JPH07228628A - Catalytic component for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain the subject catalytic component capable of giving high- molecular weight olefin polymers with relatively wide molecular weight distribu tion in high yield under conditions of small use of a modified aluminum com pound. CONSTITUTION:This catalytic component for olefin polymerization is obtained by mutual contact of (1) a compound of the formula Me<1>R<1>p(OR<2>)qX<1>4-p-q (X<1> is a halogen atom; Me<1> is Zr, Ti or Hf; (p) and (q) satisfy the following relationships: 0<=(p)<=4, 0<=q<=4 and 0<=(p+q)<=4), (2) a compound of the formula Me<2>R<3>m(OR<4>)nX<2>z-m-n (X<2> is a halogen atom; Me<2> is a group I-III element; (z) is the valence of Me<2>; (m) and (n) satisfy the following relationships: 0<=(m)<=z, 0<=(n)<=z and 0<=(m+n)<=z), (3) a cyclic organic compound having two or more conjugated double bonds, and (4) a compound of the formula R<1>aR<2>bR<3>cSi(OH)d(OR<4>)4-(a+b+c+d).

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. Relates to a catalyst component for polymerizing olefins, in which a polymer having a relatively wide range and having a narrow composition distribution in the case of a copolymer can be produced, and the molecular weight and the molecular weight distribution can be easily controlled. 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]

The object of the present invention is to produce an olefin polymer with high yield in a high yield under the condition that the amount of the modified organoaluminum compound such as methylaluminoxane is high and the molecular weight distribution is relatively wide and methylaluminoxane is extremely small. It is to provide a catalyst component to be produced, a catalyst, and a method for producing a polymer using the catalyst.

[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 general formula R ¹ _a R ² _b R ³ _c.
A compound represented by Si (OH) _d (OR ⁴ ) _{4- (a + b + c + d)} (in the formula, R ¹ , R ² , and R ³ are independently hydrogen,
Halogen or a hydrocarbon group having 1 to 24 carbon atoms, R ⁴ represents a hydrocarbon group having 1 to 24 carbon atoms, and a, b, c and d are 0 ≦ a <4, 0 ≦ b <4, 0 ≦ c. <4, 0 <d <4 and 0 <a + b + c <4, 1 <a + b + c + d ≦ 4), 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.
A polymer having a relatively wide molecular weight distribution and a narrow composition distribution in the case of a copolymer can be produced. Further, when molding a polymer produced by using the olefin polymerization catalyst of the present invention, there is no stickiness in either the inflation method or the T-die method, high-speed molding is possible, and the moldability is extremely good. Is. 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.

The present invention will be described in detail below. First, the general formula of the component (1) Me ¹ R ¹ _p (OR ² ) _q X ¹
_The compound represented by _4-pq will be described. In the formula, R ¹ and R ² have 1 to 24 carbon atoms, preferably 1
To 12 and more preferably 1 to 8 hydrocarbon groups, and such hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tert- Butyl, cyclobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, isohexyl, cyclohexyl, heptyl, octyl, decyl, dodecyl, and other alkyl groups; vinyl, allyl, etc. Alkenyl group; aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, phenylpropyl group, neofil group And aralkyl groups such as. These may have branches. X ¹ is a halogen atom of fluorine, iodine, chlorine and bromine, Me ¹
Represents Zr, Ti or Hf, and is preferably Zr. p and q are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, and 0 ≦, respectively.
p + q ≦ 4, preferably 0 <p + q ≦ 4.

Specific examples of the compound represented by the above general formula include tetramethylzirconium, tetraethylzirconium, tetrapropylzirconium and tetra-n-.
Butylzirconium, tetrapentylzirconium, tetraphenylzirconium, tetratolylzirconium, tetrabenzylzirconium, tetraallylzirconium, tetraneophyllzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrapentyloxyzirconium, tetra Phenoxyzirconium, tetratolyloxyzirconium,
Tetrabenzyloxyzirconium, tetraallyloxyzirconium, tetraneophyloxyzirconium,

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, trineo. Phil monochlorozirconium, dimethyldichlorozirconium, diethyldichlorozirconium, dipropyldichlorozirconium, di-n-butyldichlorozirconium, dipentyldichlorozirconium, diphenyldichlorozirconium, ditolyldichlorozirconium, dibenzyldichlorozirconium, diallyldichlorozirconium,
Dineofildichlorozirconium, monomethyltrichlorozirconium, monoethyltrichlorozirconium, monopropyltrichlorozirconium, mono-n-butyltrichlorozirconium, monopentyltrichlorozirconium, monophenyltrichlorozirconium,
Monotolyltrichlorozirconium, 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, monoallyloxytrichlorozirconium, trineo I oxy monochloro zirconium, di neophyl oxy zirconium dichloride, mono neophyl oxy trichloro zirconium,

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- butyl tribromo zirconium, mono pen tilt Li bromo zirconium, monophenyl tribromo zirconium, mono tolyl tribromo zirconium, monobenzyl tribromo zirconium, monoallyl tribromo zirconium, mono neophyl tribromo zirconium,

Tetrabromozirconium, trimethoxymonobromozirconium, dimethoxydibromozirconium, monomethoxytribromozirconium, triethoxymonobromozirconium, diethoxydibromozirconium, triethoxytribromozirconium, tripropoxymonobromozirconium, dipropoxydibromozirconium , Monopropoxytribromozirconium, tri-n-butoxymonobromozirconium, di-n
-Butoxydibromozirconium, mono-n-butoxytribromozirconium, tripentyloxymonobromozirconium, dipentyloxydibromozirconium, monopentyloxytribromozirconium, triphenoxymonobromozirconium, diphenoxydibromozirconium, monophenoxytribromozirconium, tri Trilyloxymonobromozirconium, ditolyloxydibromozirconium, monotolyloxytribromozirconium, tribenzyloxymonobromozirconium, dibenzyloxydibromozirconium, monobenzyloxytribromozirconium, triallyloxymonobromozirconium, diallyloxydibromozirconium , Monoallyloxytribromozirconium, trineo I oxy mono bromo zirconium, di neophyl oxy dibromo zirconium, mono neophyl oxy tribromo zirconium,

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, mono pen tilt Li iodo zirconium, monophenyl triiodo zirconium, mono-tolyl-triiodo zirconium, monobenzyl triiodo zirconium,

Tetraiodozirconium, trimethoxymonoiodozirconium, dimethoxydiiodozirconium, monomethoxytriiodozirconium, triethoxymonoiodozirconium, diethoxydiiodozirconium, monoethoxytriiodozirconium, tripropoxymonoiodozirconium, dipropoxy. Diiodozirconium, monopropoxytriiodozirconium, tri-n-butoxymonoiodozirconium, di-n
-Butoxydiiodozirconium, mono-n-butoxytriiodozirconium, tripentyloxymonoiodozirconium, dipentyloxydiiodozirconium, monopentyloxytriiodozirconium, triphenoxymonoiodozirconium, diphenoxydiiotozirconium, monophenoxytriiodo Zirconium, tritolyloxymonoiodozirconium, ditolyloxydiiodozirconium, monotolyloxytriiodozirconium, tribenzyloxymonoiodozirconium, dibenzyloxydiiodozirconium, monobenzyloxytriiodozirconium, triallyloxymonoiodozirconium , Diallyloxydiiodozirconium, monoallyloxytriiodozirconium, trineo I oxy mono yaw preparative zirconium, di neophyl oxy diiodo zirconium, mono neophyl oxy-triiodo zirconium,

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,
Monobenzyltriethoxyzirconium, monobenzyltripropoxyzirconium, monobenzyltributoxyzirconium, monobenzyltripentyloxyzirconium, monobenzyltriphenoxyzirconium,
Monobenzyltritolyloxyzirconium, monobenzyltribenzyloxyzirconium, monobenzyltriallyloxyzirconium, monobenzyltrineophylloxyzirconium, trineofilmonomethoxyzirconium, trineofilmonoethoxyzirconium, trineofilmonopropoxyzirconium, Trineofil monobutoxy zirconium, Trineophyll monophenoxy zirconium, Dineofil dimethoxyzirconium, Dineofil diethoxyzirconium,
Dineofil dipropoxy zirconium, Dyneofil dibutoxy zirconium, Dyneofil diphenoxy zirconium, Mononeophile trimethoxy zirconium, Mononeophile triethoxy zirconium, Mononeophile tripropoxy zirconium, Mononeophile tributoxy zirconium, Mono Neofil triphenoxy zirconium,

Tetramethyl titanium, tetraethyl titanium, tetrapropyl titanium, tetra n-butyl titanium, tetrapentyl titanium, tetraphenyl titanium, tetratolyl titanium, tetrabenzyl titanium, tetraallyl titanium, tetra neofiltitanium, tetramethoxy titanium, tetra Ethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentyloxytitanium, tetraphenoxytitanium, tetratolyloxytitanium, tetrabenzyloxytitanium, tetraallyloxytitanium, tetraneophyloxytitanium,

Trimethyl monochlorotitanium, triethyl monochlorotitanium, tripropyl monochlorotitanium, tri-n-butyl monochlorotitanium, tribenzyl monochlorotitanium, dimethyldichlorotitanium, diethyldichlorotitanium, di-n-butyldichlorotitanium, dibenzyldichlorotitanium, monomethyltrichloro. Titanium, monoethyltrichlorotitanium, mono-n-butyltrichlorotitanium, monobenzyltrichlorotitanium, tetrachlorotitanium, trimethoxymonochlorotitanium, dimethoxydichlorotitanium, monomethoxytrichlorotitanium, triethoxymonochlorotitanium, diethoxydichlorotitanium, monoethoxytrichloro. Titanium, tripropoxy Bruno chloro titanium, dipropoxy dichloro titanium, mono-propoxy trichlorotitanium, tri n- butoxy monochloro titanium, di n
-Butoxydichlorotitanium, mono-n-butoxytrichlorotitanium, tripentyloxymonochlorotitanium, dipentyloxydichlorotitanium, monopentyloxytrichlorotitanium, triphenoxymonochlorotitanium, diphenoxydichlorotitanium, monophenoxytrichlorotitanium, tritolyloxymonochlorotitanium, Ditolyloxydichlorotitanium, monotolyloxytrichlorotitanium,
Tribenzyloxy monochlorotitanium,

Dibenzyloxydichlorotitanium, monobenzyloxytrichlorotitanium, tetrabromotitanium, trimethylmonobromotitanium, triethylmonobromotitanium, tripropylmonobromotitanium, tri-n-butylmonobromotitanium, tribenzylmonobromotitanium, dimethyl Dibromotitanium, diethyldibromotitanium, di-n-butyldibromotitanium, dibenzyldibromotitanium, monomethyltribromotitanium, monoethyltribromotitanium, mono-n-butyltribromotitanium, monobenzyltribromotitanium, tetrabromotitanium, trimethoxy Monobromotitanium, dimethoxydibromotitanium, trimethoxytribromotitanium, triethoxy Bruno bromo titanium, diethoxy-dibromo titanium, mono-ethoxy tribromo titanium tripropoxy monobromophenol titanium, dipropoxy dibromo titanium, mono-propoxy tribromo titanium, tri n- butoxy mono bromo titanium, di n
-Butoxydipromotitanium, mono-n-butoxytribromotitanium, tripentyloxymonobromotitanium, dipentyloxydibromotitanium, monopentyloxytribromotitanium, triphenoxymonobromotitanium, diphenoxydibromotitanium, monophenoxytribromotitanium, Tritolyloxymonobromotitanium, 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,

Mononeophyll trimethoxy hafnium,
Mononeophyll triethoxy hafnium, mononeophyll tripropoxy hafnium, mononeophyll tributoxy hafnium, mononeophyll 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 iso-, s-, t-, n.
It also includes cases in which there are various structural isomer groups such as eo-. Among these specific compounds, tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetrabutoxyzirconium, tetrabutoxytitanium and tetrabutoxyhafnium are preferable. Particularly preferably Z such as tetrapropoxyzirconium and tetrabutoxyzirconium.
r (OR) ₄ compound. 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. Me in ^{_{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 the compound 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 mag Nitrosium iodide, phenyl magnesium bromide, phenyl magnesium iodide, benzyl bromide, benzyl magnesium iodide,

Dimethyl zinc, diethyl zinc, dipropyl zinc, diisopropyl zinc, di-n-butyl zinc, di-t-
Butyl zinc, dipentyl zinc, dioctyl zinc, diphenyl zinc, dibenzyl zinc, trimethylboron, triethylboron, tripropylboron, triisopropylboron, tributylboron, tri-t-butylboron, tripentylboron, trioctylboron, triphenylboron, tri Benzylboron, trimethylaluminum,
Triethyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum fluoride, diethyl aluminum iodide, ethyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum difluoride, ethyl aluminum 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 one butylaluminum 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), a cyclic organic compound having two or more conjugated double bonds is used. Ingredient (3)
Includes two or more, preferably 2 to 4 conjugated double bonds,
More preferably, it has 2-3, and the total carbon number is 4-24,
A cyclic hydrocarbon compound preferably having 4 to 12; the cyclic hydrocarbon compound is partially substituted with 1 to 6 hydrocarbon residues (typically, an alkyl group having 1 to 12 carbon atoms or an aralkyl group) A cyclic hydrocarbon compound having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds and having a total carbon number of 4 to 24, preferably 4 to 1
An organosilicon compound having a cyclic hydrocarbon group of 2; an organosilicon compound in which the cyclic hydrocarbon group is partially substituted with 1 to 6 hydrocarbon residues or an alkali metal salt (sodium salt or lithium salt) included. Particularly preferably, one having a cyclopentadiene structure in any of the molecules is desirable.

Incidentally, the organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. A _L SiR _4-L where A 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, Alkyl groups such as propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, octyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group; aryl groups such as phenyl group; phenoxy group etc. An aryloxy group of: a hydrocarbon residue or hydrogen having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, as exemplified by an aralkyl group such as a benzyl group, L is 1
≦ L ≦ 4, preferably 1 ≦ L ≦ 3.

Therefore, specific examples of the organic cyclic hydrocarbon compound 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, biscyclopentadienylsilane, triscyclopentadienylsilane, tetrakiscyclopentadienylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadienylmonoethylsilane, monocyclo Pentadienyldimethylsilane, Monocyclopentadienyldiethylsilane, Monocyclopentadienyltrimethylsilane, Monocyclopentadienyltriethylsilane, Monocyclopentadienylmonomethoxysilane, Monocyclopentadienylmonoethoxysilane, Monocyclo Pentadienylmonophenoxysilane,

Biscyclopentadienylmonomethylsilane, biscyclopentadienylmonoethylsilane, biscyclopentadienyldimethylsilane, biscyclopentadienyldiethylsilane, biscyclopentadienylmethylethylsilane, biscyclopentadienyl Dipropylsilane, biscyclopentadienylethylpropylsilane, biscyclopentadienyldiphenylsilane,
Biscyclopentadienylphenylmethylsilane, Biscyclopentadienylmonomethoxysilane, Biscyclopentadienylmonoethoxysilane, Triscyclopentadienylmonomethylsilane, Triscyclopentadienylmonoethylsilane, Triscyclopentadienylmonosilane Methoxysilane, triscyclopentadienyl monoethoxysilane, 3-methylcyclopentadienylsilane, bis-3-methylcyclopentadienylsilane, 3-
Methylcyclopentadienylmethylsilane, 1,2-dimethylcyclopentadienylsilane, 1,3-dimethylcyclopentadienylsilane, 1,2,4-trimethylcyclopentadienylsilane, 1,2,3,4 -Tetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsilane,

Monoindenylsilane, bisindenylsilane, trisindenylsilane, tetrakisindenylsilane, monoindenylmonomethylsilane, monoindenylmonoethylsilane, monoindenyldimethylsilane, monoindenyldiethylsilane, monoindene. Nyltrimethylsilane, monoindenyltriethylsilane, monoindenylmonomethoxysilane, monoindenylmonoethoxysilane, monoindenylmonophenoxysilane, bisindenylmonomethylsilane, bisindenylmonoethylsilane, bisindenyldimethylsilane, Bisindenyldiethylsilane, bisindenylmethylethylsilane, bisindenyldipropylsilane, bisindenylethylpropylsilane, bisindenyldiphenylsilane, bisyne Cycloalkenyl phenylmethyl silane, bis indenyl monomethoxy silane, bis indenyl mono-ethoxysilane,

Trisindenyl monomethylsilane, trisindenyl monoethylsilane, trisindenyl monomethoxysilane, trisindenyl monoethoxysilane, 3-methylindenylsilane, bis-3-methylindenylsilane, 3-methylindenyl Methylsilane,
1,2-dimethylindenylsilane, 1,3-dimethylindenylsilane, 1,2,4-trimethylindenylsilane, 1,2,3,4-tetramethylindenylsilane, pentamethylindenylsilane, etc. is there.

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.

Component (4) is a compound represented by the following general formula. R ¹ _a R ² _b R ³ _c Si (OH) _d (OR ⁴ )
_{In the 4- (a + b + c + d)} formula, R ¹ , R ² , and R ^{3 each} independently represent hydrogen, halogen, or a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and R ⁴ Represents a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms.

The hydrocarbon group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group and a hexyl group. , Alkyl groups such as isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, dodecyl group; alkenyl groups such as vinyl group, allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group Aryl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group,
It includes an aralkyl group such as a phenylbutyl group, a phenylpropyl group and a neophyll group, and these may have a branch. Halogen includes fluorine, chlorine, bromine and iodine. R ¹ , R ² and R ³ may be the same or different from each other. When R ⁴ is a hydrocarbon group,
R ¹ , R ² , R ³ and R ⁴ may be the same or different from each other.

A, b, c and d are 0≤a <4, 0≤b <
4,0 ≦ c <4,0 <d <4 and 0 <a + b + c +
<4, 1 <a + b + c + d ≦ 4. Among the above compounds, preferred examples include general formulas R ¹ Si (OH) ₃ and R ¹
Si (OH) ₂ (OR ⁴ ), R ¹ Si (OH) (O
R ⁴ ) ₂ , R ¹ R ² Si (OH) ₂ , R ¹ R ² Si (O
H) (OR ⁴ ) and compounds represented by R ¹ R ² R ³ Si (OH). Specific examples of the component (4) include C
_{H 3 Si (OH) 3,} (CH 3) 2 Si (OH) 2,
(CH ₃ ) ₃ Si (OH), C ₂ H ₅ Si (OH) ₃ ,
_{(C 2 H 5) 2 Si} (OH) 2, (C 2 H 5) 3 Si
_{(OH), i-C 3} H 7 Si (OH) 3, (i-C 3 H
₇ ) ₂ Si (OH) ₂ , (i-C ₃ H ₇ ) ₃ Si (O
_{H), n-C 3 H} 7 Si (OH) 3, (n-C 3 H 7)
_{2 Si (OH) 2, (} n-C 3 H 7) 3 Si (OH),
_{n-C 4 H 9 Si (} OH) 3, (n-C 4 H 9) 2 Si
_{(OH) 2, (n-} C 4 H 9) 3 Si (OH), i-C
_{4 H 9 Si (OH) 3} , (i-C 4 H 9) 2 Si (O
H) ₂ , (t-C ₄ H ₉ ) ₃ Si (OH),

[0046]

[Chemical 1]

CH ₃ Si (OH) ₂ (OCH ₃ ), CH
₃ Si (OH) ₂ (OC ₂ H ₅ ), CH ₃ Si (OH)
_{2 (Oi-C 3 H 7} ), CH 3 Si (OCH 3) 2 (O
_{H), CH 3 Si (OC} 2 H 5) 2 (OH), CH 3 S
_{i (Oi-C 3 H 7} ) 2 (OH), C 2 H 5 Si (O
H) ₂ (OCH ₃ ), C ₂ H ₅ Si (OH) ₂ (OC _{2
H 5), C 2 H 5} Si (OH) 2 (Oi-C 3 H 7),
C ₂ H ₅ Si (OCH ₃ ) ₂ (OH), C ₂ H ₅ Si
_{(OC 2 H 5) 2 (} OH), C 2 H 5 Si (Oi-C 3
H ₇ ) ₂ (OH), (CyH) Si (OH) ₂ (OCH
₃ ), (CyH) Si (OH) ₂ (OC ₂ H ₅ ), (C
_{yH) Si (OH) 2 (} Oi-C 3 H 7), (CH 3)
_{(T-C 4 H 9)} Si (Oi-C 3 H 7) OH, (CH
_{3) (Ph) Si (Oi} -C 3 H 7) OH, (CH 3)
_{(CyH) Si (Oi-C} 3 H 7) OH, (CH 3) 2
_{(T-C 4 H 9)} Si (OH), (CH 3) 2 (Ph)
_{Si (OH), (CH 3} ) 2 (CyH) Si (OH),

(T-C ₄ H ₉ ) ₂ Si (OH) F, (t
_{-C 4 H 9) 2 Si (} OH) Cl, (t-C 4 H 9) 2
_{Si (OH) Br, (t} -C 4 H 9) 2 Si (OH)
_{I, (CH 3) 2 SiF} (OH), (CH 3) 2 SiC
l (OH), (CH ₃ ) ₂ SiBr (OH), (C
Compounds such as H ₃ ) ₂ SiI (OH) can be given. Among these compounds, especially (CH ₃ ) ₃ Si
(OH), (Ph) ₃ Si (OH), (C ₂ H ₅ ) ₃ S
i (OH) is preferred. Of course, it is also possible to use a plurality of these compounds in combination.

The catalyst component of the present invention is the above-mentioned four components, that is, (1) the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹
A compound represented by the _4-p-q (component (1)), represented by (2) the general formula _{^{Me 2 R 3 m (OR 4}} ) n X 2 z-m-n ( component (2)), (3) a cyclic organic compound having two or more conjugated double bonds (component (3)), and (4) general formula R
¹ _a R ² _b R ³ _c Si (OH) _d (OR ⁴ )
_The compound (component (4)) represented by _{4- (a + b + c + d)} is obtained by bringing them into contact with each other.

As the contact ratio, the usual component (1) is used.
The component (2) is 0.01 to 1,000 moles, preferably 0.1 to 100 moles, more preferably 0.5 to 50 moles, and the component (3) is 0.01 to 1,000 moles.
Mol, preferably 0.1 to 100 mol, more preferably 0.5 to 50 mol, and component (4) 0.01 to 1.00.
It is prepared by bringing them into contact with each other in an amount of 0 mol, preferably 0.1 to 50 mol, and more preferably 0.5 to 20 mol. At this time, the component (4) is 0.001 to 10 moles, preferably 0.01 to 1 mole of the component (2).
It is desirable to bring them into contact with each other in an amount of 1 to 1 mol, more preferably 0.05 to 0.5 mol.

The order of contacting the four components is arbitrary, but as a suitable method, the components can be contacted by the following method to obtain the catalyst component of the present invention. 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). 25. A method of simultaneously contacting components (1) to (4). 26. A method of simultaneously contacting the components (1) to (3) and then contacting the component (4). 27. Part of the component (3) is brought into contact with the component (1), and the rest of the component (3) is brought into contact with the component (2), and
Then, a method of contacting the component (4). 28. A method of contacting the components (1), (3), and (4) in advance, and then contacting the component (2). And the like, but in particular, 4. A method of adding (3) to (1), further adding (4), and further adding (2). 6. A method of adding (4) to (1), further adding (3), and further (2). 17. A method of adding (4) to (3), further adding (1), and further adding (2). 28. A method in which the components (1), (3) and (4) are contacted with each other in advance and then the component (2) is contacted with each other is preferable.

Although the method of contacting the four components is optional,
Component (1), component (2), component (3) and component (4), usually in an inert atmosphere such as nitrogen or argon,
The contact is preferably performed in the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene, xylene. The temperature condition in this case is usually -100 ° C to 200 ° C.
C., preferably in the range of −50 ° C. to 100 ° C., and the contact time is in the range of 30 minutes to 50 hours, preferably 2 hours to 24 hours. When each component is contacted in an inert hydrocarbon solvent, the produced catalyst component can be directly subjected to polymerization together with the solvent, and once taken out as a solid catalyst component by means of precipitation, drying, etc., It can also be used for polymerization. Of course, each component may be contacted multiple times.

The catalyst component of the present invention obtained by bringing the components (1) to (4) into contact with each other as described above is usually combined with a further promoter-like catalyst component to polymerize or copolymerize olefins. It becomes a useful catalyst. As the promoter-like catalyst component, any one kind or a combination of two or more kinds may be used as long as it does not impair the object of the present invention and the performance of the catalyst part. For this, the following modified organoaluminum compounds are used.

Modified Organoaluminum Compound (Component (5)) The modified organoaluminum compound which can be used in the present invention is a reaction product of an organoaluminum compound and water. Is 1
It contains 50 Al-O-Al bonds. 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, xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. It is preferred to use group hydrocarbons.

The organoaluminum compound used to prepare the modified organoaluminum compound has the general formula R ⁴ _a AlX ³
_3-a (In the formula, R ⁴ has 1 to 18 carbon atoms, preferably 1 to
12 are hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups and aralkyl groups, X is a hydrogen atom or a halogen atom, and a is an integer of 1 ≦ a ≦ 3. Although possible, preferably trialkylaluminum is used. The alkyl group of trialkylaluminum includes a methyl group, an ethyl group, a propyl group,
Any of an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group may be used, but a methyl group 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 polymerized in the presence of a catalyst composed of the above-mentioned catalyst component and a promoter-like catalyst component exemplified by the modified organoaluminum compound (component (5)). Copolymerized.
In this case, the catalyst component and the modified organoaluminum compound are
It can be fed separately or previously mixed or contacted into the polymerization reaction system. When the catalyst component and the modified organoaluminum compound are mixed or contacted in advance,
In addition to the case of simply contacting or mixing the catalyst component and the modified organoaluminum compound obtained by bringing the components (1) to (4) into contact with each other, by further bringing the components (1) to (5) into contact with each other. It also includes a method of obtaining a catalyst. The order of contacting the components (1) to (5) is also arbitrary. The following method can be given as a specific example.

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, a catalyst was prepared from the components (1), (2), (3), (4) and (5) by the method shown from Method A to AAF (referred to as 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, 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 the polymerization in a solution state after the 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. Further, the catalyst component, the promoter-like catalyst component or the catalyst can be used by supporting them on an inorganic carrier represented by alumina or silica and / or mainly on a particulate polymer carrier. In any case, the proportion of the catalyst component and the modified organoaluminum compound used is such that the atomic ratio of aluminum in the modified organoaluminum compound to the transition metal in the catalyst component is 1 to 1.
It is selected to be in the range of 0,000, preferably 5 to 1,000.

In the catalyst of the present invention, the components (1) to (5)
The following combinations are mentioned as one of the preferable combinations of. A tetraalkylzirconium compound such as tetramethylzirconium or a tetraaralkylzirconium compound such as tetrabenzylzirconium in the component (1), triethylaluminum in the component (2),
Trialkylaluminum compounds such as triisobutylaluminum, trihexylaluminum or tridecylaluminum, or halogen-containing alkylaluminum compounds such as diethylaluminum chloride or ethylaluminum dichloride, and indene derivatives such as indene, methylindene or trimethylsilylindene among component (3) Cyclopentadiene derivatives such as cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene; indene derivatives such as bisindenylethane or isopropylbiscyclopentadiene or cyclopentadiene derivatives bound via alkylene groups Compound or dimethylsilylbi The compound represented by the general formula A _L SiR _4-L, such as cyclopentadiene, triaryl silanol compound, such as trialkyl silanol or triphenyl silanol, such as trimethyl silanol or triethyl silanol of the components (4), and component (5 ) Out of methylaluminoxane.

The following combinations are mentioned as one of other suitable combinations. Tetraalkyltitanium compounds such as tetramethyltitanium among the components (1); tetraalkoxytitanium compounds such as tetranormalbutoxytitanium or tetraisopropoxytitanium or tetraaralkyltitanium compounds such as tetrabenzyltitanium; trimethylaluminum among the components (2) , Triethylaluminum, triisobutylaluminum, trihexylaluminum or tridecylaluminum or other trialkylaluminum compounds or halogen-containing alkylaluminum compounds such as diethylaluminum chloride or ethylaluminum dichloride, indene, methylindene or trimethylsilylindene among the components (3) Indene derivatives such as: cyclopentadiene, methylcyclo A cyclopentadiene derivative such as pentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene; a compound in which an indene derivative or a cyclopentadiene derivative such as bisindenylethane or isopropylbiscyclopentadiene is bound via an alkylene group or dimethylsilylbiscyclo The above general formula A _L SiR such as pentadiene
A compound represented by _4-L , a trialkylsilanol such as trimethylsilanol or triethylsilanol or a triarylsilanol compound such as triphenylsilanol among the components (4), and methylaluminoxane among the components (5).

The following combinations are mentioned as one of other suitable combinations. A tetraalkoxyzirconium compound such as tetranormal butoxyzirconium or tetraisopropoxyzirconium among the components (1),
Of the component (2), a trialkylaluminum compound such as triethylaluminum, triisobutylaluminum, trihexylaluminum or tridecylaluminum or an alkylaluminum alkoxide compound such as diethylaluminum butoxide, ethyldibutoxyaluminum or diethylethoxyaluminum. Indene derivatives such as indene, methylindene or trimethylsilylindene among the components (3); cyclopentadiene derivatives such as cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene; bisindenylethane or isopropylbis Indene derivatives such as cyclopentadiene or cyclopen Compounds diene derivative represented by the general formula A _L SiR _4-L, such as a compound or dimethylsilyl bis cyclopentadiene bonded through an alkylene group, trialkyl silanols such as trimethyl silanol or triethyl silanol of the components (4) Alternatively, a triarylsilanol compound such as triphenylsilanol, and methylaluminoxane among the components (5).

The following combinations are mentioned as one of other suitable combinations. Of the component (1), a zirconium chloride compound such as zirconium tetrachloride, phenoxyzirconium chloride, trichloroisopropoxyzirconium or benzylzirconium trichloride, and an alkyllithium compound such as butyllithium or methyllithium or dibutylmagnesium in the component (2). , An alkylmagnesium compound such as ethylmagnesium bromide or butylmagnesium chloride, an indene derivative such as indene, methylindene or trimethylsilylindene among the components (3); cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene Derivatives such as cyclopentadiene; bisindenylethane or isopropylbisshi Compound indene derivative or cyclopentadiene derivative such as Ropentajien are bonded through an alkylene group or the formula A _L SiR compound represented by the _4-L, such as dimethylsilyl bis cyclopentadiene, trimethyl silanol of the components (4) Alternatively, a trialkylsilanol such as triethylsilanol or a triarylsilanol compound such as triphenylsilanol, and methylaluminoxane among the components (5).

The following combinations are mentioned as one of the other suitable combinations. A tetraalkoxyzirconium compound such as tetranormal butoxyzirconium or tetraisopropoxyzirconium among the components (1),
Of the component (2), a trialkylaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum or tridecylaluminum, or a halogen-containing alkylaluminum compound such as diethylaluminum chloride or ethylaluminum dichloride, the component (3) Indene derivatives such as indene, methylindene or trimethylsilylindene; cyclopentadiene derivatives such as cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene; indene derivatives such as bisindenylethane or isopropylbiscyclopentadiene Or cyclopentadiene Conductor Formula A _L SiR compound represented by the _4-L, such as a compound or dimethylsilyl bis cyclopentadiene bonded through an alkylene group, dimethylethoxy silanol of the components (4), diphenyl-tert-butoxy silanol or methyl Alkoxysilanol compounds such as diethoxysilanol, and methylaluminoxane among the components (5).

The following combinations are mentioned as one of the other suitable combinations. A tetraalkylzirconium compound such as tetramethylzirconium or a tetraaralkylzirconium compound such as tetrabenzylzirconium in the component (1), and a trialkyl such as triethylaluminum, triisobutylaluminum, trihexylaluminum or tridecylaluminum in the component (2). Aluminum compounds or halogen-containing alkylaluminum compounds such as diethylaluminum chloride or ethylaluminum dichloride, indene derivatives such as indene, methylindene or trimethylsilylindene among components (3); cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene Or cyclo such as trimethylsilylcyclopentadiene Ntajien derivatives; bisindenylethane or indene derivative or cyclopentadiene derivative such as isopropyl bis cyclopentadiene represented by the general formula A _L SiR _4-L, such as a compound or dimethylsilyl bis cyclopentadiene bonded through an alkylene group Compound,
Disilanol compounds such as dimethyldisilanol, diphenyldisilanol or methylethyldisilanol among the components (4), and methylaluminoxane among the components (5).

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 and the like are included. The cyclic olefin is usually copolymerized with the above-mentioned α-olefin, and in this case, the amount of the cyclic olefin is 50 mol% or less of the copolymer, usually 1 to 50 mol%, preferably 2 to 50 mol. It is in the range of%.

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%.

The styrene analogs that can be used in the present invention are styrene and styrene derivatives, and examples of the derivatives include 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 also be suitably used in the case where a homopolymer or copolymer of olefins is further polymerized with a polar monomer to modify the homopolymer or copolymer. Examples of polar monomers include unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, monomethyl maleate, diethyl fumarate, and dimethyl itaconate. it can. The polar monomer content of the modified copolymer is usually 0.1 to 10 mol%, preferably 0.2 to
It is in the range of 2 mol%.

The polymerization reaction can be carried out by slurry polymerization, solution polymerization or gas phase polymerization in the presence of the catalyst component and promoter component described above. In particular, slurry polymerization or gas phase polymerization is preferable, and in a state where oxygen, water and the like are substantially cut off, hexane, aliphatic hydrocarbons such as heptane, aromatic hydrocarbons 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. Further, using the catalyst of the present invention,
It is possible to carry out a multi-step polymerization reaction of two steps or more with different polymerization conditions such as hydrogen concentration and polymerization temperature without any trouble.

[0078]

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. Modified organoaluminum compound (methylaluminoxane)
Preparation of 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 suspended with 50 ml of toluene. 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 Thereafter, the reaction product was filtered to remove toluene in the liquid containing the reaction product, and 4 g of white crystalline methylaluminoxane (MAO) was obtained.
Got The physical properties of the polymers obtained in Examples and Comparative Examples were evaluated by the following methods. Melt Flow Rate (MI) ASTM D 1238-57T 190 ° C, 2.16
It was measured based on the kg load.

The density was measured according to ASTM D 1505-68. Melting point measurement by differential 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,
Then, the melting point was measured by cooling to 0 ° C. at 10 ° C./min, holding at 0 ° C. for 10 minutes, and then raising the temperature at 10 ° C./min. Measurement of Mw / Mn Using a 150C type GPC device manufactured by Waters Co., a column Toyo Soda GMH-6, a solvent O-dichlorobenzene, a temperature of 135 ° C., and a flow rate of 1.0 ml / min were measured. Mn was determined. Temperature rising elution fractionation (Temperature Risi
ng Elution Fractionation [Below
Measurement by TREF]): The obtained olefin (co) polymer was dissolved in o-dichlorobenzene and then cooled to form a polymer layer on diatomaceous earth, which was continuously heated to elute. The components were detected continuously.

Measurement of degree of branching Using an NMR apparatus manufactured by JEOL Ltd., by ¹³ C-NMR, solvent ODCB / deuterated benzene, measurement temperature: 120
The butene-1 concentration (pieces / 1000C) was measured at ° C, and this was taken as the degree of branching.

Example 1 Purified toluene 1 in a 300 cc three neck flask under N _2.
00 ml was added, followed by zirconium tetranormal butoxide 3.8 g, indene 9.3 g and (C
H ₃ ) ₃ Si (OH) 14.4 g was added, and the mixture was stirred at room temperature for 30 minutes, and then slowly added with 31 ml of triethylaluminum.
Was added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst component of the present invention. A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added, 1 mg of Zr of the catalyst component solution and 1 ml of a methylaluminoxane 1 mol / l solution were added, and the mixture was stirred under stirring 60
Heated to ° C. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was added at 9 kgf /
The polymerization was initiated by squeezing so that the pressure became cm ^2, and the total pressure was 9 kgf / c while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05).
Polymerization was carried out for 1 hour while maintaining m ² . After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 221 g of a white polymer. The catalyst efficiency is 221 kg / gZr.
and the MI of the obtained polymer is 0.9 g / 10 m
in, density 0.9223 g / cm ³ , melting point 114.
It was 6 ° C.

Example 2 Toluene 5 purified in a 100 cc three neck flask under N _2.
0 ml was added, then 0.3 g of zirconium tetraisopropoxide, 0.53 g of cyclopentadiene and 2.7 g of (Ph) ₃ Si (OH) 2 were added, and after stirring at room temperature for 30 minutes, 4 m of triisobutylaluminum was gradually added.
1 was added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst component of the present invention. N
₂ After introducing 2 mg as Zr of the above catalyst component solution into a 50 cc flask, methylaluminoxane 1 mol /
2.2 ml of the 1 solution was added and stirred at room temperature for 30 minutes to obtain a reaction solution containing the catalyst of the present invention. Polymerization was carried out under the polymerization conditions of Example 1 by adding 1 mg as the Zr component of the above catalyst component solution. 230 g of white polymer obtained after completion of polymerization
was gotten. The catalyst efficiency was 230 kg / gZr · h, the MI of the obtained polymer was 5 g / 10 min, the density was 0.9219 g / cm ³ , and the melting point was 114.4 ° C.

Example 3 10 ml of purified toluene in a 100 cc three-necked flask
And then 0.38 g of zirconium tetra-normal butoxide and 1,3 dimethylcyclopentadiene.
74 g and (CH ₃ ) ₂ PhSi (OH) 1.5 g were added and stirred at room temperature for 30 minutes, then 6.2 ml of trihexylaluminum was gradually added dropwise at room temperature to give a reaction solution containing the catalyst component of the present invention. Got Further, after stirring the above catalyst component solution at room temperature for 30 minutes, methylaluminoxane 1mo
50 ml of the 1 / l solution was added and stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst of the present invention. Polymerization was carried out under the polymerization conditions of Example 1 by adding 1 mg as the Zr component of the above catalyst solution. The white polymer obtained after the polymerization was 150
g was obtained. The catalyst efficiency was 150 kg / gZr · h, and the MI of the obtained polymer was 0.05 g / 10 mi.
n, density 0.9231 g / cm ³ , melting point 113.8
It was ℃.

Comparative Example 1 Toluene 1 purified in a 300 cc three neck flask under N _2.
00 ml was added, then 3.8 g of zirconium tetra-normal butoxide and 9.3 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, and then gradually added with triethylaluminum.
1 ml was added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution. A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added, and further 1 mg of Zr of the above catalyst component solution and 1 mol / l of methylaluminoxane were added.
1 ml of the solution was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / While continuously supplying an ethylene molar ratio of 0.05), the total pressure was maintained at 9 kgf / cm ² and polymerization was carried out for 1 hour. After the polymerization is completed, the surplus mixed gas is discharged,
After cooling and removing the salt, 152 g of a white polymer was obtained.
The catalyst efficiency was 152 kg / gZr · h, the MI of the obtained polymer was 1.5 g / 10 min, and the density was 0.92.
The melting point was 21 g / cm ³ and the melting point was 114.9 ° C.

Example 4 Purified Toluene 1 in 500 cc three neck flask under N ₂
00 ml was added, followed by 3.4 g of titanium tetra-normal butoxide, 13.8 g of 1,2,4-trimethylsilylcyclopentadiene and (CH ₃ ) Si (O).
H) (OC ₂ H ₇ ) ₂ (1.7 g) was added, and the mixture was stirred at room temperature for 30 minutes, and then gradually added to a hexane solution of butyllithium (1.
113 ml of 6 mol / l) was added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst component of the present invention. A stainless steel autoclave with a capacity of 3 L equipped with a stirrer was purged with nitrogen, 250 g of dried salt was added, 1 mg of Ti of the above catalyst component solution and 4 ml of a methylaluminoxane 1 mol / l solution were added, and the mixture was heated to 40 ° C. with stirring. did. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.2) was introduced so as to be 9 kgf / cm ² to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / butene-1 / While continuously supplying ethylene molar ratio 0.10), the total pressure was maintained at 9 kgf / cm ² and polymerization was carried out for 1 hour. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the common salt was removed to obtain 108 g of a white polymer. The catalyst efficiency was 108 kg / gTi · h, the MI of the obtained polymer was 3.5 g / 10 min, and the density was 0.9123 g /
It had a cm ³ and a melting point of 90.4 ° C.

Example 5 10 ml of purified toluene in a 100 cc three-necked flask
Then, 0.38 g of zirconium tetranormal butoxide, 0.75 g of trimethylsilylindene,
_{(I-C 3 H 7)} 2 Si (OH) 2 1.2g and the mixture was stirred at room temperature for 30 minutes, gradually heptane dibutylmagnesium solution (1mol / l) 18.0ml was added dropwise at room temperature, the A reaction solution containing the catalyst component of the invention was obtained. Further, the catalyst component solution was stirred at room temperature for 30 minutes, 50 ml of a methylaluminoxane 1 mol / l solution was added, and the mixture was stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst of the present invention. Polymerization was carried out under the polymerization conditions of Example 1 by adding 1 mg as the Zr component of the above catalyst. After the completion of the polymerization, 93 g of the white polymer obtained was obtained. Catalyst efficiency is 93 kg / g
Zr · h, the MI of the obtained polymer is 0.2 g /
10 min, density 0.9331 g / cm ³ , melting point 1
It was 15.6 ° C.

Example 6 10 ml of purified toluene in a 100 cc three-necked flask
And then 0.47 g of hafnium tetranormal butoxide, 0.68 g of methylcyclopentadiene,
Add 0.4 g of (CyH) ₃ Si (OH), and add 30 at room temperature.
After stirring for a minute, 1.0 ml of diethylaluminum chloride was gradually added dropwise at room temperature to obtain a reaction solution containing the catalyst component of the present invention. Further, the above catalyst component solution is allowed to stand at room temperature for 3
After stirring for 0 minutes, 100 ml of a methylaluminoxane 1 mol / l solution was added and stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst of the present invention. Polymerization was carried out under the polymerization conditions of Example 1 by adding 1 mg as the Hf component of the above catalyst solution. After the polymerization was completed, 44 g of the white polymer was obtained. The catalyst efficiency was 44 kg / gHf · h, the MI of the obtained polymer was 0.01 g / 10 min, and the density was 0.1.
It was 9300 g / cm ³ and the melting point was 115.5 ° C.

Example 7 Purified Toluene 1 in a 300 cc three neck flask under N _2.
00 ml was added, followed by zirconium tetranormal butoxide 3.8 g, indene 9.3 g and (t-C
2.2 g of ₄ H ₉ ) ₃ Si (OH) was added, and the mixture was stirred at room temperature for 30 minutes, and then gradually added to triisobutylaluminum 46.
ml was added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst component of the present invention.
A 3 L capacity stainless steel autoclave equipped with a stirrer was purged with nitrogen, 500 ml of dry toluene was added, 1 mg of Zr of the catalyst component solution and 1 ml of a methylaluminoxane 1 mol / l solution were added, and the mixture was heated to 60 ° C. with stirring. did. Then ethylene 6kgf /
to initiate the polymerization by Harikon so cm ^2, and while continuously feeding ethylene to maintain the total pressure at 6 kgf / cm ^2, was carried out for 15 minutes polymerization. After the completion of the polymerization, the excess mixed gas was discharged, a large amount of methanol was immediately added to stop the polymerization, the mixture was decalcified using an ethanol-hydrochloric acid solution, filtered, and toluene was removed to obtain 113 g of a white polymer. The catalyst efficiency is 452 kg / gZr · h, the MI of the obtained polymer is 0.6 g / 10 min, and the density is 0.9503 g.
/ Cm ³ , melting point 134.8 ° C.

Comparative Example 2 Toluene 1 purified in a 300 cc three neck flask under N _2.
00 ml was added, then 3.8 g of zirconium tetranormal butoxide and 9.3 g of indene were added, and after stirring at room temperature for 30 minutes, 46 ml of triisobutylaluminum was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution. Volume 3 with stirrer
The L autoclave made of stainless steel was purged with nitrogen, 500 ml of dried toluene was added, 1 mg of Zr of the catalyst component solution and 1 ml of a methylaluminoxane 1 mol / l solution were further added, and the mixture was heated to 60 ° C. with stirring. Then, ethylene was introduced so as to be 6 kgf / cm ² to start the polymerization, and while continuously supplying ethylene, the total pressure was maintained at 6 kgf / cm ² , and the polymerization was performed for 15 minutes. After the completion of the polymerization, the excess mixed gas was discharged, a large amount of methanol was immediately added to stop the polymerization, the mixture was decalcified using an ethanol-hydrochloric acid solution, filtered, and toluene was removed to obtain 72 g of a white polymer. Catalytic efficiency is 288kg / gZ
r · h, MI of the obtained polymer is 0.3 g / 1
0 min, density 0.9498 g / cm ³ , melting point 13
It was 5.2 ° C.

Example 8 Toluene 1 purified in a 300 cc three neck flask under N _2.
00 ml was added, followed by zirconium tetratert-butoxide 3.8 g and bisindenylethane 21 g.
And (Ph) ₃ Si (OH) 28 g were added and
After stirring for 0 minutes, 19 ml of diethylaluminum ethoxide was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst component of the present invention. A 3 L stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and dried toluene 5
00 ml was added, and further 1 mg as Zr of the above catalyst component solution, 1 m of methylaluminoxane 1 mol / l solution
1 was added and heated to 60 ° C. with stirring. Then mixed gas of ethylene and propylene (propylene / ethylene molar ratio
0.10) was charged to 9 kgf / cm ² to start the polymerization, and while the mixed gas of ethylene and propylene (propylene / ethylene molar ratio 0.07) was continuously supplied, the total pressure was 9 kgf / cm 2. ^It was maintained at ² and polymerized for 15 minutes. After the polymerization was completed, the excess mixed gas was discharged, and a large amount of methanol was immediately added to stop the polymerization, and ethanol-
After deashing with a hydrochloric acid solution and filtration, toluene was removed to obtain 87 g of a white polymer. Catalyst efficiency is 348kg / g
Zr · h, MI of the obtained polymer is 3.5 g /
10 min, density 0.9175 g / cm ³ , melting point 1
It was 06.3 ° C.

Example 9 Purified benzene 1 in 300 cc three neck flask under N ₂
00 ml was added, followed by 4.0 g of zirconium benzyltrinormal butoxide and (CH ₃ ) ₃ Si (O
H) (14.4 g) was added and the mixture was stirred at 80 ° C. for 3 hours, then indene (9.3 g) was added, and 70 ml of trihexylaluminum was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst component of the present invention. A stainless steel autoclave with a volume of 3 L equipped with a stirrer was replaced with nitrogen, and dried salt 200 g
And 1 mg as Zr of the above catalyst component solution,
1 ml of a 1 mol / l solution of methylaluminoxane was added, and the mixture was heated to 60 ° C. with stirring. Then ethylene and butene
1 mixed gas (butene-1 / ethylene molar ratio 0.25)
To 9 kgf / cm ² to start the polymerization, and continuously supply a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.05) while keeping the total pressure at 9 kgf / cm. ^It was maintained at ² and polymerized for 1 hour. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 201 g of a white polymer. Catalyst efficiency is 201k
g / gZr · h, and the MI of the obtained polymer was 1.
The melting point was 2 g / 10 min, the density was 0.9188 g / cm ³ , and the melting point was 109.9 ° C.

Example 10 Toluene 5 purified in a 100 cc three neck flask under N _2.
0 ml was added, then 0.23 g of zirconium tetrachloride,
0.6 g of (Ph) ₃ Si (OH) and 0.88 g of 1,2,4 trimethylcyclopentadiene were added, and the mixture was stirred at room temperature for 3 hours.
After stirring for 0 minutes, 4 ml of triisobutylaluminum was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst component of the present invention. Zr of the above catalyst component solution in a 50 cc flask under N _2.
After introducing 2 mg as a product, methylaluminoxane 1 m
2.2 ml of the ol / l solution was added and stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst of the present invention. Polymerization was carried out under the polymerization conditions of Example 1 by adding 1 mg as the Zr component of the above catalyst component solution. After the polymerization was completed, 140 g of a white polymer was obtained. Catalyst efficiency is 140kg / gZr
-H, MI of the obtained polymer is 53 g / 10 m
in, density 0.9233 g / cm ³ , melting point 115.
It was 4 ° C.

Example 11 Toluene 5 purified in a 100 cc three neck flask under N ₂
0 ml was added, then 0.3 g of zirconium tetraisopropoxide and 0.53 g of cyclopentadiene were added, and after stirring at room temperature for 30 minutes, 4 ml of triisobutylaluminum was gradually added dropwise at room temperature. Further, 2.8 g of (Ph) ₃ Si (OH) 2 was added to this solution and stirred at room temperature for 4 hours to obtain a reaction solution containing the catalyst component of the present invention.
After introducing 2 mg of the above catalyst component solution as Zr into a 50 cc flask under N ₂ , methylaluminoxane 1 mo was added.
2.2 ml of 1 / l solution was added and stirred at room temperature for 30 minutes,
A reaction solution containing the catalyst of the present invention was obtained. Polymerization was carried out under the polymerization conditions of Example 1 by adding 1 mg as the Zr component of the above catalyst component solution. The white polymer obtained after the polymerization was 1
75 g were obtained. Catalyst efficiency is 175kg / gZr · h
And the MI of the obtained polymer was 2.2 g / 10 mi.
n, density 0.9284 g / cm ³ , melting point 111.2
It was ℃.

Example 12 Toluene 5 purified in a 100 cc three neck flask under N _2.
0 ml was added, and then cyclopentadiene 0.53 g,
After 0.6 g of (Ph) ₃ Si (OH) was added and stirred at room temperature for 30 minutes, 4 ml of triisobutylaluminum was gradually added.
Was added dropwise at room temperature. Thereafter, 0.3 g of zirconium triethoxy chloride was added, and this solution was further stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst component of the present invention. Z the above catalyst component solution into a 50 cc flask under N _2.
After introducing 2 mg as r, methylaluminoxane 1
2.2 ml of mol / l solution was added and stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst of the present invention. Polymerization was carried out under the polymerization conditions of Example 1 by adding 1 mg as the Zr component of the above catalyst solution. The white polymer obtained after the polymerization was 1
77 g were obtained. The catalyst efficiency is 177kg / gZr · h
And the MI of the obtained polymer was 16 g / 10 mi.
n, density 0.9313 g / cm ³ , melting point 112.2
It was ℃.

Example 13 Toluene 1 purified in a 300 cc three neck flask under N _2.
00 ml was added, followed by 4.6 g of tetrabenzyl zirconium, 9.3 g of indene, and (Ph) ₃ Si.
After adding (OH) 22 g and stirring at 111 ° C. for 4 hours,
56 ml of trihexylaluminum was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst component of the present invention. A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, and 200 g of dried salt was added, and further 1 mg as Zr of the above catalyst component solution, methylaluminoxane 1
1 ml of mol / l solution was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-
1 / ethylene molar ratio of 0.25) was added so as to be 9 kgf / cm ² to start polymerization, and ethylene and butene-
1 mixed gas (butene-1 / ethylene molar ratio 0.05)
Was continuously supplied, the total pressure was maintained at 9 kgf / cm ² , and polymerization was carried out for 1 hour. After the polymerization was completed, the excess mixed gas was discharged, the mixture was cooled and the salt was removed to obtain 195 g of a white polymer. The catalyst efficiency is 195 kg / gZr · h,
The MI of the obtained polymer was 0.8 g / 10 min, the density was 0.9230 g / cm ³ , and the melting point was 110.4 ° C.

Example 14 Purified benzene 1 in 300 cc three neck flask under N ₂
00 ml was added, followed by 4.0 g of zirconium benzyltrinormal butoxide and (CH ₃ ) ₃ Si (O
H) (14.4 g) was added and the mixture was stirred at 80 ° C. for 3 hours, then indene (9.3 g) was added, and 70 ml of trihexylaluminum was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution containing the catalyst component of the present invention. A toluene-dried 50-liter stainless steel autoclave equipped with a stirrer and replaced with nitrogen.
0 ml was added, and 1 was added as Zr of the above catalyst component solution.
18 mg of methyl aluminoxane 1 mol / l solution
1 was added and kept at 20 ° C. with stirring. Then, propylene was charged so as to have a pressure of 3.5 kgf / cm ² to start the polymerization, and while the propylene was continuously supplied, the total pressure was 3.5.
Polymerization was carried out for 1 hour while maintaining the pressure at kgf / cm ² . After the completion of the polymerization, a surplus mixed gas was discharged, a large amount of methanol was immediately added to stop the polymerization, deashing was performed using an ethanol-hydrochloric acid solution, filtration was performed, and then toluene was removed to obtain a white polymer 153.
g was obtained. The catalyst efficiency was 153 kg / gZr · h, and the melting point of the obtained polymer was 141.1 ° C.

Comparative Example 3 00 ml of purified toluene in a 100 cc three-necked flask
And then 0.38 g of zirconium tetra-normal butoxide and 1,3 dimethylcyclopentadiene.
74 g, (CH ₃ ) ₂ (Ph) Si (OH) 0.15 g
Was added and stirred at room temperature for 30 minutes, 50 ml of a methylaluminoxane 1 mol / l solution was added, and the mixture was stirred at room temperature for 1 hour to obtain a reaction solution. 1 as Zr of the above catalyst solution
Polymerization was carried out under the polymerization conditions of Example 1 by adding mg. The white polymer obtained after the completion of the polymerization was 65 g. The catalyst efficiency was 65 kg / gZr · h, the MI of the obtained polymer was 6.3 g / 10 min, and the density was 0.9291 g /
It was cm ³ , and the melting point was 114.7 ° C.

Comparative Example 4 Toluene 5 purified in a 100 cc three neck flask under N ₂
0 ml was added, followed by 0.3 g of zirconium tetraisopropoxide, and (Ph) ₃ Si (OH) 2.7.
After adding g, the mixture was stirred at room temperature for 30 minutes, and then 4 ml of triisobutylaluminum was gradually added dropwise at room temperature. Further, this solution was stirred at room temperature for 1 hour to obtain a reaction solution. N ₂ 2 under 50cc flask above catalyst component solution as Zr
After introducing mg, methyl aluminoxane 1 mol / l
2.2 ml of the solution was added and stirred at room temperature for 30 minutes. Polymerization was carried out under the polymerization conditions of Example 1 by adding 1 mg as the Zr component of the above catalyst solution. The white polymer obtained after the completion of the polymerization was 2 g. The catalyst efficiency was 2 kg / gZr · h, the MI of the obtained polymer was 1.2 g / 10 min,
The density was 0.9355 g / cm ³ and the melting point was 118.2 ° C.

[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 general formula R ¹ _a R ² _b R ³ _c Si (OH) _d. (OR ⁴ )
A compound represented by _{4- (a + b + c + d)} (in the formula,
R ¹ , R ² and R ³ are individually hydrogen, halogen or 1 carbon atom.
To 24 hydrocarbon groups, R ⁴ represents a hydrocarbon group having 1 to 24 carbon atoms, and a, b, c and d are 0 ≦ a <4 and 0 ≦ b <.
4, 0 ≦ c <4, 0 <d <4 and 0 <a + b + c <
4, 1 <a + b + c + d ≦ 4), which are obtained by bringing them into contact with each other. 2. (1) The 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 general formula R ¹ _a R ² _b R ³ _c Si (OH) _d. (OR ⁴ )
A compound represented by _{4- (a + b + c + d)} (in the formula,
R ¹ , R ² and R ³ are individually hydrogen, halogen or 1 carbon atom.
To 24 hydrocarbon groups, R ⁴ represents a hydrocarbon group having 1 to 24 carbon atoms, and a, b, c and d are 0 ≦ a <4 and 0 ≦ b <.
4, 0 ≦ c <4, 0 <d <4 and 0 <a + b + c <
4, 1 <a + b + c + d ≦ 4), and (5) Al obtained by reacting an organoaluminum compound with water.
A catalyst for olefin polymerization obtained by bringing modified organoaluminum compounds containing -O-Al bond into contact with each other. 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.