolyloxytribromozirconium, tribenzyloxymonobromozirconium, dibenzyloxydibromozirconium, monobenzyloxytribromozirconium, triallyloxymonobromozirconium, diallyloxydibromozirconium, monoallyloxy Tribromozirconium, trineophylloxy monobromozirconi Um, dineofiloxydibromozirconium, mononeophylloxytribromozirconium,

Tetraiodozirconium, trimethylmonoiodozirconium, triethylmonoiodozirconium, tripropylmonoiodozirconium, tri-n-
Butyl monoiodo zirconium, tripentyl monoiodo zirconium, triphenyl monoiodo zirconium, tritolyl monoiodo zirconium, tribenzyl monoiodo zirconium, triallyl monoiodo zirconium, trineophyll monoiodo zirconium, dimethyldiiodo zirconium, diethyl diiodo zirconium , Dipropyldiiodozirconium, di-n-butyldiiodozirconium, dipentyldiiodozirconium, diphenyldiiodozirconium, ditolyldiiodozirconium, dibenzyldiiodozirconium, diallyldiiodozirconium, dineofildiiodozirconium, monomethyltriiod Iodozirconium, monoethyltriiodozirconium, monopropyltriiodozirconium, n-Butyl triiodo zirconium, monopentyl triiodo zirconium, monophenyl triiodo zirconium, monotolyl triiodo zirconium, monobenzyl triiodo zirconium, tetraiodo zirconium, trimethoxy monoiodo zirconium, dimethoxydiiodo zirconium, monomethoxy triiodo Zirconium, triethoxy monoiodo zirconium, diethoxy diiodo zirconium, monoethoxy triiodo zirconium, tripropoxy monoiodo zirconium, dipropoxy diiodo zirconium, monopropoxy triiodo zirconium, tri n-
Butoxymonoiodozirconium, di-n-butoxydiiodozirconium, mono-n-butoxytriiodozirconium, tripentyloxymonoiodozirconium,
Dipentyloxydiiodozirconium, monopentyloxytriiodozirconium, triphenoxymonoiodozirconium, diphenoxydiiodozirconium, monophenoxytriiodozirconium, tritolyloxymonoiodozirconium, ditolyloxydiiodozirconium, monotolyloxytriiodo Zirconium, tribenzyloxymonoiodozirconium,
Dibenzyloxydiiodozirconium, monobenzyloxytriiodozirconium, triallyloxymonoiodozirconium, diallyloxydiiodozirconium, monoallyloxytriiodozirconium, trineophylloxymonoiodozirconium, dineofiloxydiiodozirconium, Mononeophyll oxytriiodozirconium,

Tribenzylmonomethoxyzirconium,
Tribenzyl monoethoxy zirconium, tribenzyl monopropoxy zirconium, tribenzyl monobutoxy zirconium, tribenzyl monopentyloxy zirconium, tribenzyl monophenoxy zirconium,
Tribenzyl monotolyloxy zirconium, tribenzyl monobenzyloxy zirconium, tribenzyl monoallyloxy zirconium, tribenzyl mononeophyloxy zirconium, dibenzyl dimethoxy zirconium, dibenzyl diethoxy zirconium, dibenzyl dipropoxy zirconium, dibenzyl dibutoxy Zirconium, dibenzyldipentyloxyzirconium, dibenzyldiphenoxyzirconium, dibenzylditolyloxyzirconium, dibenzyldibenzyloxyzirconium, dibenzyldiallyloxyzirconium, dibenzyldineophyloxyzirconium, monobenzyltrimethoxyzirconium, monobenzyl Triethoxyzirconium, monobenzyltripropoxyzirconium, mono Benzyltributoxyzirconium, monobenzyltripentyloxyzirconium, monobenzyltriphenoxyzirconium, monobenzyltritolyloxyzirconium, monobenzyltribenzyloxyzirconium, monobenzyltriallyloxyzirconium, monobenzyltrineophyloxyzirconium, trineo Fill monomethoxy zirconium, trineofil monoethoxy zirconium, trineofil monopropoxy zirconium, trineofil monobutoxy zirconium, trineofil monophenoxy zirconium, dineofil dimethoxyzirconium, dineofil diethoxyzirconium, dineofildi Propoxy zirconium, Dineofil dibutoxy Zirconium, Dineofil diphenoxy Rukoniumu, mono neophyl trimethoxy zirconium, mono neophyl triethoxy zirconium, mono neophyl tripropoxy zirconium, mono neophyl tributoxyzirconium, mono- neophyl triphenoxy zirconium,

Tetramethyltitanium, tetraethyltitanium, tetrapropyltitanium, tetra-n-butyltitanium, tetrapentyltitanium, tetraphenyltitanium, tetratolyltitanium, tetrabenzyltitanium, tetraallyltitanium, tetraneofiltitanium, tetramethoxytitanium, tetra Ethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentyloxytitanium, tetraphenoxytitanium, tetratolyloxytitanium, tetrabenzyloxytitanium, tetraallyloxytitanium, tetraneophyloxytitanium, trimethylmonochlorotitanium, triethylmonochlorotitanium, tri Propyl monochlorotitanium, tri-n- Till monochlorotitanium, tribenzyl monochlorotitanium, dimethyldichlorotitanium, diethyldichlorotitanium, di-n-butyldichlorotitanium, dibenzyldichlorotitanium, monomethyltrichlorotitanium, monoethyltrichlorotitanium, mono-n-butyltrichlorotitanium, monobenzyltrichlorotitanium, Tetrachlorotitanium, trimethoxymonochlorotitanium, dimethoxydichlorotitanium, monomethoxytrichlorotitanium, triethoxymonochlorotitanium,

Diethoxydichlorotitanium, monoethoxytrichlorotitanium, tripropoxymonochlorotitanium, dipropoxydichlorotitanium, monopropoxytrichlorotitanium, tri-n-butoxymonochlorotitanium, di-n-butoxydichlorotitanium, mono-n-butoxytrichlorotitanium, tri Pentyloxy monochlorotitanium, dipentyloxydichlorotitanium, monopentyloxytrichlorotitanium, triphenoxymonochlorotitanium, diphenoxydichlorotitanium, monophenoxytrichlorotitanium, tritolyloxymonochlorotitanium,
Ditolyloxydichlorotitanium, monotolyloxytrichlorotitanium, tribenzyloxymonochlorotitanium, dibenzyloxydichlorotitanium, monobenzyloxytrichlorotitanium, tetrabromotitanium, trimethylmonobromotitanium, triethylmonobromotitanium, tripropylmonobromo Titanium, tri-n-butylmonobromotitanium, tribenzylmonobromotitanium, dimethyldibromotitanium, diethyldibromotitanium, di-n-butyldibromotitanium, dibenzyldibromotitanium, monomethyltribromotitanium, monoethyltribromotitanium, monon- Butyltribromotitanium, Monobenzyltribromotitanium, Tetrabromotitanium, Trimethoxy Monobromotitanium, dimethoxydibromotitanium, trimethoxytribromotitanium, triethoxymonobromotitanium, diethoxydibromotitanium, monoethoxytribromotitanium, tripropoxymonobromotitanium, dipropoxydibromotitanium, monopropoxytribromotitanium, trin -Butoxymonobromotitanium, di-n
-Butoxydibromotitanium, mono-n-butoxytribromotitanium, tripentyloxymonobromotitanium, dipentyloxydibromotitanium, monopentyloxytribromotitanium, triphenoxymonobromotitanium, diphenoxydibromotitanium, monophenoxytribromotitanium, tri Trilyloxymonobromotitanium, ditolyloxydibromotitanium, monotolyloxytribromotitanium,
Tribenzyloxymonobromotitanium, dibenzyloxydibromotitanium,

Monobenzyloxytribromotitanium, tetraiodotitanium, trimethylmonoiodotitanium, triethylmonoiodotitanium, tripropylmonoiodotitanium, tri-n-butylmonoiodotitanium, tribenzylmonoiodotitanium, dimethyldiiodotitanium, diethyl Diiodotitanium, di-n-butyldiiodotitanium, dibenzyldiiodotitanium, monomethyltriiodotitanium, monoethyltriiodotitanium, monon-butyltriiodotitanium, monobenzyltriiodotitanium,
Tetraiodotitanium, trimethoxymonoiodotitanium, dimethoxydiiodotitanium, monomethoxytriiodotitanium, triethoxymonoiodotitanium, diethoxydiiodotitanium, monoethoxytriiodotitanium, tripropoxymonoiodotitanium, dipropoxydiiodotitanium , Monopropoxytriiodotitanium, tri-n-butoxymonoiodotitanium, di-n-butoxydiiodotitanium, mono-n-butoxytriiodotitanium, tripentyloxymonoiodotitanium, dipentyloxydiiodotitanium, monopentyloxytriiodotitanium ,
Triphenoxymonoiodotitanium, diphenoxydiiodotitanium, monophenoxytriiodotitanium, tritolyloxymonoiodotitanium, ditolyloxydiiodotitanium, monotolyloxytriiodotitanium, tribenzyloxymonoiodotitanium, dibenzyloxydi Iodo titanium,

Monobenzyloxytriiodotitanium, tribenzylmonomethoxytitanium, tribenzylmonoethoxytitanium, tribenzylmonopropoxytitanium, tribenzylmonobutoxytitanium,
Tribenzyl monophenoxytitanium, dibenzyldimethoxytitanium, dibenzyldiethoxytitanium, dibenzyldipropoxytitanium, dibenzyldibutoxytitanium, dibenzyldiphenoxytitanium, monobenzyltrimethoxytitanium, monobenzyltriethoxytitanium, monobenzyltri Propoxytitanium, monobenzyltributoxytitanium,
Monobenzyltriphenoxytitanium, Trineophyll monomethoxytitanium, Trineophyll monoethoxytitanium, Trineophyll monopropoxytitanium, Trineophyll monobutoxytitanium, Trineophyll monophenoxytitanium, Dineofil dimethoxytitanium, Dineofil Diethoxytitanium,
Dineofil dipropoxytitanium, Dineofil dibutoxytitanium, Dineofil diphenoxytitanium, Mononeophile trimethoxytitanium, Mononeophile triethoxytitanium, Mononeophile tripropoxytitanium, Mononeophile tributoxytitanium, Mono Neophyll triphenoxytitanium,

Tetramethyl hafnium, tetraethyl hafnium, tetrapropyl hafnium, tetra n-butyl hafnium, tetrapentyl hafnium, tetraphenyl hafnium, tetratolyl hafnium, tetrabenzyl hafnium, tetraallyl hafnium, tetraneophyll hafnium, tetramethoxy hafnium, tetra Ethoxyhafnium, tetrapropoxyhafnium, tetrabutoxyhafnium, tetrapentyloxyhafnium, tetraphenoxyhafnium, tetratolyloxyhafnium, tetrabenzyloxyhafnium, tetraallyloxyhafnium, tetraneophyloxyhafnium, trimethylmonochlorohafnium, triethylmonochlorohafnium, tri Propyl monochlorohafnium, tri n- Till monochlorohafnium, tribenzyl monochlorohafnium, dimethyldichlorohafnium, diethyldichlorohafnium, di-n-butyldichlorohafnium, dibenzyldichlorohafnium, monomethyltrichlorohafnium, monoethyltrichlorohafnium, mono-n-butyltrichlorohafnium, monobenzyltrichlorohafnium, Tetrachlorohafnium, trimethoxymonochlorohafnium, dimethoxydichlorohafnium,

Monomethoxytrichlorohafnium, triethoxymonochlorohafnium, diethoxydichlorohafnium, monoethoxytrichlorohafnium, tripropoxymonochlorohafnium, dipropoxydichlorohafnium, monopropoxytrichlorohafnium, tri-n-butoxymonochlorohafnium, di-n-butoxydichloro. Hafnium, mono-n-butoxytrichlorohafnium, tripentyloxymonochlorohafnium, dipentyloxydichlorohafnium, monopentyloxytrichlorohafnium, triphenoxymonochlorohafnium, diphenoxydichlorohafnium, monophenoxytrichlorohafnium, tritolyloxymonochlorohafnium, ditolyloxy. Dichlorohafnium,
Monotolyloxytrichlorohafnium, tribenzyloxymonochlorohafnium, dibenzyloxydichlorohafnium, monobenzyloxytrichlorohafnium, tetrabromohafnium, trimethylmonobromohafnium, triethylmonobromohafnium, tripropylmonobromohafnium, tri-n-butylmonobromo Hafnium, tribenzylmonobromohafnium, dimethyldibromohafnium, diethyldibromohafnium,

Di-n-butyldibromohafnium, dibenzyldibromohafnium, monomethyltribromohafnium, monoethyltribromohafnium, mono-n-butyltribromohafnium, monobenzyltribromohafnium, tetrabromohafnium, trimethoxymonobromohafnium, Dimethoxydibromohafnium, monomethoxytribromohafnium, triethoxymonobromohafnium, diethoxydibromohafnium, monoethoxytribromohafnium, tripropoxymonobromohafnium, dipropoxydibromohafnium, monopropoxytribromohafnium, tri-n-butoxymonobromo Hafnium, di-n-butoxydibromohafnium, mono-n-butoxytribromohafnium, tripentyloxymonobu Mohafnium, dipentyloxydibromohafnium, monopentyloxytribromohafnium, triphenoxymonobromohafnium, diethoxydibromohafnium, monophenoxytribromohafnium, tritolyloxymonobromohafnium, ditolyloxydibromohafnium, monotolyloxytribromohafnium , Tribenzyloxymonobromohafnium, dibenzyloxydibromohafnium, monobenzyloxytribromohafnium, tetraiodohafnium, trimethylmonoiodohafnium, triethylmonoiodohafnium, tripropylmonoiodohafnium, tri-n-butylmonoiodohafnium, tri Benzylmonoiodohafnium, dimethyldiiodohafnium, diethyldiiodohafnium

Di-n-butyldiiodohafnium, dibenzyldiiodohafnium, monomethyltriiodohafnium, monoethyltriiodohafnium, mono-n-butyltriiodohafnium, monobenzyltriiodohafnium, tetraiodohafnium, trimethoxymonoiodo Hafnium, dimethoxydiiodohafnium, monomethoxytriiodohafnium, triethoxymonoiodohafnium, diethoxydiiodohafnium, monoethoxytriiodohafnium, tripropoxymonoiodohafnium, dipropoxydiiodohafnium, monopropoxytriiodohafnium, tri n-butoxymonoiodohafnium, di-n-butoxydiiodohafnium, mono-n-butoxytriiodohafnium, tripentyloxymonoyo De hafnium, dipentyl oxy diiodo hafnium, mono-pentyloxy triiodo hafnium, triphenoxy mono- iodo hafnium, diphenoxylate Siji iodo hafnium, mono phenoxy triiodo hafnium, tri tolyl oxy mono-iodo hafnium,
Ditolyloxydiiodohafnium, monotolyloxytriiodohafnium, tribenzyloxymonoiodohafnium, dibenzyloxydiiodohafnium, monobenzyloxytriiodohafnium, tribenzylmonomethoxyhafnium, tribenzylmonoethoxyhafnium,

Tribenzyl monopropoxy hafnium,
Tribenzyl monobutoxy hafnium, tribenzyl monophenoxy hafnium, dibenzyl dimethoxy hafnium, dibenzyl diethoxy hafnium, dibenzyl dipropoxy hafnium, dibenzyl dibutoxy hafnium, dibenzyl diphenoxy hafnium, monobenzyl trimethoxy hafnium, monobenzyl tri Ethoxy hafnium, monobenzyl tripropoxy hafnium, monobenzyl tributoxy hafnium, monobenzyl triphenoxy hafnium, trineophyll monomethoxy hafnium, trineophyll monoethoxy hafnium, trineophyll monopropoxy hafnium, trineophyll monobutoxy hafnium, tri Neofil monophenoxy hafnium, dineofil dimethoxy hafnium,
Dineofildiethoxyhafnium, Dineofildipropoxyhafnium, Dineofildibutoxyhafnium, Dineofildiphenoxyhafnium, Mononeophile trimethoxyhafnium, Mononeophile triethoxyhafnium, Mononeophile tripropoxyhafnium, Mono Neofil tributoxy hafnium, mono neophyll triphenoxy hafnium, and the like. Of course, in these compounds listed as specific examples of the above component (2), R ¹ and R ² are not only n-, but also various structural isomer groups such as iso-, s-, t-, and neo-. It also includes cases. Among these specific compounds, tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetrabutoxyzirconium, tetrabutoxytitanium and tetrabutoxyhafnium are preferable. Particularly preferred are Zr (OR) ₄ compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium.
These compounds can be used as a mixture of two or more kinds. The component (2) is a compound represented by the following general formula. In the general formula _{^{Me 2 R 3 m (OR 4}} ) n X 2 z-m-n type, Me ² represents one of the periodic table I~III group element, this lithium, sodium, potassium, magnesium , Calcium, zinc, boron, aluminum and the like. R ³ and R ⁴ represent a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 and more preferably 1 to 8 carbon atoms, which include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, Alkyl group such as butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, dodecyl group; vinyl group , Alkenyl groups such as allyl groups, phenyl groups, tolyl groups, xylyl groups, mesityl groups, indenyl groups, naphthyl groups and other aryl groups; benzyl groups, trityl groups, phenethyl groups, styryl groups, benzhydryl groups, phenylbutyl groups, phenylpropyi groups. And aralkyl groups such as ru group and neophyll group. These may have branches. X ² represents halogen such as fluorine, iodine, chlorine or bromine. z represents the valence of Me ² . m is 0 ≦ m ≦ z,
n is 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z, preferably 0 <m + n ≦ z.

Specific examples of compounds usable as the component (2) include methyllithium, ethyllithium, propyllithium, isopropyllithium, butyllithium, t-butyllithium, pentyllithium, octyllithium, phenyllithium and benzyllithium. , Dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, di t-butyl magnesium, dipentyl magnesium, dioctyl magnesium, diphenyl magnesium, dibenzyl magnesium, methyl magnesium chloride, ethyl magnesium chloride,
Propyl magnesium chloride, isopropyl magnesium chloride, butyl magnesium chloride, t
-Butyl magnesium chloride, pentyl magnesium chloride, octyl magnesium chloride, phenyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium bromide, ethyl magnesium iodide, propyl magnesium bromide, propyl magnesium iodide, isopropyl magnesium Bromide, isopropyl magnesium iodide, butyl magnesium bromide, butyl magnesium iodide, t-butyl magnesium bromide, t-butyl magnesium iodide, pentyl magnesium bromide, pentyl magnesium iodide, octyl magnesium bromide,

Octyl magnesium iodide, phenyl magnesium bromide, phenyl magnesium iodide, benzyl magnesium bromide, benzyl magnesium iodide, dimethyl zinc, diethyl zinc, dipropyl zinc, diisopropyl zinc, di-n-butyl zinc, di t-butyl zinc, Dipentylzinc, dioctylzinc, diphenylzinc, dibenzylzinc, trimethylboron, triethylboron, tripropylboron, triisopropylboron, tributylboron, tri-t-butylboron, tripentylboron, trioctylboron, triphenylboron, tribenzylboron, Trimethyl aluminum, triethyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethyl al Pyridinium fluoride, diethylaluminum iodide, ethylaluminum dichloride, ethylaluminum dibromide, ethylaluminum difluoride, ethylaluminum diiodide, tripropyl aluminum, dipropyl aluminum chloride, dipropyl aluminum bromide,
Dipropyl aluminum fluoride, dipropyl aluminum iodide,

Propyl aluminum dichloride, propyl aluminum dibromide, propyl aluminum difluoride, propyl aluminum diiodide, triisopropyl aluminum, diisopropyl aluminum chloride, diisopropyl aluminum bromide, diisopropyl aluminum fluoride,
Diisopropyl aluminum iodide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, propyl aluminum sesquichloride,
Propyl aluminum sesquibromide, butyl aluminum sesquibromide, butyl aluminum sesquibromide, isopropyl aluminum dichloride, isopropyl aluminum dibromide, isopropyl aluminum difluoride, isopropyl aluminum diiodide, tributyl aluminum, dibutyl aluminum chloride, dibutyl aluminum bromide, dibutyl aluminum fluoride Ride, dibutyl aluminum iodide, butyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum difluoride, butyl aluminum diiodide, tri sec-butyl aluminum, di sec-butyl aluminum chloride, di sec-butyl aluminum bromide, sec- butyl aluminum fluoride, di-sec- butyl aluminum iodide,
sec-Butyl aluminum dichloride, sec-butyl aluminum dibromide, sec-butyl aluminum difluoride, sec-butyl aluminum diiodide, tri-tert-butyl aluminum, di-tert-butyl aluminum chloride, di-tert.
-Butyl aluminum bromide, di-tert-butyl aluminum fluoride, di-tert-butyl aluminum iodide,

Tert-Butyl aluminum dichloride, tert-butyl aluminum dibromide, te
rt-Butyl aluminum difluoride, tert-
Butyl aluminum diiodide, triisobutyl aluminum, diisobutyl aluminum chloride, diisobutyl aluminum bromide, diisobutyl aluminum fluoride, diisobutyl aluminum iodide, isobutyl aluminum dichloride, isobutyl aluminum dibromide, isobutyl aluminum difluoride, isobutyl aluminum diiodide, tri Hexyl aluminum, dihexyl aluminum chloride, dihexyl aluminum bromide, dihexyl aluminum fluoride, dihexyl aluminum iodide, hexyl aluminum dichloride, hexyl aluminum dibromide, hexyl aluminum difluoride, hexyl aluminum diiodide, Pentyl aluminum, dipentyl aluminum chloride, dipentyl aluminum bromide, dipentyl aluminum fluoride, dipentyl aluminum iodide, pentyl aluminum dichloride, pentyl aluminum dibromide,
Pentyl aluminum difluoride and pentyl aluminum diiodide, methyl aluminum methoxide, methyl aluminum ethoxide, methyl aluminum propoxide, methyl aluminum butoxide, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, dimethyl aluminum propoxide, dimethyl aluminum butoxide, Ethyl aluminum methoxide,

Ethyl aluminum ethoxide, ethyl aluminum propoxide, ethyl aluminum butoxide, diethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum propoxide, diethyl aluminum butoxide, propyl aluminum methoxide, propyl aluminum ethoxide,
Propyl aluminum propoxide, propyl aluminum butoxide, dipropyl aluminum methoxide,
Dipropyl aluminum ethoxide, dipropyl aluminum butoxide, dipropyl aluminum butoxide, butyl aluminum methoxide, butyl aluminum ethoxide, butyl aluminum propoxide, butyl aluminum butoxide, dibutyl aluminum methoxide, dibutyl aluminum ethoxide, dibutyl aluminum propoxide , Dibutyl aluminum butoxide and the like.

As the component (3), an organic cyclic compound having two or more conjugated double bonds is used. The component (3) has two or more conjugated double bonds, preferably 2 to 4, more preferably 2 to 3, and has a total carbon number of 4 to 24, preferably 4 to 12 Hydrogen compound; Cyclic hydrocarbon compound in which the cyclic hydrocarbon compound is partially substituted with 1 to 6 hydrocarbon residues (typically, an alkyl group or aralkyl group having 1 to 12 carbon atoms); Two or more heavy bonds, preferably 2 to 4, more preferably 2 to
An organosilicon compound having 3 cyclic carbon groups having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon group being partially substituted with 1 to 6 hydrocarbon residues. Included organosilicon compounds. Particularly preferably, one having a cyclopentadiene structure in any of the molecules is preferable.

Incidentally, the organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. (CP) _L SiR _4-L Here, Cp represents the cyclohydrocarbon group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R represents a methyl group, an ethyl group. Group, propyl group, isopropyl group, butyl group, t-
An alkyl group such as a butyl group, a hexyl group, an octyl group;
An alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group; an aryl group such as a phenyl group; an aryloxy group such as a phenoxy group; a carbon number of 1 to 24 as exemplified by an aralkyl group such as a benzyl group, It preferably represents 1 to 12 hydrocarbon residues or hydrogen, and L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Therefore, specific examples of the organic cyclic hydrocarbon compounds usable as the component (3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2
-Dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4
-Methyl-1-indene, 4,7-dimethylindene,
Carbon number 7 such as 4,5,6,7-tetrahydroindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, methylcyclooctatetraene, azulene, methylazulene, ethylazulene, fluorene, methylfluorene ~ 24 cyclopolyene or substituted cyclopolyene, monocyclopentadienylsilane, dicyclopentadienylsilane, tricyclopentadienylsilane, tetracyclopentadienylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadiene Enylmonoethylsilane, monocyclopentadienyldimethylsilane,

Monocyclopentadienyldiethylsilane, monocyclopentadienyltrimethylsilane, monocyclopentadienyltriethylsilane, monocyclopentadienylmonomethoxysilane, monocyclopentadienylmonoethoxysilane, monocyclopentadienyl Monophenoxysilane, dicyclopentadienylmonomethylsilane, dicyclopentadienylmonoethylsilane, dicyclopentadienyldimethylsilane, dicyclopentadienyldiethylsilane, dicyclopentadienylmethylethylsilane, dicyclopentadiene Phenyldipropylsilane, dicyclopentadienylethylpropylsilane, dicyclopentadienyldiphenylsilane, dicyclopentadienylphenylmethylsilane, dicyclopentadienylmonometh Shishiran, dicyclopentadienyl mono silane, tri cyclopentadienyl monomethyl silane, tri cyclopentadienyl monoethyl silane, tri cyclopentadienyl monomethoxy silane, tri cyclopentadienyl mono silane, 3
-Methylcyclopentadienylsilane, bis3-methylcyclopentadienylsilane, 3-methylcyclopentadienylmethylsilane, 1,2-dimethylcyclopentadienylsilane, 1,3-dimethylcyclopentadienylsilane, 1,2,4-trimethylcyclopentadienylsilane,

1,2,3,4-tetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsilane, monoindenylsilane, diindenylsilane,
Triindenylsilane, tetraindenylsilane, monoindenylmonomethylsilane, monoindenylmonoethylsilane, monoindenyldimethylsilane, monoindenyldiethylsilane, monoindenyltrimethylsilane, monoindenyltriethylsilane, monoindenyl Monomethoxysilane, monoindenylmonoethoxysilane, monoindenylmonophenoxysilane, diindenylmonomethylsilane, diindenylmonoethylsilane,
Diindenyldimethylsilane, diindenyldiethylsilane, diindenylmethylethylsilane, diindenyldipropylsilane, diindenylethylpropylsilane, diindenyldiphenylsilane, diindenylphenylmethylsilane, diindenylmonosilane Methoxysilane,
Diindenyl monoethoxysilane, triindenyl monomethylsilane, triindenyl monoethylsilane, triindenyl monomethoxysilane, triindenyl monoethoxysilane, 3-methylindenyl silane, bis 3-
Methylindenylsilane, 3-methylindenylmethylsilane, 1,2-dimethylindenylsilane, 1,3-
Examples include dimethylindenylsilane, 1,2,4-trimethylindenylsilane, 1,2,3,4-tetramethylindenylsilane, and pentamethylindenylsilane.

Further, any one of the above-mentioned compounds may have an alkylene group (the carbon number thereof is usually 2 to 8, preferably 2 to
A compound bound via 3) can also be used as the component (3) of the present invention. For example, bisindenylethane, bis (4,5,6,7-tetrahydro-1-indenyl)
Ethane, 1,3-propanedinyl bisindene, 1,3
-Propandinylbis (4,5,6,7-tetrahydro) indene, propylenebis (1-indene), isopropyl (1-indenyl) cyclopentadiene, diphenylmethylene (9-fluorenyl) cyclopentadiene, isopropylcyclopentadienyl All such as -1-fluorene are compounds that can be used as the component (3) of the present invention.

The sulfide as the component (4) is represented by, for example, the following general formula.

[0035]

[Chemical 1]

R ⁵ in the formula represents an alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group and a nonyl group. To be R ⁶ in the formula represents a cycloalkyl group having 3 to 30 carbon atoms, preferably 5 to 10 carbon atoms. Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. R ⁷ in the formula has 6 to 30 carbon atoms, preferably 6 to 1 carbon atoms.
5 represents an aryl group. Specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group and a naphthyl group, and a phenyl group, a tolyl group and a xylyl group are preferable. R ⁸ in the formula represents an aralkyl group having 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms. Specific examples thereof include a benzyl group, a phenethyl group, a benzhydryl group, a trityl group and the like, and a benzyl group and a trityl group are preferable. R ⁹ in the formula represents hydrogen or a methyl group or an ethyl group, and may be the same or different. For example, those which are all hydrogen atoms or those which have only one methyl group and the rest are hydrogen atoms are used. n represents the number of n = 2-6, Preferably it is n = 2,4,5.

Specific compounds represented by the general formula (A) include diethyl sulfide, dipropyl sulfide,
Diisopropyl sulfide, dibutyl sulfide, diisobutyl sulfide, ditert-butyl sulfide,
Examples thereof include dipentyl sulfide and dihexyl sulfide. Among these, diisopropyl sulfide,
Diisobutyl sulfide and ditert-butyl sulfide are preferred.

Specific compounds represented by the general formula (B) include cyclopentyl methyl sulfide, cyclopentyl ethyl sulfide, cyclopentyl propyl sulfide, cyclopentyl isopropyl sulfide, cyclopentyl butyl sulfide, cyclopentyl isobutyl sulfide, cyclopentyl tert-butyl sulfide, cyclopentyl sulfide. Pentyl sulfide, cyclopentyl hexyl sulfide, cyclohexyl methyl sulfide, cyclohexyl ethyl sulfide, cyclohexyl propyl sulfide, cyclohexyl isopropyl sulfide, cyclohexyl butyl sulfide, cyclohexyl isobutyl sulfide, cyclohexyl tert-
Butyl sulfide, cyclohexyl pentyl sulfide, cyclohexyl hexyl sulfide and the like can be mentioned. Of these, cyclohexyl isopropyl sulfide, cyclohexyl isobutyl sulfide, cyclohexyl tert-butyl sulfide, cyclopentyl isopropyl sulfide, cyclopentyl isobutyl sulfide and cyclopentyl tert-butyl sulfide are preferable.

Specific compounds represented by the general formula (C) include phenylethyl sulfide, phenylpropyl sulfide, phenylisopropyl sulfide, phenylbutyl sulfide, phenylisobutyl sulfide,
Phenyl tert-butyl sulfide, phenyl pentyl sulfide, phenyl hexyl sulfide, tolyl ethyl sulfide, tolyl propyl sulfide, tolyl isopropyl sulfide, tolyl butyl sulfide, tolyl isobutyl sulfide, tolyl tert-butyl sulfide, tolyl pentyl sulfide, tolyl hexyl sulfide and the like. To be Of these, phenyl isopropyl sulfide, phenyl isobutyl sulfide, phenyl tert-butyl sulfide, tolyl isopropyl sulfide, tolyl isobutyl sulfide, and tolyl tert-butyl sulfide are preferable.

Specific compounds represented by the general formula (D) include benzyl ethyl sulfide, benzyl propyl sulfide, benzyl isopropyl sulfide, benzyl butyl sulfide, benzyl isobutyl sulfide,
Benzyl tert-butyl sulfide, benzyl pentyl sulfide, benzyl hexyl sulfide, trityl ethyl sulfide, trityl propyl sulfide, trityl isopropyl sulfide, trityl butyl sulfide, trityl isobutyl sulfide, trityl tert.
-Butyl sulfide, trityl pentyl sulfide, trityl hexyl sulfide and the like. Among these, benzyl isopropyl sulfide, benzyl isobutyl sulfide, benzyl tert-butyl sulfide, trityl isopropyl sulfide, trityl isobutyl sulfide, and trityl tert-butyl sulfide are preferable.

Specific compounds represented by formula (E) include dicyclopentyl sulfide and dicyclohexyl sulfide. Specific examples of the compound represented by the general formula (F) include cyclopentyl phenyl sulfide, cyclopentyl triyl sulfide, cyclohexyl phenyl sulfide and cyclohexyl tolyl sulfide. Specific examples of the compound represented by the general formula (G) include cyclopentylbenzyl sulfide, cyclopentyltril sulfide, cyclohexylbenzyl sulfide, cyclohexyltrityl sulfide and the like. Specific examples of the compound represented by the general formula (H) include diphenyl sulfide and ditolyl sulfide. Specific compounds represented by the general formula (I) include phenylbenzyl sulfide, tolylbenzyl sulfide, phenyltrityl sulfide and tolyltrityl sulfide. As a specific compound represented by the general formula (J), dibenzyl sulfide,
Examples thereof include ditrityl sulfide and dibenzyl trityl sulfide. Specific examples of the compound represented by the general formula (K) include tetrahydrothiophene and thiane. Of course, two or more kinds of these compounds may be used.

The modified organoaluminum compound which can be used in the present invention is a reaction product of an organoaluminum compound and water, which is 1 to 100, preferably 1 to 50, Al-O- in the molecule. It contains an Al bond.
The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. It is preferred to use group hydrocarbons.

The organoaluminum compound used for preparing the modified organoaluminum compound has the general formula R ¹⁰ _a AlX
³ _3-a ^{(wherein, R 10} is 1 to 18 carbon atoms, preferably 1 to 12 alkyl group, an alkenyl group, an aryl group, a hydrocarbon group such as an aralkyl group, X represents a hydrogen atom or a halogen atom, Any compound represented by a represents an integer of 1 ≦ a ≦ 3) can be used, but trialkylaluminum is preferably used. The alkyl group of trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. Is particularly preferable.

The reaction ratio of water and the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / l to 1.2 / l, and particularly preferably 0.5 / l to 1 / l. The reaction temperature is usually -70 to 100 ° C, preferably -20 to 20 ° C.
Is in the range. The reaction time is usually selected in the range of 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As water required for the reaction, so-called water can be used, and also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like can be used.

According to the present invention, olefins are homopolymerized or copolymerized in the presence of a catalyst composed of the above catalyst component and a promoter component exemplified by the modified organoaluminum compound. In this case, the catalyst component and the modified organoaluminum compound can be separately or premixed and supplied into the polymerization reaction system, and one or both of them are represented by a magnesium compound, alumina, silica, or silica-alumina. It can also be used by supporting it on an inorganic carrier and / or a polymer carrier mainly in the form of particles. In any case, the use ratio of the catalyst component and the modified organoaluminum compound is such that the atomic ratio of aluminum in the modified organoaluminum compound to the transition metal in the catalyst component is 1 to 100,000, preferably 5 to 1,0.
It is chosen to be in the range of 00.

The olefin polymerization catalyst component of the present invention is
As described above, (1) the general formula Me ¹ R ¹ _p (OR ² ) _q X
Compound represented by ¹⁴ _-pq (component (1)), (2)
The compound represented by the general formula Me ² R ³ _m (OR ⁴ ) _n X ² _z-mn (component (2)), (3) a cyclic organic compound having two or more conjugated double bonds (component (component (2)). 3)), and (4)
Al-OA, which is obtained by contacting each other with a sulfide (component (4)) as an essential component, and further obtained by the reaction of (5) an organoaluminum compound and water.
The catalyst of the present invention can be obtained by adding a modified organoaluminum compound containing an l bond (component (5)) and bringing them into contact with each other, but the order of contacting these components is not particularly limited. For example, the catalyst component of the present invention can be obtained by contacting each component with the following method.

1. A method of adding (2) to (1), further adding (3), and further adding (4). 2. A method of adding (2) to (1), further adding (4), and further adding (3). 3. A method of adding (3) to (1), further adding (2), and further adding (4). 4. A method of adding (3) to (1), further adding (4), and further adding (2). 5. A method of adding (4) to (1), further adding (2), and further (3). 6. A method of adding (4) to (1), further adding (3), and further (2). 7. A method of adding (1) to (2), further adding (3), and further (4). 8. A method of adding (1) to (2), further adding (4), and further (3). 9. A method of adding (3) to (2), further adding (1), and further adding (4). 10. A method of adding (3) to (2), further adding (4), and further adding (1). 11. A method of adding (4) to (2), further adding (1), and further (3). 12. A method of adding (4) to (2), further adding (3), and further (1). 13. A method of adding (1) to (3), further adding (2), and further adding (4). 14. A method of adding (1) to (3), further adding (4), and further adding (2). 15. A method of adding (2) to (3), further adding (1), and further adding (4). 16. A method of adding (2) to (3), further adding (4), and further adding (1). 17. A method of adding (4) to (3), further adding (1), and further adding (2). 18. A method of adding (4) to (3), further adding (2), and further (1). 19. A method of adding (1) to (4), further adding (2), and further adding (3). 20. A method of adding (1) to (4), further adding (3), and further (2). 21. A method of adding (2) to (4), further adding (1), and further adding (3). 22. A method of adding (2) to (4), further adding (3), and further (1). 23. A method of adding (3) to (4), further adding (1), and further adding (2). 24. A method of adding (3) to (4), further adding (2), and further (1). Further, the catalyst of the present invention can be obtained by contacting each component with the following method.

A. (1), (2), (3), (4),
A method of adding (5) at the same time. B. (1), (2), (3), (4) are mixed (hereinafter,
Component (6)) and component (5) are added. C. (1), (2), (3), (5) are mixed (hereinafter,
Component (7)) and component (4) are added. D. (1), (2), (4), (5) are mixed (hereinafter,
A method of adding component (8)) and component (3). E. (1), (3), (4), (5) are mixed (hereinafter,
A method of adding component (9)) and component (2). F. (2), (3), (4), (5) are mixed (hereinafter,
Component (10)), a method of adding component (1). G. (2), (3) and (4) were mixed (hereinafter, component (1
1)), components (1) and (5). H. (2), (3) and (5) were mixed (hereinafter, component (1
2)), components (1) and (4). I. (2), (4) and (5) are mixed (hereinafter, the component (1
3)), components (1) and (3). J. (3), (4) and (5) were mixed (hereinafter, the component (1
4)), components (1) and (2). K. (1), (4), and (5) were mixed (hereinafter, component (1
5)), components (2) and (3). L. (1), (3) and (5) are mixed (hereinafter, the component (1
6)), components (2) and (4). M. (1), (3) and (4) are mixed (hereinafter, the component (1
7)), components (2) and (5). N. (1), (2) and (4) are mixed (hereinafter, the component (1
8)), components (3) and (5). O. (1), (2) and (5) are mixed (hereinafter, the component (1
9)), and components (3) and (4). P. (1), (2) and (3) are mixed (hereinafter, the component (2
0)), components (4) and (5).

R. A method of mixing the components (6) and (7). S. A method of mixing the components (6) and (8). T. A method of mixing the components (6) and (9). U. A method of mixing the components (6) and (10). V. A method of mixing the components (7) and (8). X. A method of mixing the components (7) and (9). Y. A method of mixing the components (7) and (10). Z. A method of mixing the components (8) and (9). AA. A method of mixing the components (8) and (10). AB. A method of mixing the components (9) and (10).

AC. A method of further adding (1) to method A. AD. A method of further adding (2) to method A. AE. A method of further adding (3) to method A. AF. A method of further adding (4) to method A. AG. A method of further adding (5) to method A. AH. A method of further adding (1) to the method B. AI. A method of further adding (2) to the method B. AJ. A method of further adding (3) to the method B. AK. A method of further adding (4) to method B. AL. A method of further adding (5) to method B. AM. A method of further adding (1) to method C. AN. A method of further adding (2) to method C. AO. A method of further adding (3) to method C. AP. A method of further adding (4) to method C. AQ. A method of further adding (5) to method C. AR. A method of further adding (1) to the method D. AS. A method of further adding (2) to the method D. AT. A method of further adding (3) to the method D. AU. A method of further adding (4) to the method D. AV. A method of further adding (5) to the method D. AW. A method of further adding (1) to method E. AX. A method of further adding (2) to the method E. AY. A method of further adding (3) to the method E. AZ. A method of further adding (4) to the method E. AAA. A method of further adding (5) to the method E. AAB. A method of further adding (1) to method F. AAC. A method of further adding (2) to method F. AAD. A method of further adding (3) to method F. AAE. A method in which (4) is added to method F. AAF. A method of further adding (5) to method F.

The above is a method of mixing the catalyst components outside the polymerization system and introducing the resulting catalyst into the system. Further, the catalyst components may be added directly to the polymerization system in the order shown from the above method A to the method AAF. In addition, a method in which the component (6), the component (7), the component (8), the component (9), and the component (10) prepared outside the polymerization system and the remaining one component are added to the polymerization system, and Component (11), component (12), component (1
3), component (14), component (15), component (16), component (17), component (18), component (19), component (2)
It is also possible to add the prepared component (0) and the following components to the polymerization system.

A. A method in which (1) and (5) are added in this order to the polymerization system. b. A method in which (1) and (4) are added in this order to the polymerization system. c. A method in which (1) and (3) are added in this order to the polymerization system. d. A method in which (1) and (2) are added in this order to the polymerization system. e. A method in which (2) and (3) are added in this order to the polymerization system. f. A method in which (2) and (4) are added in this order to the polymerization system. g. A method in which (2) and (5) are added in this order to the polymerization system. h. A method in which (3) and (5) are added in this order to the polymerization system. i. A method in which (3) and (4) are added in this order to the polymerization system. j. A method of adding to the polymerization system in the order of (4) and (5).

Further, the catalyst was prepared from the components (1), (2), (3), (4) and (5) by the method shown from the A method to the AAF method (referred to as the component (21)). It can also be added to the polymerization system according to the following. k. A method of adding (21), (4) and (5) in this order to the polymerization system. l. A method in which (21), (5) and (4) are added in this order to the polymerization system. m. A method in which (4), (5) and (21) are added in this order to the polymerization system. n. A method in which (5), (4) and (21) are added in this order to the polymerization system.

Although a method other than these may be used, a method in which the components (1), (2) and (3) are mixed in advance, added to the component (5), and the component (4) is further added thereto Alternatively, a method in which the components (1), (2), (3) and (4) are mixed and added to the component (5) is particularly preferable.
In addition, the method of contacting the five components is optional, but usually, the components (1), (2), (3), (4) and (5) are added in an inert atmosphere such as nitrogen or argon. In the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene and xylene, usually -100 ° C to 200 ° C.
It is possible to employ a method of contacting at 30 ° C., preferably −50 ° C. to 100 ° C. for 30 minutes to 50 hours, preferably 2 hours to 24 hours.

When the components are brought into contact with each other in an inert hydrocarbon solvent, the produced catalyst may be directly subjected to polymerization in a solution state after completion of all the catalytic reactions, or, if possible, precipitated. Alternatively, the solid catalyst component may be once taken out by a means such as drying, and then used for polymerization. of course,
The contact reaction of each component may be performed multiple times. The proportion of these five components used is 0.01 to 1,000 mol, preferably 0.1 to 1,000 mol of the component (2) per 1 mol of the component (1).
To 100 mol, more preferably 0.5 to 50 mol, and component (3) 0.01 to 1,000 mol, preferably 0.1.
1 to 100 mol, more preferably 0.5 to 50 mol,
The component (4) is 0.01 to 100 mol, preferably 0.1.
It is preferable to prepare ˜50 mol, more preferably 0.1 to 10 mol, and the component (5) in a ratio of 1 to 1,000 mol, preferably 1 to 500 mol, more preferably 1 to 100 mol.

The olefins referred to in the present invention include α-olefins, cyclic olefins, dienes, trienes and styrene analogs. The α-olefins include those having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specifically, ethylene, propylene, butene-1,
Hexene-1, 4-methylpentene-1 and the like are exemplified. The α-olefins can be homopolymerized by using the catalyst component of the present invention, and also two or more kinds of α-olefins can be copolymerized. The copolymerization is alternating copolymerization, random copolymerization. It does not matter whether it is polymerization or block copolymerization.

For the copolymerization of α-olefins, ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, such as ethylene and carbon number 3 to 12, preferably. Is 3 to 8
-When copolymerizing with an olefin, propylene and butene-1, propylene and 4-methylpentene-1, propylene and 4-methylbutene-1, propylene and hexene-
1, such as propylene and octene-1, the case of copolymerizing propylene with an α-olefin having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms is included. When ethylene or propylene is copolymerized with other α-olefin, the amount of the other α-olefin can be arbitrarily selected within the range of 90 mol% or less of all monomers, but generally ethylene copolymer is used. In the case of a polymer, it is 40 mol% or less, preferably 30
Mol% or less, more preferably 20 mol% or less,
In the propylene copolymer, it is selected in the range of 1 to 90 mol%, preferably 5 to 90 mol%, and more preferably 10 to 70 mol%.

The cyclic olefin has 3 to 2 carbon atoms.
4, preferably 3 to 18 can be used in the present invention, for example cyclopentene, cyclobutene,
Cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, norbornene, 5-methyl-2-norbornene, 5-ethyl-
2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,5,6
-Trimethyl-2-norbornene, ethylidene norbornene and the like are included. The cyclic olefin is usually copolymerized with the above-mentioned α-olefin, in which case the amount of the cyclic olefin is 50 mol% or less of the copolymer,
It is usually in the range of 1 to 50 mol%, preferably 2 to 50 mol%.

The dienes and trienes usable in the present invention are polyenes having 4 to 26 carbon atoms, preferably 6 to 26 carbon atoms. Specifically, butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene,
1,4-hexadiene, 1,5-hexadiene, 1,3
-Cyclohexadiene, 1,4-cyclohexadiene,
1,9-decadiene, 1,13-tetradecadiene,
2,6-Dimethyl-1,5-heptadiene, 2-methyl-2,7-octadiene, 2,7-dimethyl-2,6-
Octadiene, 2,3-dimethylbutadiene, ethylidene norbornene, dicyclopentadiene, isoprene,
Examples include 1,3,7-octatriene and 1,5,9-decatriene. When a chain diene or triene is used in the present invention, it is usually copolymerized with the above-mentioned α-olefin, but the content of diene and / or triene in the copolymer is generally 0. 0.1 to 50 mol%, preferably 0.2 to 10 mol%.

Styrene analogs that can be used in the present invention are styrene and styrene derivatives such as t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene and 1,1-diphenyl. Examples thereof include ethylene, N, N-dimethyl-p-aminoethylstyrene and N, N-diethyl-p-aminoethylstyrene.

The catalyst component of the present invention can be preferably used also when a homopolymer or copolymer of olefins is further polymerized with a polar monomer to modify the homopolymer or copolymer. As the polar monomer, methyl acrylate,
Unsaturated carboxylic acid esters exemplified by methyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate and the like can be mentioned. The polar monomer content of the modified copolymer is usually in the range of 0.1 to 10 mol%, preferably 0.2 to 2 mol%.

The polymerization reaction can be carried out by slurry polymerization, solution polymerization or gas phase polymerization in the presence of the above catalyst component and promoter component. Slurry polymerization or gas phase polymerization is particularly preferable, and in a state where oxygen, water and the like are substantially cut off, hexane, an aliphatic hydrocarbon such as heptane, an aromatic hydrocarbon such as benzene, toluene and xylene, cyclohexane,
The olefin is polymerized in the presence or absence of an inert hydrocarbon solvent selected from alicyclic hydrocarbons such as methylcyclohexane. The polymerization conditions at this time are a temperature of 20 to 2
00 ° C., preferably 50 to 100 ° C., pressure normal pressure to 70 k
It is usually in the range of g / cm ² G, preferably atmospheric pressure to 20 kg / cm ² G, and the polymerization time is usually 5 minutes to 10 hours, preferably 5 minutes to 5 hours. The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it is possible to more effectively control the molecular weight by adding hydrogen to the polymerization reaction system. it can.

[0063]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but prior to that, preparation of modified organoaluminum compounds and catalyst components used in Examples and Comparative Examples will be described. [Preparation of modified organoaluminum compound (methylaluminoxane)] 13 g of copper sulfate pentahydrate was placed in a three-necked flask with a capacity of 300 ml equipped with an electromagnetic induction stirrer, and toluene 50 was added.
Suspended in ml. Then, 150 ml of a solution of trimethylaluminum having a concentration of 1 mmol / ml was added dropwise to the above suspension under the temperature condition of 0 ° C. over 2 hours, and after the addition was completed, the temperature was raised to 25 ° C. and the reaction was performed at that temperature for 24 hours. Let After that, the reaction product is filtered to remove toluene in the liquid containing the reaction product to obtain white crystalline methylalumoxane (M
AO) 4g was obtained. The physical properties of the polymers obtained in Examples and Comparative Examples were evaluated by the following methods. Melt Flow Rate (MFR) ASTM D 1238-57T 1
It measured based on 90 degreeC and a 2.16 kg load.

[Density] The density was measured according to ASTM D 1505-68. [Melting Point Measurement by Differential Thermal Scanning Calorimeter (DSC)] Using a DSC-20 type melting point measuring device manufactured by Seiko Denshi KK, a 5 mg sample was held at 180 ° C. for 3 minutes, and then 0 at 10 ° C./minute. The melting point was measured by cooling to 0 ° C, holding at 0 ° C for 10 minutes, and then raising the temperature at 10 ° C / min. [Mw / Mn measurement] 150C GP manufactured by Waters
Using a C device, column GMH-6 made by Toyo Soda, solvent o-dichlorobenzene, temperature 135 ° C., flow rate 1.0 m
It was measured under the condition of 1 / min, and Mw / Mn was obtained. [Temperature rising elution fractionation (Temperature Ris
ing Elution Fractionation
[Measurement by [hereinafter referred to as TREF]]] TREF was performed as follows. That is, the olefin copolymer was dissolved in o-dichlorobenzene and then cooled to form a polymer layer on diatomaceous earth, which was continuously heated and the eluted components were continuously detected.

Example 1 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxyzirconium (0.11 g), trihexylaluminum (0.69 ml), 1,2-bisindenylethane (0.1 g), diisopropyl sulfide (3.0 ×)
10 ⁻⁴ mol) was dissolved in 13 ml of toluene to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst. This catalyst solution was introduced into a 2 L autoclave, and the total pressure was maintained at 9 atm while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2).
Polymerization was carried out at 0 ° C. for 2 hours. Catalyst efficiency is 130kg /
gZr, density 0.9218 g / cm ³ , MFR 3.0 g / 10 min (190 ° C.), melting point 112.0
C., Mw / Mn = 8.0. The TREF peak was sharp and it was found that the composition distribution was very narrow.

Example 2 2 g of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxy zirconium (0.22 g), triethylaluminum (0.19 ml), indene (0.23 ml), cyclohexyl tert-butyl sulfide (5.0 × 1)
^0-4 mol) was dissolved in 13 ml of toluene to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst.
This catalyst solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and 60 ° C.
Polymerization was carried out for 2 hours. Catalyst efficiency is 135kg / gZ
r, density 0.9220 g / cm ³ , MFR 0.2
g / 10 min (190 ° C), melting point 116.2 ° C, M
It was w / Mn = 9.8.

Example 3 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tributoxy monochlorozirconium (0.26 g), diethylaluminium chloride (0.28 ml), indene (0.28 ml) and phenylisobutyl sulfide (4.4 × 10 ⁻⁵ mol) were dissolved in 17 ml of toluene to obtain a catalyst component. It was To 0.5 ml of this catalyst component solution was added a toluene solution of methylaluminoxane (Al / Zr
= 100 (molar ratio)), and stirred at room temperature for 30 minutes to obtain a target catalyst. This catalyst solution was introduced into a 2 L autoclave, and ethylene and 1-butene (butene / ethylene = 0.
While continuously supplying the mixed gas of 2), the total pressure was maintained at 9 atm and polymerization was carried out at 60 ° C. for 2 hours. Catalyst efficiency is 2
At 0 kg / gZr, the density is 0.9294 g / cm ³ , M
FR is 0.5g / 10min (190 ° C), melting point is 11
It was 6.7 degreeC and Mw / Mn: 9.6.

Example 4 2 g of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Dibutoxydichlorozirconium (0.26 g), diethylaluminum chloride (0.28 ml), indene (0.2
8 ml), tolyl tert-butyl sulfide (4.4
(× 10 ⁻⁵ mol) was dissolved in 17 ml of toluene to obtain a catalyst component. To 0.5 ml of this catalyst component solution was added a toluene solution of methylaluminoxane (Al / Zr = 100
(Molar ratio)), and stirred at room temperature for 30 minutes to obtain a target catalyst. This catalyst solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and the temperature was 60 ° C. for 2 hours. Polymerization was carried out. Catalyst efficiency is 22 kg /
gZr, density: 0.9211 g / cm ³ , MFR: 0.2 g / 10 min (190 ° C.), melting point: 112.3
C., Mw / Mn = 8.0.

Example 5 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxytitanium (0.13 g), triethylaluminum (0.29 ml), indene (0.35 ml) and dicyclopentyl sulfide (3.8 × 10 ⁻⁴ mol) were dissolved in 17 ml of toluene to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Ti = 1000 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst. This catalyst solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and the temperature was 60 ° C. for 2 hours. Polymerization was carried out. The catalyst efficiency is 25 kg / gTi, the density is 0.9240 g / cm ³ , and the MFR is 0.7 g / 10 mi.
n (190 ° C.), melting point 117.0 ° C., Mw / Mn =
It was 9.0.

Example 6 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrapropoxy zirconium (0.29g), diethyl ethoxy aluminum (1.16g), indene (0.41m)
l) was dissolved in 40 ml of toluene. Further, cyclohexyl tolyl sulfide (8.9 × 10 ⁻⁵ mol) was added and stirred at room temperature for 30 minutes to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 3 minutes.
The mixture was stirred for 0 minutes to obtain the target catalyst. 2 parts of this catalyst solution
It was introduced into an L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), polymerization was carried out at 60 ° C. for 2 hours while maintaining the total pressure at 9 atm. . The catalyst efficiency is 130 kg / gZr and the density is 0.
9242 g / cm ³ , MFR is 0.9 g / 10 min
(190 ° C.), melting point 114.1 ° C., Mw / Mn = 8.
It was 0.

Example 7 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrapropoxy hafnium (0.23 g), triethyl aluminum (0.38 ml), indene (0.23 ml) and cyclopentyl trityl sulfide (1.1 × 10 ⁻³ mol) were dissolved in 25 ml of toluene to obtain a catalyst component. Furthermore, a toluene solution of methylaluminoxane (Al / Hf
= 500 (molar ratio)) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst. This catalyst solution was introduced into a 2 L autoclave and the total pressure was adjusted to 9 while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2).
Polymerization was carried out at 60 ° C. for 2 hours while maintaining the atmospheric pressure. The catalyst efficiency is 40 kg / gHf and the density is 0.9241 g / cm.
³ , the MFR was 0.5 g / 10 min (190 ° C.), the melting point was 117.0 ° C., and Mw / Mn = 9.5.

Example 8 500 ml of purified toluene was introduced into a sufficiently dried 2 L autoclave. Tetrabutoxy zirconium (0.11 g), trihexyl aluminum (0.69
ml), 1,2,4-trimethylcyclopentadiene (0.31 g), diphenyl sulfide (2.2 x 10
^-4 mol) was dissolved in 13 ml of toluene to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 500 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst.
This catalyst solution was introduced into a 2 L autoclave, and propylene gas was continuously supplied, while maintaining the total pressure at 9 atm to carry out polymerization at 60 ° C. for 2 hours. Catalyst efficiency is 160kg
/ GZr, Mw = 15000, and Mw / Mn = 3.7.

Example 9 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxyzirconium (0.11 g), trihexylaluminum (0.69 ml) and indene (0.23 ml) were dissolved in 13 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Zr
= 100 (molar ratio)), and stirred at room temperature for 30 minutes. Furthermore, phenyltrityl sulfide (2.2 × 10 ⁻⁵ mol)
Was added and stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and polymerization was performed at 60 ° C for 2 hours. I went.
The catalyst efficiency is 134 kg / gZr and the density is 0.9218.
g / cm ³ , MFR is 2.0 g / 10 min (190
C.), the melting point was 112.1 ° C., and Mw / Mn = 8.0.

Example 10 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxy zirconium (0.22 g), n-butyllithium (5 mmol), and indene (0.23 ml) were dissolved in 13 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Zr = 100).
(Molar ratio)) and stirred at room temperature for 30 minutes. Further, benzyltrityl sulfide (2.2 × 10 ⁻⁵ mol) was added,
The mixture was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and ethylene and 1-butene (butene / ethylene =
Polymerization was carried out at 60 ° C. for 2 hours while continuously supplying the mixed gas of 0.2) and maintaining the total pressure at 9 atm. The catalyst efficiency is 20 kg / gZr and the density is 0.9230 g / c.
m ³ and MFR were 0.7 g / 10 min (190 ° C.), the melting point was 116.1 ° C., and Mw / Mn = 9.9.

Example 11 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxytitanium (0.13 g), dibutylmagnesium (5 mmol) and indene (0.35 ml) were dissolved in 17 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Ti = 100
0 (molar ratio)) and stirred at room temperature for 30 minutes. Further cyclohexylbenzyl sulfide (2.2 × 10 ⁻⁵ mol)
Was added and stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and polymerization was performed at 60 ° C for 2 hours. I went.
The catalyst efficiency is 30 kg / g Ti and the density is 0.9280 g.
/ Cm ³ , MFR is 0.01 g / 10 min (190
C.), the melting point was 119.4 ° C., and Mw / Mn = 8.5.

Example 12 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrapropoxy zirconium (0.29 g), diethylethoxyaluminum (0.12 g) and 1,3-dimethylcyclopentadiene (0.08 g) were dissolved in 40 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Zr = 100 (molar ratio)),
The mixture was stirred at room temperature for 30 minutes. Furthermore, thian (2.2 × 10
^-5 mol) was added, and the mixture was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and polymerization was performed at 60 ° C for 2 hours. I went. The catalyst efficiency is 120 kg / gZr, the density is 0.9210 g / cm ³ , and the MFR is 0.3 g / 10 mi.
n (190 ° C.), melting point 113.2 ° C., Mw / Mn =
It was 7.2.

Example 13 2 L of 200 g of sea sand that had been heat treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrapropoxy zirconium (0.29 g), diethylethoxyaluminum (0.67 g) and 1,3-dimethylcyclopentadiene (0.41 g) were dissolved in 40 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Zr = 100 (molar ratio)),
The mixture was stirred at room temperature for 30 minutes. Furthermore, thian (2.2 × 10
^-5 mol) was added, and the mixture was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and while continuously supplying ethylene gas, polymerization was carried out at 60 ° C. for 2 hours while maintaining the total pressure at 9 atm. The catalyst efficiency is 30 kg / gZr, the density is 0.9640 g / cm ³ , and the MFR is 0.2 g / 10 mi.
n (190 ° C.), melting point 135.1 ° C., Mw / Mn =
It was 5.3.

Example 14 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabenzyl zirconium (0.29 g), diethyl ethoxy aluminum (0.04 g), indene (0.41 ml)
Was dissolved in 40 ml of toluene. To 0.5 ml of this solution was added a toluene solution of methylaluminoxane (Al / Z
r = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes. Furthermore, cyclopentyl isopropyl sulfide (2.2 × 1
0 ^-5 mol) was added and stirred for 30 minutes at room temperature. This solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and polymerization was performed at 60 ° C for 2 hours. I went. The catalyst efficiency is 25 kg / gZr, the density is 0.9254 g / cm ³ , and the MFR is 0.5 g / 10 mi.
n (190 ° C.), melting point 114.0 ° C., Mw / Mn =
It was 8.4.

Example 15 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrachlorozirconium (0.19 g), ethylmagnesium chloride (8.2 × 10 ⁻⁵ mol), indene (0.4
1 ml) was dissolved in 40 ml of toluene. This solution 0.
A toluene solution of methylaluminoxane was added to 5 ml (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes. Further, benzyl tert-butyl sulfide (2.2 × 10 ⁻⁵ mol) was added, and the mixture was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave and the total pressure was maintained at 9 atm while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2) at 60 ° C.
Polymerization was carried out for 2 hours. Catalyst efficiency is 30kg / gZr
With a density of 0.9254 g / cm ³ and an MFR of 0.4 g
/ 10 min (190 ° C.), melting point 114.2 ° C., Mw
/Mn=5.5.

Example 16 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxyzirconium (0.11 g), trihexylaluminum (0.69 ml) and indene (0.23 ml) were dissolved in 13 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Zr
= 100 (molar ratio)), and stirred at room temperature for 30 minutes. Further, trityl isopropyl sulfide (2.2 × 10 ⁻⁵ mol) was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and polymerization was performed at 60 ° C for 2 hours. I went.
The catalyst efficiency is 90 kg / g Zr and the density is 0.9228 g.
/ Cm ³ , MFR is 2.1 g / 10 min (190
C.), the melting point was 112.4 ° C., and Mw / Mn = 7.0.

Example 17 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxyzirconium (0.11 g), trihexylaluminum (0.69 ml) and indene (0.23 ml) were dissolved in 13 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Zr
= 100 (molar ratio)), and stirred at room temperature for 30 minutes. Furthermore, dicyclohexyl sulfide (2.2 × 10 ⁻⁵ mol)
Was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and polymerization was performed at 60 ° C for 2 hours. I went. The catalyst efficiency is 85 kg / gZr and the density is 0.9228 g / c.
m ³ and MFR were 2.2 g / 10 min (190 ° C.), the melting point was 112.3 ° C., and Mw / Mn = 7.2.

Example 18 2 L of 200 g of sea sand which had been heat treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxyzirconium (0.11 g), trihexylaluminum (0.69 ml) and indene (0.23 ml) were dissolved in 13 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Zr
= 100 (molar ratio)), and stirred at room temperature for 30 minutes. Furthermore, cyclopentyl phenyl sulfide (2.2 × 10 ⁻⁵
Mol) was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and ethylene and 1-butene (butene /
While continuously supplying a mixed gas of ethylene = 0.2),
Polymerization was carried out at 60 ° C for 2 hours while maintaining the total pressure at 9 atm. The catalyst efficiency is 80 kg / gZr and the density is 0.912.
8 g / cm ³ , MFR is 1.8 g / 10 min (190
C.), the melting point was 111.3 ° C., and Mw / Mn = 9.1.

Example 19 2 L of 200 g of sea sand that had been heat treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxyzirconium (0.11 g), trihexylaluminum (0.69 ml) and indene (0.23 ml) were dissolved in 13 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Zr
= 100 (molar ratio)), and stirred at room temperature for 30 minutes. Furthermore, tetrahydrothiophene (2.2 × 10 ⁻⁵ mol) was added,
The mixture was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and ethylene and 1-butene (butene / ethylene =
Polymerization was carried out at 60 ° C. for 2 hours while continuously supplying the mixed gas of 0.2) and maintaining the total pressure at 9 atm. The catalyst efficiency is 80 kg / gZr and the density is 0.9228 g / c.
m ³ and MFR were 0.7 g / 10 min (190 ° C.), the melting point was 116.1 ° C., and Mw / Mn = 8.3.

Example 20 2 L of 200 g of sea sand that had been heat treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Dibenzyldichlorozirconium (0.29 g), ethylmagnesium chloride (8.2 × 10 ⁻⁵ mol) and indene (0.41 ml) were dissolved in 40 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes.
Stir for minutes. Furthermore, phenylbenzyl sulfide (2.
(2 × 10 ⁻⁵ mol) was added, and the mixture was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and while continuously supplying ethylene gas, polymerization was carried out at 60 ° C. for 2 hours while maintaining the total pressure at 9 atm. Catalyst efficiency is 20kg / gZr
And has a density of 0.9210 g / cm ³ and an MFR of 0.7 g.
/ 10 min (190 ° C), melting point 117.1 ° C, Mw
/Mn=7.2.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 3 except that phenylisobutyl sulfide was not used. Catalyst efficiency is 10 kg /
gZr, density 0.9208 g / cm ³ , MFR 0.3 g / 10 min (190 ° C.), melting point 112.3
C., Mw / Mn = 4.3.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 6 except that cyclohexyl tolyl sulfide was not used. Catalyst efficiency is 62 kg
/ GZr, density is 0.9208 g / cm ³ , MFR is 0.7 g / 10 min (190 ° C.), and melting point is 113.7.
C., Mw / Mn = 4.3.

Comparative Example 3 Polymerization was carried out in the same manner as in Example 7 except that cyclopentyl trityl sulfide was not used. Catalyst efficiency is 20k
g / g Hf, density is 0.9211 g / cm ³ , MFR
Is 0.4 g / 10 min (190 ° C.) and the melting point is 114.
It was 5 degreeC and Mw / Mn = 6.3.

Comparative Example 4 Example 8 except that no diphenyl sulfide was used.
Polymerization was carried out in the same manner as in. Catalyst efficiency is 100 kg / gZ
r, Mw = 13000, and Mw / Mn = 2.5.

Comparative Example 5 Polymerization was carried out in the same manner as in Example 9 except that phenyltrityl sulfide was not used. Catalyst efficiency is 74 kg / g
Zr, density 0.9100 g / cm ³ , MFR 1.
8g / 10min (190 ° C), melting point 111.0 ° C,
It was Mw / Mn = 5.5.

Comparative Example 6 Polymerization was carried out in the same manner as in Example 11 except that cyclohexylbenzyl sulfide was not used. Catalyst efficiency is 12
kg / g Ti, density 0.9245 g / cm ³ , MF
R is 0.02g / 10min (190 ° C), melting point is 11
It was 8.5 ° C. and Mw / Mn = 4.3.

Comparative Example 7 Polymerization was carried out in the same manner as in Example 13 except that thiane was not used. The catalyst efficiency is 15 kg / gZr and the density is 0.
9625g / cm ³ , MFR is 1.6g / 10min
(190 ° C.), melting point is 134.2 ° C., Mw / Mn = 4.
It was 0.

Comparative Example 8 Polymerization was carried out in the same manner as in Example 14 except that phenylisopropyl sulfide was not used. Catalyst efficiency is 10k
g / gZr, density 0.9274 g / cm ³ , MFR
Is 0.5 g / 10 min (190 ° C.) and the melting point is 115.
It was 7 degreeC and Mw / Mn = 6.2.

Comparative Example 9 Polymerization was carried out in the same manner as in Example 15 except that benzyl tert-butyl sulfide was not used. Catalyst efficiency is 1
At 0 kg / gZr, the density is 0.9233 g / cm ³ , M
FR is 0.5g / 10min (190 ° C), melting point is 11
It was 4.7 degreeC and Mw / Mn = 3.2.

Comparative Example 10 Polymerization was carried out in the same manner as in Example 20 except that phenylbenzyl sulfide was not used. Catalyst efficiency is 10 kg /
gZr, density was 0.9225 g / cm ³ , MFR was 0.7 g / 10 min (190 ° C.), and melting point was 117.7.
C., Mw / Mn = 4.2.

Comparative Example 11 Polymerization was carried out in the same manner as in Example 1 except that trihexylaluminum was not used. No polymer was obtained.

Comparative Example 12 Example 1 except that no bisindenylethane was used.
Polymerization was carried out in the same manner as in. Catalyst efficiency is 0.001Kg / g
It was Zr. It was found that the TREF peak was very broad and the composition distribution was wide.

[Brief description of drawings]

FIG. 1 is a flow chart showing steps for producing a catalyst of the present invention.

Claims (3)

[Claims] 1. A general formula Me ¹ R ¹ _p (OR ² ) _q.
A compound represented by X ¹ _4-pq (in the formula, R ¹ and R ² are independently a hydrocarbon group having 1 to 24 carbon atoms, X ¹ is a halogen atom, and Me ¹ is Zr, Ti, or Hf. , P and q are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4 and 0 ≦ p + q ≦ 4, respectively, and (2) the general formula Me ² R ³ _m (OR ⁴ ) _n X ²
A compound represented by _z-mn (wherein R ³ and R ⁴ are individually a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom,
Me ² is an element of Group I to III of the periodic table, z is the valence of Me ² , and m and n are 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively.
, And 0 ≦ m + n ≦ z), (3) a cyclic organic compound having two or more conjugated double bonds, and (4) a catalyst component for olefin polymerization obtained by bringing sulfides into contact with each other. . 2. A catalyst component according to claim 1, and Al—O—A obtained by reacting an organoaluminum compound with water.
A catalyst for polymerizing olefins, which comprises a modified organoaluminum compound having an l bond. 3. A method for producing an olefin polymer or copolymer, which comprises polymerizing or copolymerizing olefins in the presence of the catalyst according to claim 2.