JP3469333B2 - Catalyst component for polymerization of olefins - Google Patents

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. Here, the olefin polymer is a generic term for a homopolymer and a copolymer of olefins.

[0002]

2. Description of the Related Art A catalyst comprising a zirconium compound and an aluminoxane has recently 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 crosslinked conjugated cycloalkadienyl groups. However, the use of hafnium as the transition metal also has the drawback that the yield of the obtained polymer is low.

[0004]

The object of the present invention is to produce a high molecular weight olefin polymer having a relatively wide molecular weight distribution in a high yield, and to produce a modified organoaluminum compound such as methylaluminoxane. It is to provide a catalyst component and a catalyst that can be used in a small amount.

[0005]

That is, the present invention is as follows.
(1) In formula _{MeR p (OR ') q X} 4-p-q compounds represented by (wherein, R and R' are independently 1 to 24 carbon atoms
Hydrocarbon group, X is a halogen atom, Me is Zr, Ti or Hf, and p and q are 0 ≦ p ≦ 4 and 0 ≦, respectively.
q ≦ 4, 0 ≦ p + q ≦ 4), (2) at least one metal hydride compound selected from the following general formulas 1 to 3 general formula 1: MeH _m R _3-m general formula 2: Me ′ [MeH _p R _q (O
R) _4-pq ] _z General formula 3:

[0006]

[Chemical 3]

(In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, Me is an element of Group 13 of the periodic table, Me 'is an element of Group 1, 2 or 12 of the periodic table, When two or more Rs are present in one molecule, Rs may be the same or different, z is the valence of Me ′, and m, n, p and q are 0 <m ≦ 3 and 0 ≦ n, respectively. ≦ 4, 1 ≦ p ≦ 4, 0 ≦ q ≦ 3
In addition, 1 ≦ p + q ≦ 4. ), (3) an organic compound having a cyclopentadiene structure , and (4) a catalyst component for olefin polymerization obtained by bringing a compound containing a carbon-halogen bond into contact with each other.

The present invention also provides (1) the general formula MeR _p (O
R ′) _q X _4-p-q (wherein R and R ′ are independently a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom, Me is Zr, Ti or Hf. , P and q are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, and 0 ≦ p + q ≦ 4, respectively, and (2) at least one metal hydride compound selected from the following general formulas 1 to 3 MeH _m R _3-m general formula 2: Me _'[MeH p _R q (O
R) _4-pq ] _z General formula 3:

[0009]

[Chemical 4]

(In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, Me is an element of Group 13 of the periodic table, Me 'is an element of Group 1, Group 2 or Group 12 of the periodic table, When two or more Rs are present in one molecule, Rs may be the same or different, z is the valence of Me ′, and m, n, p and q are 0 <m ≦ 3 and 0 ≦ n, respectively. ≦ 4, 1 ≦ p ≦ 4, 0 ≦ q ≦ 3
In addition, 1 ≦ p + q ≦ 4. ), (3) an organic compound having a cyclopentadiene structure , (4) a carbon-halogen bond-containing compound, and (5) an olefin obtained by bringing the modified organoaluminum compound containing an Al—O—Al bond into contact with each other. It relates to a polymerization catalyst.

The olefin polymerization catalyst of the present invention has a high catalytic efficiency and can reduce the amount of the modified organoaluminum compound such as aluminoxane used. The produced polymer has a high molecular weight and a relatively wide molecular weight distribution. As for the copolymer, a polymer having a narrow composition distribution can be produced. Further, when molding the polymer produced using the olefins polymerization catalyst of the present invention, neither the inflation method nor the T-die method is sticky, high-speed molding is possible, and the moldability is extremely good. Is. Furthermore, the formed film may be T-shaped by the inflation method.
The die method is also excellent in transparency, anti-blocking property and strength, and particularly the inflation method is excellent in mouth opening property.

The present invention will be described in detail below. First, the compound represented by the general formula MeR _p (OR ′) _q X _4- pq of the component (1) will be described. In the formula, R and R'represent a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 and more preferably 1 to 8, and the hydrocarbon group may be a methyl group, an ethyl group, Propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tert-butyl group, cyclobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, hebutyl group, octyl group , Alkyl groups such as decyl group and dodecyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; benzyl group, trityl group, phenethyl group Group, styryl group, benzhydryl group, phenylbutyl group, phenylpropyl group, Examples thereof include aralkyl groups such as neophyll groups. These may have branches. X is a halogen atom of fluorine, iodine, chlorine and bromine, Me is Zr, Ti
Alternatively, it represents Hf, and is preferably Zr. p and q are 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, and 0 ≦ p + q ≦ 4, and preferably 0 <p + q ≦ 4.

Specific examples suitable as the component (1) include:
Tetramethylzirconium, tetraethylzirconium, tetrapropylzirconium, tetra-n-butylzirconium, tetrapentylzirconium, tetraphenylzirconium, tetratolylzirconium, tetrabenzylzirconium, tetraallylzirconium, tetraneophyllzirconium, tetramethoxyzirconium, tetraethoxyzirconium, Tetrapropoxyzirconium, tetrabutoxyzirconium, tetrapentyloxyzirconium, tetraphenoxyzirconium, 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, mofuphenyltrichlorozirconium,
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, trineophylmonobromozirconium, 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,

Trimethoxymonobromozirconium, dimethoxydibromozirconium, monomethoxytribromozirconium, triethoxymonobromozirconium, diethoxydibromozirconium, monoethoxytribromozirconium, tripropoxymonobromozirconium, dipropoxydibromozirconium, monopropoxytri Bromozirconium, tri-n-butoxymonobromozirconium, di-n-butoxydibromozirconium, mono-n-butoxytribromozirconium, tripentyloxymonobromozirconium, dipentyloxydibromozirconium, monopentyloxytribromozirconium, triphenoxymonobromozirconium , Diphenoxydibromozirconium, monophenoxytribromodiene Conium, tritolyloxymonobromozirconium, ditolyloxydibromozirconium, monotolyloxytribromozirconium, tribenzyloxymonobromozirconium, dibenzyloxydibromozirconium, monobenzyloxytribromozirconium, triallyloxymonobromozirconium, diallyl Oxydibromozirconium, monoallyloxytribromozirconium, trineophylloxymonobromozirconium, dyneophyloxydibromozirconium, mononeophylloxytribromozirconium,

Tetraiodo zirconium, trimethyl monoiodo zirconium, triethyl monoiodo zirconium, tripropyl monoiodo zirconium, 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,

Trimethoxymonoiodozirconium, dimethoxydiiodozirconium, monomethoxytriiodozirconium, triethoxymonoiodozirconium, diethoxydiiodozirconium, monoethoxytriiodozirconium, tripropoxymonoiodozirconium, dipropoxydiiodozirconium, Monopropoxytriiodozirconium, tri-n-butoxymonoiodozirconium, di-n-butoxydiiodozirconium, mono-n-butoxytriiodozirconium, tripentyloxymonoiodozirconium, dipentyloxydiiodozirconium, monopentyloxytriiodozirconium, Triphenoxy monoiodo zirconium, diphenoxy diiodo zirconium, monophenoxy triiodo di Conium, tritolyloxymonoiodozirconium, ditolyloxydiiodozirconium, monotolyloxytriiodozirconium, tribenzyloxymonoiodozirconium, dibenzyloxydiiodozirconium, monobenzyloxytriiodozirconium, triallyloxymonoiodozirconium , Diallyloxydiiodozirconium, monoallyloxytriiodozirconium, trineophylloxymonoiodozirconium, dineophylloxydiiodozirconium, mononeophylloxytriiodozirconium,

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 neophyll titanium, 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, trimethoxymonobromotitanium, Dimethoxydibromotitanium, monomethoxytribromotitanium, triethoxymonobromotitanium, di Toxidibromotitanium, monoethoxytribromotitanium, tripropoxymonobromotitanium, dipropoxydibromotitanium, monopropoxytribromotitanium, tri-n-butoxymonobromotitanium, di-n-butoxydibromotitanium, 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,
Trimethoxy monoiodotitanium, dimethoxydiiodotitanium, monomethoxytriiodotitanium, triethoxymonoiodotitanium, diethoxydiiodotitanium, monoethoxytriiodotitanium, tripropoxymonoiodotitanium, dipropoxydiiodotitanium, monopropoxytri Iodo titanium,
Tri-n-butoxymonoiodotitanium, di-n-butoxydiiodotitanium, mono-n-butoxytriiodotitanium, tripentyloxymonoiodotitanium,
Dipentyloxydiiodotitanium, Monopentyloxytriiodotitanium, Triphenoxymonoiodotitanium, Diphenoxydiiodotitanium, Monophenoxytriiodotitanium, Tritolyloxymonoiodotitanium, Ditolyloxydiiodotitanium, Monotolyloxytriiodo Titanium, tribenzyloxymonoiodotitanium, dibenzyloxydiiodotitanium,

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, trin-butoxymonochlorohafnium, din-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, trimethoxymonobromohafnium, dimethoxydibromohafnium, Monomethoxytribromohafnium, triethoxymonobromohafnium, diethoxydibromohafnium, monoethoxytribromohafnium, tripropoxymonobromohafnium, dipropoxydibromohafnium, monopropoxytribromohafnium, tri-n-butoxymonobromohafnium, din
-Butoxydibromohafnium, mono-n-butoxytribromohafnium, tripentyloxymonobromohafnium, dipentyloxydibromohafnium, monopentyloxytribromohafnium, triphenoxymonobromohafnium, diethoxydibromohafnium,
Monophenoxytribromohafnium, tritolyloxymonobromohafnium, ditolyloxydibromohafnium, monotolyloxytribromohafnium, tribenzyloxymonobromohafnium, dibenzyloxydibromohafnium, monobenzyloxytribromohafnium, tetraiodohafnium , Trimethylmonoiodohafnium, triethylmonoiodohafnium,
Tripropylmonoiodohafnium, tri-n-butylmonoiodohafnium, tribenzylmonoiodohafnium, dimethyldiiodohafnium, diethyldiiodohafnium,

Di-n-butyldiiodohafnium, dibenzyldiiodohafnium, monomethyltriiodohafnium, monoethyltriiodohafnium, mono-n-butyltriiodohafnium, monobenzyltriiodohafnium, trimethoxymonoiodohafnium, dimethoxydi Iodohafnium, monomethoxytriiodohafnium, triethoxymonoiodohafnium, diethoxydiiodohafnium, monoethoxytriiodohafnium, tripropoxymonoiodohafnium, dipropoxydiiodohafnium, monopropoxytriiodohafnium, tri-n-butoxymono Iodohafnium, di n
-Butoxydiiodohafnium, mono-n-butoxytriiodohafnium, tripentyloxymonoiodohafnium, dipentyloxydiiodohafnium, monopentyloxytriiodohafnium, triphenoxymonoiodohafnium, diphenoxydiiodohafnium, monophenoxytriiodo Hafnium, tritolyloxymonoiodohafnium, 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,
Examples include mononeophyll triethoxy hafnium, mononeophyll tripropoxy hafnium, mononeophyll tributoxy hafnium, and mononeophyll triphenoxy hafnium. Of course, in these compounds listed as specific examples of the above component (1), 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.
It is a compound represented by r (OR) ₄ . These compounds can be used as a mixture of two or more kinds.

Component (2) is at least one metal hydride compound selected from the following general formulas 1 to 3. General formula _1: MeH _{m R 3-m} General formula 2: Me _'[MeH p _R q (O
R) _4-pq ] _z General formula 3:

[0034]

[Chemical 5]

In the formula, Me represents a Group 13 element of the periodic table such as boron and aluminum. Me 'is the periodic table 1,
Indicates any of Group 2 and 12 elements, including lithium, sodium, potassium, magnesium, calcium, barium, zinc, and the like. R has 1 carbon
~ 20, preferably 1-6 hydrocarbon groups, including methyl, ethyl, propyl, iso-propyl, cyclopropyl, butyl, iso-butyl groups,
tert-butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, dodecyl group, and other alkyl groups; vinyl group, allyl group, and other alkenyl groups 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, etc. Aralkyl groups and the like. These may have branches. When two or more Rs are present in one molecule, the Rs may be the same or different. z represents the valence of Me '. m is 0
<M ≦ 3. n is 0 ≦ n ≦ 4, preferably 0 ≦ n ≦
2, more preferably 0 ≦ n ≦ 1, most preferably n =
It is 0. p and q are 1 ≦ p ≦ 4 and 0 ≦ q ≦ 3, respectively.
In addition, 1 ≦ p + q ≦ 4. M in the general formula 2
When e is boron, Me ′ is preferably sodium, lithium and zinc, and when Me is aluminum, Me ′ is preferably sodium, lithium and potassium. In the general formula 3, the substitution position of R is not particularly limited,
When n = 2, it is the 4th and 5th positions, 4th and 6th or 5th or 6th, and when n = 1, 4th or 5th.

Specific examples of the compound usable as the component (2) include aluminum hydride, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride and diiso-.
Propyl Aluminum Hydride, Dibutyl Aluminum Hydride, Diiso-Butyl Aluminum Hydride, Dihexyl Aluminum Hydride, Dicyclohexyl Aluminum Hydride, Lithium Aluminum Hydride, Sodium Aluminum Hydride, Lithium Aluminum Trimethoxy Hydride, Sodium Aluminum Trimethoxy Hydride, Lithium Aluminum Triethoxy Hydride,
Sodium aluminum triethoxy hydride, lithium aluminum tritert-butoxy hydride, sodium aluminum tritert-butoxy hydride, borane, diborane, 2,3-dimethyl-2
-Butylborane, bis (3-methyl-2-butyl) borane, dicyclohexylborane, diisopinocanphenylborane, 9-borabicyclo [3.3.1] nonane, catecholborane, lithium borohydride, sodium borohydride, zincboro Hydride, magnesium borohydride, calcium borohydride,
Barium borohydride, lithium triethylborohydride, lithium triiso-butylborohydride, potassium triiso-butylborohydride,
Sodium cyanoborohydride, potassium cyanoborohydride, catechol borane (1,3,2-benzodioxaboralol), 4-methyl-1,3,2-benzodioxaboralol, 5-methyl-1,3,3 2-benzodioxaboralol, 4,5-dimethyl-1,3
2-benzodioxaboralol, 4,6-dimethyl-
1,3,2-benzodioxaboralol, 4,7-dimethyl-1,3,2-benzodioxaboralol, 4-ethyl-1,3,2-benzodioxaboralol, 5-ethyl- 1,3,2-benzodioxaboralol, 4,5
-Diethyl-1,3,2-benzodioxaboralol,
4,6-diethyl-1,3,2-benzodioxaboralol, 4,7-diethyl-1,3,2-benzodioxaboralol, 4-propyl-1,3,2-benzodioxabora Roll, 5-propyl-1,3,2-benzodioxaboralol, 4,5-dipropyl-1,3,2-benzodioxaboralol, 4,6-dipropyl-1,
3,2-benzodioxaboralol, 4,7-dipropyl-1,3,2-benzodioxaboralol, 4,5,
6-trimethyl-1,3,2-benzodioxaboralol, 4,5,7-trimethyl-1,3,2-benzodioxaboralol, 4,5,6,7-tetramethyl-1,
3,2-benzodioxaboralol, and the like. Among them, aluminum hydride, dimethyl aluminum hydride, diethyl aluminum hydride, and di i
So-butylaluminum hydride, lithium aluminum hydride, lithium aluminum trimethoxyhydride, sodium borohydride, lithium triiso-butylborohydride, potassium triiso-butylborohydride, and the like are preferable.
Also, these may be used in combination, for example, the is
A combination of o-butyl aluminum hydride and sodium borohydride, diiso-butyl aluminum hydride and lithium aluminum hydride, lithium aluminum triethoxy hydride and sodium borohydride, lithium aluminum triethoxy hydride and lithium aluminum hydride, and the like are preferable.

As the component (3), cyclopentadiene
Organic compounds having a structure are used. Preferred ingredients
(3) has 1 or 2 or more cyclopentadiene rings.
It has a high carbon content and a total carbon number of 4 to 24, preferably 4 to 12.
A hydrocarbon compound having 1 or 2 or more cyclopentadiene rings and 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; and an alkali metal salt of these compounds (sodium Salt, lithium salt, etc.)
Included.

Incidentally, as a preferred example of the cyclic hydrocarbon compound, a compound represented by the following general formula can be mentioned.

[0039]

[Chemical 6]

In the above general formula, R ¹ , R ² , R ³ ,
R ⁴ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and any ^{two of} R ¹ , R ² , R ³ , and R ⁴ may be combined to form a cyclic hydrocarbon group. . As the hydrocarbon residue, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, alkyl group such as octyl group, aryl group such as phenyl group, methoxy group, ethoxy group, As a skeleton of the cyclic hydrocarbon group when an alkoxy group such as a propoxy group, an aryloxy group such as a phenoxy group, an aralkyl group such as a benzyl group, or any two of them jointly form a cyclic hydrocarbon group, cyclohepta is used. Triene, aryl, and condensed rings thereof are included. Suitable examples of the compound represented by the above general formula include cyclopentadiene, indene, azulene, and their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Further, a compound in which the compound represented by the above general formula is bonded (crosslinked) via an alkylene group (its carbon number is usually 2 to 8, preferably 2 to 3) is also suitably used.

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.

Specific examples of the compound usable as the component (3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene. Pentadiene, 1,3-dimethylcyclopentadiene, 1,2,
4-trimethylcyclopentadiene, 1,2,3,4-
Tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-methyl-1-indene,
Cyclopolyene or substituted cyclopolyene having 7 to 24 carbon atoms such as 4,7-dimethylindene, 4,5,6,7-tetrahydroindene , azulene, methylazulene, ethylazulene, fluorene and methylfluorene.

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 be converted into an alkylene group (the carbon number of which is usually 2-8, preferably 2
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 isopropylbiscyclopentadiene are compounds that can be used as the component (3) of the present invention.
Of course, two or more compounds can be used in combination.

The carbon-halogen bond-containing compound (component (4)), which is another essential component constituting the olefin polymerization catalyst component in the present invention, is a compound containing a carbon-halogen bond in the molecule. For more information, is one or a compound obtained by substituting two or more or all of the hydrogen with a halogen atom in an organic compound of hydrocarbon-containing, in particular the general formula R ² -R ³
_q is a carbon-halogen bond-containing compound represented by _q or R ² (A-R ³ ) _q . In the formula, q represents a number satisfying 1 ≦ q ≦ 4, preferably 1 ≦ q ≦ 3. A is -O-, -OSi
_{^{R 4 2 -, - C (}} OR 5) 2 - and -C ^(OR ₅₎ 2 O
- represents a group selected from the group consisting of, R ² is 1 to the number of carbon atoms
30 represents a halocarbon group, R ³ and R ⁴ represent a hydrogen atom, a halogen atom or a hydrocarbon residue having 1 to 30 carbon atoms, R ⁵ represents a hydrocarbon residue having 1 to 30 carbon atoms, R 3
^{When a} plurality of ³ , R ⁴ or R ⁵ are contained, they may be the same or different and R ² and R ³ may be bonded to each other to form a ring.

The halocarbon group for R ² is a hydrocarbon group in which one methylene group in the molecular chain may be replaced by an oxygen atom, and some or all of the hydrogen atoms in the molecule are fluorine atoms. , A hydrocarbon group substituted with one or more halogen atoms such as chlorine, bromine and iodine. Particularly, those substituted with one or more fluorine atoms are preferable. The hydrocarbon group usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 carbon atom.
A monovalent hydrocarbon group having 1 to 12 or a polyvalent hydrocarbon group having 2 to 4 free valences, for example,
Methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tertiary butyl group, cyclobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group , Heptyl group, octyl group, decyl group, dodecyl group, and other alkyl groups; vinyl group, allyl group, and other alkenyl groups; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group, and other aryl groups, benzyl Group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, phenylpropyl group, monovalent hydrocarbon group represented by aralkyl group such as neofil group, methylene group, ethylene group, propylene group, butylene group, etc. An alkylene group of
Arylene group; divalent hydrocarbon group represented by arylalkylene group, alkanetriyl
l) group; arenetriyl
Group; arylalkanetriyl
trivalent hydrocarbon group represented by triyl group, alkanetetrayl group; arenetetrayl group; arylalkanetetrayl group
and a tetravalent hydrocarbon group represented by ayl) group. Of course, these may have branches. The number of halogen atoms substituted in the halocarbon group is not particularly limited, and one, two or more or all hydrogen atoms may be substituted with halogen atoms. Also, its replacement position,
The three-dimensional arrangement is not particularly limited, either.
It can be arbitrarily selected.

Examples of the halogen atom in R ³ , R ⁴ and R ⁵ include fluorine, chlorine, bromine and iodine. Further, the hydrocarbon residue means a hydrocarbon group or a group in which one or more hydrogen atoms of the hydrocarbon group are substituted with arbitrary functional groups. The functional group may be represented by the general formula —OR ¹¹ (wherein R
^{And 11} represents a hydrocarbon group having 1 to 20 carbon atoms as described above or a halocarbon group), or a halogen atom such as fluorine, chlorine, bromine or iodine. Examples of the hydrocarbon group as the basic skeleton of the hydrocarbon residue include those having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.

Specific examples of the hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tert-butyl group, cyclobutyl group, pentyl group, isopentyl group, neopentyl group, Alkyl groups such as cyclopentyl group, hexyl group, 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, Aryl groups such as indenyl group and naphthyl group; benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, phenylpropyl group, aralkyl group such as neofil group, methylene group, ethylene group, propylene group, iso Propylene group, cyclopropyl Group, butylene group, isobutylene group, tert-butylene group, cyclobutylene group, pentylene group, isopentylene group, neopentylene group, cyclopentylene group, hexylene group, isohexylene group, cyclohexylene group, heptylene group, octylene group and other alkylene groups An arylene group such as a phenylene group, a mesitylene group, a tolylene group, a xylylene group, an indenylene group and a naphthylene group, and an aralkylene group such as a benzylene group, a trithylene group, a phenetylene group and a styrylene group. The compound further embodying the carbon-halogen bond-containing compound (component (4)) can be represented by the general formula:

[0052]

[Chemical 7]

R ⁶ —O—R ⁸ (general formula H) R ⁶ —O—SiR ⁸ ₃ (general formula I) R ⁶ R ⁹ C (OR ⁸ ) ₂ (general formula J) R ⁸ R ⁹ C (OR ⁶ ) (OR ⁸ ) (general formula K) R ⁶ C (OR ⁸ ) ₃ (general formula L) R ⁸ C (OR ⁶ ) (OR ⁸ ) ₂ (general formula M) R ⁶ -R ¹⁰ (general formula N ) The compound represented by these is mentioned.

Here, R ⁶ represents a halocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. The halocarbon group referred to here is a hydrocarbon group in which some or all of the hydrogen atoms in the molecule are halogen atoms such as fluorine, chlorine, bromine and iodine,
Particularly preferred is a hydrocarbon group substituted with a fluorine atom. Further, as the hydrocarbon group, specifically, a methyl group,
Ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, tert-butyl group,
Cyclobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, dodecyl group and other alkyl groups; vinyl group, allyl group and other alkenyl groups; Aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group, trityl group, phenethyl group,
Examples thereof include aralkyl groups such as styryl group, benzhydryl group, phenylbutyl group, phenylpropyl group and neophyll group. Of course, these may have branches. The number of halogen atom substitutions of the halocarbon group is not particularly limited, and the substitution position, configuration, etc. thereof are not particularly limited, and can be arbitrarily selected and used.

Specifically as R ⁶ , a fluoromethyl group,
Fluoroethyl group, fluoropropyl group, fluoroisopropyl group, fluorocyclopropyl group, fluorobutyl group, fluoroisobutyl group, fluoro-tert-butyl group, fluorocyclobutyl group, fluoropentyl group, fluoroisopentyl group, fluoroneopentyl group , A fluorocyclopentyl group, a fluorohexyl group,
Fluoroisohexyl group, fluorocyclohexyl group,
Alkyl groups such as fluoroheptyl group, fluorooctyl group, fluorophenyl group, fluorobenzyl group, fluoromesityl group, fluoroindenyl group, fluoronaphthyl group, trifluoroethyl group, hexafluoroisopropyl group, pentafluoropropyl group, perfluoropropyl group Fluorobutylethyl group, perfluoroethyl group, perfluorodecylethyl group, perfluoroethylhexyl group, perfluorobutylhexyl group, perfluorohexylhexyl group, perfluorooctylhexyl group, perfluoroisoamylethyl group, perfluoroisononylethyl group Group, perfluoroisopropylhexyl group, perfluoroisoamylhexyl group, perfluoroisoheptylhexyl group, perfluoroisononylhexyl group,

Tetrafluoropropyl group, octafluoropentyl group, dodecafluoroheptyl group, hexadecafluorononyl group, bis (trifluoromethyl) propyl group, hexafluorobutyl group, perfluorohexyliodopropyl group, perfluorooctyliodopropyl group. Group, perfluoroisoheptyl iodopropyl group, perfluoroisononyl iodopropyl group, octafluoropropyl group, perfluorobutyl group, octafluorocyclobutyl group, perfluoropentyl group, perfluorocyclopentyl group, perfluorohexyl group, perfluorohexyl group Fluorocyclohexyl group, perfluoroheptyl group, perfluorocycloheptyl group, perfluorooctyl group, perfluorocyclooctyl group, perfluorononyl group, perfluoro Clonnonyl group, perfluorodecyl group, perfluorocyclodecyl group, perfluoroundecyl group, perfluorocycloundecyl group, perfluorododecyl group, perfluorocyclododecyl group, perfluorotridecyl group, perfluorocyclotridecyl group , Perfluorotetradecyl group, perfluorocyclotetradecyl group, perfluoropentadecyl group, perfluorocyclopentadecyl group, perfluorohexadecyl group, perfluorocyclohexadecyl group, perfluoroheptadecyl group, perfluorocyclohepta Decyl group, perfluorooctadecyl group, perfluorocyclooctadecyl group, perfluorononadecyl group, perfluorocyclononadecyl group, perfluorononaeicosyl group, perfluorocycloeicosyl group, -Fluorophenyl group, perfluorobenzyl group, perfluoroxylyl group, perfluoromesitylenyl group, perfluorocumyl group, perfluoronaphthalyl group, perfluorodecalyl group, fluorodichloromethyl group, 1,1- Dichloro-1-fluoroethyl group, 1-bromo-2-fluoroethyl group, 1,1-difluoroethyl group, bromotetrafluoropropyl group, octafluorobutyl iodide group,

Pentafluorophenyl group, bromotetrafluorophenyl group, chlorotetrafluorophenyl group, tetrafluorophenyl iodide group, tetrafluorophenyl group, chlorotrifluorophenyl group, dichlorotrifluorophenyl group, bromotrifluorophenyl group, Dibromotrifluorophenyl group, trifluorophenyl group, chlorodifluorophenyl group, dichlorodifluorophenyl group, trichlorofluorophenyl group, bromodifluorophenyl group, dibromodifluorophenyl group, tribromodifluorophenyl group, difluorophenyl group, chlorofluorophenyl group , Dichlorofluorophenyl group, trichlorofluorophenyl group, tetrachlorofluorophenyl group, bromofluorophenyl group, dibromofluoro Eniru group, tri-bromo-fluorophenyl group, tetrabromo-fluorophenyl group, trifluorophenyl group, hexafluoro xylyl group, a trifluoromethyl naphthyl group, di - (trifluoromethyl)
-Naphthyl group, trifluoromethyl decalyl group, di-
(Trifluoromethyl) -decalin group,

Chloromethyl group, chloroethyl group, chloropropyl group, chloroisopropyl group, chlorocyclopropyl group, chlorobutyl group, chloroisobutyl group, chloro-tert-butyl group, chlorocyclobutyl group, chloropentyl group, chloroisopentyl group. , Chloroneopentyl group, chlorocyclopentyl group, chlorohexyl group, chloroisohexyl group, chlorocyclohexyl group, chloroheptyl group, chlorooctyl group and other alkyl groups, chlorophenyl group, chlorobenzyl group, chloromesityl group,
Chloroindenyl group, chloronaphthyl group, trichloroethyl group, hexachloroisopropyl group, pentachloropropyl group, perchlorobutylethyl group, perchloroethyl group, perchlorodecylethyl group, perchloroethylhexyl group, perchlorobutylhexyl group, Perchlorohexylhexyl group, perchlorooctylhexyl group, perchloroisoamylethyl group, perchloroisononylethyl group, perchloroisopropylhexyl group, perchloroisoamylhexyl group, perchloroisoheptylhexyl group, perchloroisononylhexyl group , Tetrachloropropyl group, octachloropentyl group, dodecachloroheptyl group, hexadecachlorononyl group, bis (trichloromethyl) propyl group, hexachlorobutyl group, octachloropropyl group , Perchlorobutyl group, octachlorocyclobutyl group, perchloropentyl group, perchlorocyclopentyl group, perchlorohexyl group, perchlorocyclohexyl group, perchloroheptyl group, perchlorocycloheptyl group, perchlorooctyl group, perchloro Cyclooctyl group, perchlorononyl group, perchlorocyclononyl group, perchlorodecyl group, perchlorocyclodecyl group, perchloroundecyl group, perchlorocycloundecyl group, perchlorododecyl group, perchlorocyclododecyl group, Perchlorotridecyl group, perchlorocyclotridecyl group, perchlorotetradecyl group, perchlorocyclotetradecyl group, perchloropentadecyl group, perchlorocyclopentadecyl group, perchlorohexadecyl group, perchlorocyclohexa Syl group, perchloroheptadecyl group, perchlorocycloheptadecyl group, perchlorooctadecyl group, perchlorocyclooctadecyl group, perchlorononadecyl group, perchlorocyclononadecyl group, perchlorononaeicosyl group, perchlorocyclo Eicosyl group, perchlorophenyl group, perchlorobenzyl group, perchloroxylyl group, perchloromesitylenyl group, perchlorocumyl group, perchloronaphthalyl group, perchlorodecalyl group, 1,1-dichloroethyl group, penta Chlorophenyl group, tetrachlorophenyl group, trichlorophenyl group, dichlorophenyl group, hexachloroxylyl group, trichloromethylnaphthyl group,
Di- (trichloromethyl) -naphthyl group, trichloromethyldecalyl group, di- (trichloromethyl) -decalyl group,

Bromomethyl group, bromoethyl group, bromopropyl group, bromoisopropyl group, bromocyclopropyl group, bromobutyl group, bromoisobutyl group, bromo-tertiary butyl group, bromocyclobutyl group, bromopentyl group, bromoisopentyl group, Bromoneopentyl group,
Alkyl groups such as bromocyclopentyl group, bromohexyl group, bromoisohexyl group, bromocyclohexyl group, bromoheptyl group, bromooctyl group, bromophenyl group, bromobenzyl group, bromomesityl group, bromoindenyl group, bromonaphthyl group, tribromonaphthyl group Bromoethyl group, hexabromoisopropyl group, pentabromopropyl group, perbromobutylethyl group, perbromoethyl group, perbromodecylethyl group, perbromoethylhexyl group, perbromobutylhexyl group, perbromohexylhexyl group, perbromo Octylhexyl group, perbromoisoamylethyl group, perbromoisononylethyl group, perbromoisopropylhexyl group, perbromoisoamylhexyl group, perbromoisoheptylhexyl group, perbromoisohexyl group Nylhexyl group, tetrabromopropyl group, octapromopentyl group, dodecabromoheptyl group, hexadecabromononyl group, bis (tribromomethyl) propyl group, hexabromobutyl group, octabromopropyl group, perbromobutyl group, octabromo Cyclobutyl group, perbromopentyl group, perbromocyclopentyl group, perbromohexyl group, perbromocyclohexyl group, bar bromoheptyl group, perbromocycloheptyl group, perbromooctyl group, perbromocyclooctyl group, perbromononyl group , Perbromocyclononyl group, herbromodecyl group, perbromocyclodecyl group, perbromoundecyl group, perbromocycloundecyl group, perbromododecyl group, perbromocyclododecyl group, perbromotridecyl group, Over bromocyclopropane tridecyl group, perbromooctyl tetradecyl group, perbromododecyl cycloalkyl tetradecyl group, perbromododecyl group,
Perbromocyclopentadecyl group, perbromohexadecyl group, perbromocyclohexadecyl group, perbromoheptadecyl group, perbromocycloheptadecyl group, perbromooctadecyl group, perbromocyclooctadecyl group, perbromononadecyl group, Perbromocyclononadecyl group, perbromononaeicosyl group, perbromocycloeicosyl group, perbromophenyl group, perbromobenzyl group, perbromoxylyl group, perbromomesitylenyl group, perbromocumyl group, perbromonaphtha Cyl group, perbromodecalyl group, 1,1-dibromoethyl group, pentabromophenyl group, tetrabromophenyl group, tribromophenyl group, dibromophenyl group, tribromophenyl group, hexabromoxylyl group, tribromomethyl Naphthyl group, - (tribromomethyl) - naphthyl group, tribromomethyl deca Lil group, di - (tribromomethyl) - such as decalyl group. The substitution position of the halogen atom of these halocarbon groups is selected arbitrarily and any of them can be used.

R ⁸ represents R ⁶ or a hydrocarbon group having 1 to 30, preferably 1 to 20 and more preferably 1 to 12 carbon atoms. When a plurality of R ^8's are contained in one molecule, they may be the same or different. As the hydrocarbon group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, an isopentyl group, a neopentyl group, Cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group,
Alkyl group such as heptyl group, octyl group, decyl group and dodecyl group; Amenyl group such as vinyl group and allyl group;
Aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group; benzyl group,
Examples thereof include aralkyl groups such as a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, a phenylpropyl group and a neophyll group. Of course, these may have branches. R ⁹ represents R ⁸ or a hydrogen atom. R ¹⁰ represents a hydrogen atom or a halogen atom such as fluorine, chlorine, bromine or iodine.

As the compound represented by the general formula A, 3-
Perfluorohexyl-1,2-epoxypropane, 3
-Perfluorooctyl-1,2-epoxypropane,
3-perfluorodecyl-1,2-epoxypropane,
3- (perfluoro-3-methylbutyl) -1,2-epoxypropane, 3- (perfluoro-5-methylhexyl) -1,2-epoxypropane, 3- (perfluoro-7-methyloctyl) -1 , 2-epoxypropane, 3- (perfluoro-9-methyldecyl) -1,2
-Epoxypropane,

3-perchlorohexyl-1,2-epoxypropane, 3-perchlorooctyl-1,2-epoxypropane, 3-perchlorodecyl-1,2-epoxypropane, 3- (perchloro-3-methylbutyl) ) −
1,2-epoxypropane, 3- (perchloro-5-methylhexyl) -1,2-epoxypropane, 3- (perchloro-7-methyloctyl) -1,2-epoxypropane, 3- (perchloro-9- Methyldecyl) -1,
2-epoxypropane, 3-perbromohexyl-1,
2-epoxypropane, 3-perbromooctyl-1,
2-epoxypropane, 3-perbromodecyl-1,2
-Epoxypropane, 3- (perbromo-3-methylbutyl) -1,2-epoxypropane, 3- (perbromo-5-methylhexyl) -1,2-epoxypropane,
Examples thereof include 3- (perbromo-7-methyloctyl) -1,2-epoxypropane and 3- (perbromo-9-methyldecyl) -1,2-epoxypropane.

As the compound represented by the general formula B, 3-
(2,2,3,3-tetrafluoropropoxy) -1,
2-epoxypropane, 3- (1H, 1H, 5H-octafluoropentyloxy) -1,2-epoxypropane, 3- (1H, 1H, 7H-dodecafluoroheptyloxy) -1,2-epoxypropane, 3 -(1H, 1
H, 9H-hexadecafluorononyloxy) -1,2
-Epoxypropane, 3- (2,2,3,3-tetrachloropropoxy) -1,2-epoxypropane, 3-
(1H, 1H, 5H-octachloropentyloxy)-
1,2-epoxypropane, 3- (1H, 1H, 7H-
Dodecachloroheptyloxy) -1,2-epoxypropane, 3- (1H, 1H, 9H-hexadecachlorononyloxy) -1,2-epoxypropane,

3- (2,2,3,3-tetrabromopropoxy) -1,2-epoxypropane, 3- (1H, 1
H, 5H-octabromopentyloxy) -1,2-epoxypropane, 3- (1H, 1H, 7H-dodecabromoheptyloxy) -1,2-epoxypropane, 3-
(1H, 1H, 9H-hexadecabromononyloxy)
Examples include -1,2-epoxypropane.

Examples of the compound represented by the general formula C include 2-
Trifluoromethylfuran, 2- (1,1,1-trifluoroethyl) furan, 2- (2-trifluoromethyl-1,1,1-trifluoroethyl) furan, 2-trichloromethylfuran, 2- ( 1,1,1-trichloroethyl) furan, 2- (2-trichloromethyl-1,1,1
1-trichloroethyl) furan, 2-tribromomethylfuran, 2- (1,1,1-tribromoethyl) furan, 2- (2-tribromomethyl-1,1,1-tribromoethyl) furan, etc. Is mentioned.

The compound represented by the general formula D includes 2-
Trifluoromethyltetrahydrofuran, 2- (1,
1,1-trifluoroethyl) tetrahydrofuran, 2
-(2-trifluoromethyl-1,1,1-trifluoroethyl) tetrahydrofuran, 2-trichloromethyltetrahydrofuran, 2- (1,1,1-trichloroethyl) tetrahydrofuran, 2- (2-trichloromethyl-1,2) 1,1-trichloroethyl) tetrahydrofuran, 2-tribromomethyltetrahydrofuran, 2-
(1,1,1-tribromoethyl) tetrahydrofuran, 2- (2-tribromomethyl-1,1,1-tribromoethyl) tetrahydrofuran and the like can be mentioned.

The compound represented by the general formula E includes 2-
Trifluoromethyltetrahydropyran, 2- (1,
1,1-trifluoroethyl) tetrahydropyran, 2
-(2-Trifluoromethyl-1,1,1-trifluoroethyl) tetrahydropyran, 2-trichloromethyltetrahydropyran, 2- (1,1,1-trichloroethyl) tetrahydropyran, 2- (2-trichloromethyl) -1,1,1-Trichloroethyl) tetrahydropyran, 2-tribromomethyltetrahydropyran, 2-
(1,1,1-Tribromoethyl) tetrahydropyran, 2- (2-tribromomethyl-1,1,1-tribromoethyl) tetrahydropyran and the like can be mentioned.

The compound represented by the general formula F is preferably a derivative of so-called tetrahydrofuranyl ether, specifically, 2- (2 ', 2', 2'-trifluoroethoxy) -tetrahydrofuran, 2 -(1'-methyl-2 ', 2', 2'-trifluoroethoxy) -tetrahydrofuran, 2- (1'-trifluoromethyl-
2 ', 2', 2'-trifluoroethoxy) -tetrahydrofuran, 2- (2 ', 2', 3 ', 3', 3'-pentafluoropropoxy) -tetrahydrofuran, 2-
(6 '-(perfluoroethyl) -hexyloxy)-
Tetrahydrofuran, 2- (1'H, 1'H-hexafluorobutoxy) -tetrahydrofuran, 2- (2'-
(Perfluorobutyl) -ethoxy) -tetrahydrofuran, 2- (2 '-(perfluorobutyl) -hexyloxy) -tetrahydrofuran, 2- (2', 2 ',
2'-trichloroethoxy) -tetrahydrofuran, 2
-(1'-methyl-2 ', 2', 2'-trichloroethoxy) -tetrahydrofuran, 2- (1'-trichloromethyl-2 ', 2', 2'-trichloroethoxy) -tetrahydrofuran, 2- (2 ', 2', 3 ', 3',
3'-pentachloropropoxy) -tetrahydrofuran, 2- (6 '-(perchloroethyl) -hexyloxy) -tetrahydrofuran, 2- (1'H, 1'H-hexachlorobutoxy) -tetrahydrofuran, 2-
(2 '-(perchlorobutyl) -ethoxy) -tetrahydrofuran, 2- (2'-(perchlorobutyl) -hexyloxy) -tetrahydrofuran, 2- (2 ',
2 ', 2'-tribromoethoxy) -tetrahydrofuran, 2- (1'-methyl-2', 2 ', 2'-tribromoethoxy) -tetrahydrofuran, 2- (1'-tribromomethyl-2', 2 ', 2'-tribromoethoxy) -tetrahydrofuran, 2- (2', 2 ', 3',
3 ', 3'-pentabromopropoxy) -tetrahydrofuran, 2- (6'-(perbromoethyl) -hexyloxy) -tetrahydrofuran, 2- (1'H, 1'H
-Hexabromobutoxy) -tetrahydrofuran, 2-
(2 '-(perbromobutyl) -ethoxy) -tetrahydrofuran, 2- (2'-(perbromobutyl) -hexyloxy) -tetrahydrofuran and the like.

The compound represented by the general formula G is preferably a derivative of so-called tetrahydropyranyl ether, specifically, 2- (2 ', 2', 2'-trifluoroethoxy) -tetrahydropyran, 2- (1'-methyl-2 ', 2', 2'-trifluoroethoxy) -tetrahydropyran, 2- (1'-trifluoromethyl-
2 ', 2', 2'-trifluoroethoxy) -tetrahydropyran, 2- (2 ', 2', 3 ', 3', 3'-pentafluoropropoxy) -tetrahydropyran, 2-
(6 '-(perfluoroethyl) -hexyloxy)-
Tetrahydropyran, 2- (1'H, 1'H-hexafluorobutoxy) -tetrahydropyran, 2- (2'-
(Perfluorobutyl) -ethoxy) -tetrahydropyran, 2- (2 '-(perfluorobutyl) -hexyloxy) -tetrahydropyran, 2- (2', 2 ',
2'-trichloroethoxy) -tetrahydropyran, 2
-(1'-methyl-2 ', 2', 2'-trichloroethoxy) -tetrahydropyran, 2- (1'-trichloromethyl-2 ', 2', 2'-trichloroethoxy) -tetrahydropyran, 2- (2 ', 2', 3 ', 3',
3'-pentachloropropoxy) -tetrahydropyran, 2- (6 '-(perchloroethyl) -hexyloxy) -tetrahydropyran, 2- (1'H, 1'H-hexachlorobutoxy) -tetrahydropyran, 2-
(2 '-(Perchlorobutyl) -ethoxy) -tetrahydropyran, 2- (2'-(perchlorobutyl) -hexyloxy) -tetrahydropyran, 2- (2 ',
2 ', 2'-Tripromoethoxy) -tetrahydropyran, 2- (1'-methyl-2', 2 ', 2'-tribromoethoxy) -tetrahydropyran, 2- (1'-tribromomethyl-2) ', 2', 2'-Tribromoethoxy) -tetrahydropyran, 2- (2 ', 2', 3 ',
3 ', 3'-Pentabromopropoxy) -tetrahydropyran, 2- (6'-(perbromoethyl) -hexyloxy) -tetrahydropyran, 2- (1'H, 1'H
-Hexabromobutoxy) -tetrahydropyran, 2-
(2 '-(perbromobutyl) -ethoxy) -tetrahydropyran, 2- (2'-(perbromobutyl) -hexyloxy) -tetrahydropyran and the like.

Examples of the compound represented by the general formula H include ether compounds containing at least one halogen, and specifically, 2,2,3,3,3-pentafluoropropyl-methyl. Ether, 2, 2, 3,
3,3-pentafluoropropyl-1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, 1,1,2-trifluoro-2-chloroethyl-2, 2,2-trifluoroethyl ether, 1,1,3,3,3-pentafluoro-
2-trifluoromethylpropyl ether, 2,2,2
-Trifluoroethyl ether, 2,2,2-trifluoroethyl ethyl ether, 2,2,2-trifluoroethyl butyl ether, 2,2,2-trifluoroethyl benzyl ether, 2,2,2-trifluoroethyl Trityl ether, 2,2,3,3-pentafluoropropyltrityl ether, 6- (perfluoroethyl)
-Hexyl trityl ether, 1H, 1H-hexafluorobutyl trityl ether, 2- (perfluorobutyl) ethyl trityl ether, 6- (perfluorobutyl) hexyl trityl ether, 2-perfluorohexyl ethyl trityl ether, 2-perfluoro Octylethyltrityl ether,

2,2,3,3,3-pentachloropropyl-methyl ether, 2,2,3,3,3-pentachloropropyl-1,1,2,2-tetrachloroethyl ether, 1,1,2 , 2-tetrachloroethyl methyl ether, 1,1,3,3,3-pentachloro-2-trichloromethyl propyl ether, 2,2,2-trichloroethyl ether, 2,2,2-trichloroethyl ethyl ether, 2, 2,2-trichloroethyl butyl ether, 2,2,2-trichloroethyl benzyl ether,
2,2,2-trichloroethyltrityl ether, 2,
2,3,3-pentachloropropyltrityl ether,
6- (perchloroethyl) -hexyltrityl ether, 1H, 1H-hexachlorobutyltrityl ether, 2- (perchlorobutyl) ethyltrityl ether, 6- (perchlorobutyl) hexyltrityl ether, 2-perchlorohexylethyltrityl ether,
2-perchlorooctylethyltrityl ether,

2,2,3,3,3-pentabromopropyl-methyl ether, 2,2,3,3,3-pentabromopropyl-1,1,2,2-tetrabromoethyl ether, 1,1 , 2,2-Tetrabromoethyl methyl ether, 1,1,3,3,3-pentabromo-2-tribromomethylpropyl ether, 2,2,2-tribromoethyl ether, 2,2,2-tribromo Ethyl ethyl ether, 2,2,2-tribromoethyl butyl ether, 2,2,2-tribromoethyl benzyl ether,
2,2,2-tribromoethyltrityl ether, 2,
2,3,3-pentabromopropyltrityl ether,
6- (perbromoethyl) -hexyltrityl ether, 1H, 1H-hexabromobutyltrityl ether, 2- (perbromobutyl) ethyltrityl ether, 6- (perbromobutyl) hexyltrityl ether, 2-perbromohexylethyl Trityl ether,
2-perbromooctylethyltrityl ether and the like can be mentioned.

Examples of the compound represented by the general formula I include silyl ether compounds containing at least one halogen, specifically, 2,2,2-trifluoroethyltrimethylsilyl ether, 2, Two
3,3-Pentafluoropropyltrimethylsilyl ether, 6- (perfluoroethyl) -hexyltrimethylsilyl ether, 1H, 1H-hexafluorobutyltrimethylsilyl ether, 2- (perfluorobutyl) ethyltrimethylsilyl ether, 6- (perfluorobutyl) Hexyl trimethyl silyl ether, 2-
Perfluorohexyl ethyl trimethyl silyl ether, 2-perfluoro octyl ethyl trimethyl silyl ether, 2,2,2-trifluoroethyl triphenyl silyl ether, 2,2,3,3-pentafluoropropyl triphenyl silyl ether, 6- (per Fluoroethyl) -hexyltriphenylsilyl ether, 1
H, 1H-hexafluorobutyltriphenylsilylether, 2- (perfluorobutyl) ethyltriphenylsilylether, 6- (perfluorobutyl) hexyltriphenylsilylether, 2-perfluorohexylethyltriphenylsilylether, 2 -Perfluorooctylethyltriphenylsilyl ether,

2,2,2-trichloroethyltrimethylsilyl ether, 2,2,3,3-pentachloropropyltrimethylsilyl ether, 6- (perchloroethyl) -hexyltrimethylsilyl ether, 1H, 1H
-Hexachlorobutyl trimethylsilyl ether, 2-
(Perchlorobutyl) ethyltrimethylsilyl ether, 6- (perchlorobutyl) hexyltrimethylsilyl ether, 2-perchlorohexylethyltrimethylsilyl ether, 2-perchlorooctylethyltrimethylsilyl ether,

2,2,2-trichloroethyltriphenylsilyl ether, 2,2,3,3-pentachloropropyltriphenylsilyl ether, 6- (perchloroethyl) -hexyltriphenylsilyl ether, 1H,
1H-hexachlorobutyltriphenylsilyl ether, 2- (perchlorobutyl) ethyltriphenylsilylether, 6- (perchlorobutyl) hexyltriphenylsilylether, 2-perchlorohexylethyltriphenylsilylether, 2-perchloro Octylethyltriphenylsilyl ether,

2,2,2-tribromoethyltrimethylsilyl ether, 2,2,3,3-pentabromopropyltrimethylsilyl ether, 6- (perbromoethyl) -hexyltrimethylsilyl ether, 1H, 1H
-Hexabromobutyl trimethylsilyl ether, 2-
(Perbromobutyl) ethyltrimethylsilyl ether, 6- (perbromobutyl) hexyltrimethylsilyl ether, 2-perbromohexylethyltrimethylsilyl ether, 2-perbromooctylethyltrimethylsilyl ether,

2,2,2-tribromoethyl triphenylsilyl ether, 2,2,3,3-pentabromopropyltriphenylsilyl ether, 6- (perbromoethyl) -hexyltriphenylsilyl ether, 1H,
1H-hexabromobutyl triphenylsilyl ether, 2- (perbromobutyl) ethyl triphenylsilyl ether, 6- (perbromobutyl) hexyltriphenylsilyl ether, 2-perbromohexylethyltriphenylsilyl ether, 2-per Bromooctylethyl triphenylsilyl ether and the like can be mentioned.

Examples of the compound represented by the general formula J include acetal and ketal compounds having at least one halogen in the carbon skeleton derived from a ketone or an aldehyde, and specifically, 2,2 -Dimethoxy-
1,1,1-trifluoropropane, 2,2-diethoxy-1,1,1-trifluoropropane, 2,2-dimethoxy-1,1,1,3,3,3-hexafluoropropane, 2, 2-diethoxy-1,1,1,3,3,3-
Hexafluoropropane, 1,1-dimethoxy-1-pentafluorophenylethane, 1,1-diethoxy-1
-Pentafluorophenylethane, dimethoxydipentafluorophenylmethane, diethoxydipentafluorophenylmethane,

2,2-dimethoxy-1,1,1-trichloropropane, 2,2-diethoxy-1,1,1-trichloropropane, 2,2-dimethoxy-1,1,1,
3,3,3-hexachloropropane, 2,2-diethoxy-1,1,1,3,3,3-hexachloropropane,
1,1-dimethoxy-1-pentachlorophenylethane, 1,1-diethoxy-1-pentachlorophenylethane, dimethoxydipentachlorophenylmethane, diethoxydipentachlorophenylmethane,

2,2-dimethoxy-1,1,1-tribromopropane, 2,2-diethoxy-1,1,1-tribromopropane, 2,2-dimethoxy-1,1,1,
3,3,3-hexabromopropane, 2,2-diethoxy-1,1,1,3,3,3-hexabromopropane,
1,1-dimethoxy-1-pentabromophenylethane, 1,1-diethoxy-1-pentabromophenylethane, dimethoxydipentabromophenylmethane, diethoxydipentabromophenylmethane and the like can be mentioned.

Examples of the compound represented by the general formula K include acetal and ketal compounds having at least one fluorine in the carbon skeleton derived from alcohol, and specifically, 2,2-bis. (2,2,2-trifluoroethoxy) -propane, 1,1-bis (2,2
2,2-trifluoroethoxy) -cyclohexane,
1,1-bis (2,2,2-trifluoroethoxy)-
1-phenylethane, di (2,2,2-trifluoroethoxy) diphenylmethane, di (2,2,2-trifluoroethoxy) phenylmethane,

2,2-bis (2,2,2-trichloroethoxy) -proban, 1,1-bis (2,2,2-trichloroethoxy) -cyclohexane, 1,1-bis (2,2,2) -Trichloroethoxy) -1-phenylethane, di (2,2,2-trichloroethoxy) diphenylmethane, di (2,2,2-trichloroethoxy) phenylmethane,

2,2-bis (2,2,2-tribromoethoxy) -propane, 1,1-bis (2,2,2-tribromoethoxy) -cyclohexane, 1,1-bis (2,2) , 2-tribromoethoxy) -1-phenylethane, di (2,2,2-tribromoethoxy) diphenylmethane, di (2,2,2-tribromoethoxy) phenylmethane and the like.

Examples of the compound represented by the general formula L include orthoester compounds having at least one halogen in the carbon skeleton derived from carboxylic acid, and specifically, 1,1,1 -Trimethoxy-2,2
2-trifluoroethane, 1,1,1-triethoxy-
2,2,2-trifluoroethane, 1,1,1-trimethoxy-2,2,2-trichloroethane, 1,1,1-
Triethoxy-2,2,2-trichloroethane, 1,
1,1-trimethoxy-2,2,2-tribromoethane, 1,1,1-triethoxy-2,2,2-tribromoethane and the like can be mentioned.

Examples of the compound represented by the general formula M include orthoester compounds having at least one halogen in the carbon skeleton derived from alcohol, and specifically, 1,1,1- Tri (2,2,2-trifluoroethoxy) -ethane, 1,1,1-tri (2,2
2,2-trichloroethoxy) -ethane, 1,1,1-
Tri (2,2,2-tribromoethoxy) -ethane,
1,1,1-tri (2,2,2-triiodoethoxy)
Includes ethane.

Examples of the compound represented by the general formula N include hydrocarbons containing at least one halogen, and specific examples include perfluorohexane, perfluorocyclohexane, perfluoroheptane and perfluoromethyl. Cyclohexane, perfluorooctane,
1-bromoheptadecafluorooctane, perfluorododecane, perfluoro-2,7-dimethyloctane,
Perfluoro-2,11-dimethyldodecane, tribromofluoromethane, dibromofluoromethane, 1-bromo-2-fluoromethane, 1,2-dibromo-1,1-
Difluoroethane, 1,1,1-trichlorotrifluoroethane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,2-dibromohexafluoropropane, 1,1,3,4-tetrachlorohexafluorobutane, 1,1,1,3,5,6-hexachlorooctafluorohexane, 1,1,3,5,6-pentachlorononafluorohexane, hexafluorobenzene, chloropentafluorobenzene, bromopentafluorobenzene, pentafluorobenzene , Dichlorotetrafluorobenzene, dibromotetrafluorobenzene, tetrafluorobenzene, trichlorotrifluorobenzene, tribromotrifluorobenzene, trifluorobenzene, tetrachlorodifluorobenzene, tetrabromodifluorobenzene, 1, - difluorobenzene, 1,
3-difluorobenzene, 1,4-difluorobenzene, fluorobenzene, perfluorotoluene, perfluoromethylcyclohexane, trifluoromethylbenzene, benzyl fluoride, 1,2-bistrifluoromethylbenzene, 1,3-bisfluoromethylbenzene , 1,4-bistrifluoromethylbenzene, octafluoronaphthalene, perfluorodecalin, perfluorobiphenyl,

Dichloromethane, chloroform, 1,1-
Dichloroethane, 1,2-dichloroethane, 1,1,1
-Trichloroethane, 1,1,2-trichloroethane,
1,1-dichloropropane, 1,2-dichloropropane, 1,3-dichloropropane perchlorohexane, perchloroheptane, perchloromethylcyclohexane,
Perchlorooctane, perchlorododecane, perchloro-2,7-dimethyloctane, perchloro-2,11-
Dimethyldodecane, hexachlorobenzene, pentachlorobenzene, tetrachlorobenzene, trichlorobenzene, dichlorobenzene, chlorobenzene, perchlorotoluene, perchloromethylcyclohexane, trichloromethylbenzene, benzyl chloride, bistrichloromethylbenzene, octachloronaphthalene, perchlorodecalin, perchlorodecane Chlorobiphenyl,

Perbromohexane, perbromoheptane, perbromomethylcyclohexane, perbromooctane, perbromododecane, perbromo-2,7-dimethyloctane, perbromo-2,1-dimethyldodecane, hexabromobenzene, pentabromobenzene, Tetrabromobenzene, tribromobenzene, dibromobenzene, bromobenzene, perbromotoluene, perbromomethylcyclohexane, tribromomethylbenzene, benzyl bromide, bistribromomethylbenzene, octabromonaphthalene, perbromodecalin, perbromobiphenyl, etc. To be

Preferred among the above general formulas are general formula H, general formula I and general formula N. Among the above specific examples, preferred specific examples include 3-perfluorohexyl-1,2-epoxypropane, 2-trifluoromethylfuran, 2-trifluoromethyltetrahydrofuran, 2-trifluoromethyltetrahydropyran, 2,
2,2-trifluoroethylbenzyl ether, 2,
2,2-trifluoroethyltrityl ether, 2,
2,3,3-Pentafluoropropyltrityl ether, 1H, 1H-hexafluorobutyltrityl ether, 2,2,2-Trifluoroethyltriphenylsilyl ether, 2,2,3,3-Pentafluoropropyltriphenylsilyl Ether, 1H, 1H-hexafluorobutyltriphenylsilyl ether, 2,2-dimethoxy-1,1,1-trifluoropropane, 2,2-
Diethoxy-1,1,1-trifluoropropane, 2,
2-dimethoxy-1,1,1,3,3,3-hexafluoropropane, 2,2-diethoxy-1,1,1,3
3,3-hexafluoropropane, 2,2-bis (2,2
2,2-trifluoroethoxy) -propane, 1,1-
Bis (2,2,2-trifluoroethoxy) -cyclohexane, 1,1,1-trimethoxy-2,2,2-trifluoroethane, 1,1,1-triethoxy-2,2
2-trifluoroethane, 1,1,1-tri (2,2,
2-trifluoroethoxy) -ethane, hexafluorobenzene, 1,2-difluorobenzene, monofluorobenzene, perfluorotoluene, bistrifluoromethylbenzene, perfluorodecalin, perfluoromethyldecalin, dichloromethane, chloroform, 1,1
-Dichloroethane, 1,2-dichloroethane, 1,1,
1-trichloroethane, 1,1,2-trichloroethane, 2- (2 ', 2', 2'-trifluoroethoxy)
-Tetrahydrofuran, 2- (1'-methyl-2 ',
2 ', 2'-trifluoroethoxy) -tetrahydrofuran, 2- (1'-trifluoromethyl-2', 2 ',
2'-trifluoroethoxy) -tetrahydrofuran,
2- (2 ', 2', 2'-trifluoroethoxy) -tetrahydropyran, 2- (1'-methyl-2 ', 2',
2'-trifluoroethoxy) -tetrahydropyran,
2- (1'-trifluoromethyl-2 ', 2', 2'-
Trifluoroethoxy) -tetrahydropyran.

Of course, two or more of these may be used in combination. The modified organoaluminum compound that can be used in the present invention has 1 to 100, preferably 1 to 100 in the molecule.
It contains 50 Al-O-Al bonds. The modified organoaluminum compound may be linear or cyclic. Such a modified organoaluminum compound is usually obtained by reacting an organoaluminum compound with water. The reaction between the organoaluminum compound and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. It is preferred to use group hydrocarbons.

The organoaluminum compound used to prepare the modified organoaluminum compound has the general formula R ¹¹ _a AlX ³
_3-a (In the formula, R ¹¹ has 1 to 18 carbon atoms, preferably 1
A hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc., X ³ represents a hydrogen atom or a halogen atom, and a represents an integer of 1 ≦ a ≦ 3). However, trialkylaluminum is preferably used. The alkyl group of trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. Is particularly preferable.

The reaction ratio of water and the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, and particularly preferably 0.5 / 1 to 1/1. The reaction temperature is usually -70 to 100 ° C, preferably -20 to 20 ° C.
Is in the range. The reaction time is generally 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 as well as water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like. Among these modified organoaluminums, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, and methylaluminoxane (or a substance essentially consisting of methylaluminoxane) is particularly preferable. Of course, it is also possible to use two or more modified organoaluminum compounds in combination.

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

The olefin polymerization catalyst component of the present invention is
As described above, (1) Me ¹ R ¹ _p (OR ² ) _q X ¹
_4-p-q compounds represented by (component (1)), (2) the general formula _{^{Me 3 H m R 5 3-}} m, the general formula Me ^{4 [Me} 3 _{H p
^{R 6 q (OR 7) 4}} -p-q ] _z, formula

[0095]

[Chemical 8]

(Component (2)), (3) cyclic organic compound having two or more conjugated double bonds (Component (3)), and (4) carbon-halogen bond-containing compound (Component (4)) Obtained by contacting each other as essential components, and further adding (5) a modified organoaluminum compound containing Al-O-Al bond (component (5)) and contacting each other to obtain the catalyst of the present invention. However, the order of contact of these components is not particularly limited. For example, the catalyst component of the present invention can be obtained by contacting each component with the following method.

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

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

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

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

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

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

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

Although methods 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 completion of all the catalytic reactions, or, if possible, precipitated. Alternatively, the solid catalyst component may be once taken out by a means such as drying, and then used for polymerization. of course,
The contact reaction of each component may be performed multiple times. The use ratio of these 5 components is 0.01-1,000 mol, preferably 0.1-1000 mol of the component (2) per 1 mol of the component (1).
To 100 mol, more preferably 0.5 to 50 mol, and component (3) 0.01 to 1,000 mol, preferably 0.1.
1 to 100 mol, more preferably 0.5 to 50 mol,
The component (4) is 0.01 to 100 mol, preferably 0.1.
It is preferable to prepare -50 mol, more preferably 0.5-10 mol, and the component (5) at 1-1,000 mol, preferably 1-500 mol, more preferably 1-100 mol.

In the present invention, the following combinations are mentioned as one of the preferable combinations when the components (1) to (4) and, if desired, (5) are used. A. Tetrapropoxy zirconium among the components (1),
A tetraalkoxyzirconium compound such as tetrabutoxyzirconium, an alkylaluminum hydride compound such as diethylaluminum hydride or diisobutylaluminum hydride among the components (2),
Indene derivatives such as indene and methylindene among the components (3); cyclopentadiene derivatives such as cyclopentadiene, methylcyclopentadiene and dimethylcyclopentadiene, fluorobenzene among the components (4),
Fluorine-containing aromatic compounds such as 1,2-difluorobenzene, hexafluorobenzene, trifluoromethylbenzene, 1,4-bistrifluoromethylbenzene, and 1,3-bistrifluoromethylbenzene, and optionally methylaluminoxane as the component (5). .

B. Tetraalkoxyzirconium compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium among the components (1), alkylaluminum hydride compounds such as diethylaluminum hydride and diisobutylaluminum hydride among the components (2), and indene and methylindene among the components (3). Indene derivatives such as; cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, and other cyclopentadiene derivatives; fluorinated naphthene-based compounds such as perfluorocyclohexane, perfluoromethylcyclohexane, and perfluorodecalin among the components (4), and optionally components Methylaluminoxane as (5).

C. Tetraalkoxyzirconium compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium in the component (1), alkylaluminum hydride compounds such as diethylaluminum hydride and diisobutylaluminum hydride in the component (2), and bisindenylethane in the component (3). Or a compound in which an indene derivative such as cyclopentadienylfluorenylisopropane, a cyclopentadiene derivative, or a fluorene derivative is bonded via an alkylene group, or a compound represented by the above general formula A _L SiR _4-L such as dimethylsilylbiscyclopentadiene Compound, among the components (4), fluorobenzene, 1,2-difluorobenzene, hexafluorobenzene, trifluoromethylbenzene, 1,4-bistrifluoro Methylbenzene,
Fluorine-containing aromatic compounds such as 1,3-bistrifluoromethylbenzene, and optionally methylaluminoxane as the component (5).

D. Tetraalkoxyzirconium compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium in the component (1), alkylaluminum hydride compounds such as diethylaluminum hydride and diisobutylaluminum hydride in the component (2), and bisindenylethane in the component (3). Or a compound in which an indene derivative such as cyclopentadienylfluorenylisopropane, a cyclopentadiene derivative, or a fluorene derivative is bonded via an alkylene group, or a compound represented by the above general formula A _L SiR _4-L such as dimethylsilylbiscyclopentadiene Compound, a fluorine-containing naphthenic compound such as perfluorocyclohexane, perfluoromethylcyclohexane, or perfluorodecalin among the components (4), Ri methylaluminoxane as component (5).

Thus, the catalyst of the present invention is obtained.

In the present invention, an olefin polymer or copolymer can be produced by polymerizing or copolymerizing olefins in the presence of such a catalyst.

In the polymerization reaction of the present invention, in addition to supplying the catalyst produced as described above into the polymerization system, the components (1) to (4) are optionally contacted with a part of the component (5). It is also preferably carried out when the catalyst component thus obtained and the rest of the catalyst component are substantially brought into contact with each other in the polymerization system. In the case of bringing them into substantial contact in the polymerization system, a method of preparing a catalyst component by alternately contacting the components (1) to (3) and then bringing them into substantial contact with the component (5) in the polymerization system, , A catalyst component is prepared by bringing the components (1) to (4) into contact with each other, and the component (5) is substantially brought into contact with the polymerization system. Another example of the catalyst supply method is a method of introducing the catalyst obtained above into the polymerization system and further introducing the component (5) into the polymerization system.

In any case when the component (5) is used in combination in the polymerization system, the ratio of the catalyst component and the modified organoaluminum compound used is such that the aluminum atom in the modified organoaluminum compound relative to the transition metal in the catalyst component is used. The ratio is 100,000 or less, usually 0.1 to 100,000
It is selected to be 0, preferably 0.55 to 1,000.

The olefins used 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-silane. Examples thereof include phenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and the like. 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 composed of the catalyst component and the promoter component described above. In particular, slurry polymerization or gas phase polymerization is preferable, and in a state where oxygen, water, etc. are substantially cut off, hexane, an aliphatic hydrocarbon such as heptane,
The olefin is polymerized in the presence or absence of an inert hydrocarbon solvent selected from aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. The polymerization conditions at this time are as follows: temperature 20 to 200 ° C., preferably 50 to 100 ° C., pressure normal pressure to 70 kg / cm ² G, preferably normal pressure to 20 k.
It is in the range of g / cm ² G, and the polymerization time is 5 minutes to 1
It is common to employ 0 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, it can be carried out without any trouble even if a component for removing water, so-called scavenging, is added to the polymerization system. In addition, as such scavenging,
Organoaluminum compounds represented by trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, the modified organoaluminum compounds, modified organoaluminum compounds containing branched alkyl, butyllithium, etc. Organic magnesium, such as organic lithium, diethyl magnesium, dibutyl magnesium, butyl magnesium chloride, etc. are mentioned. It can also be applied without trouble to a multi-stage polymerization mode of two or more stages in which the polymerization conditions such as hydrogen concentration, monomer concentration, polymerization pressure, and polymerization temperature are different from each other. Before the main polymerization, the olefins may be brought into contact with each other in advance to carry out the prepolymerization, and then the prepolymerization catalyst may be used for the main polymerization.

[0121]

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 (Methyl Al
Preparation of Minoxane) 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 After that, the reaction product was filtered, and toluene in the liquid containing the reaction product was removed to obtain 4 g of white crystalline methylalumoxane (MAO). The physical properties of the polymers obtained in Examples and Comparative Examples were evaluated by the following methods.

Melt Flow Rate (MFR) ASTM D 1238-57T 190 ° C, 2.16
It was measured based on the kg load.

Density : 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./minute, holding at 0 ° C. for 10 minutes, and then raising the temperature at 10 ° C./minute.

Measurement of Mw / Mn Using a 150C type GPC device manufactured by Waters Co., a column was measured under the conditions of GMH-6 manufactured by Toyo Soda Co. Ltd., solvent O-dichlorobenzene, temperature 135 ° C., and flow rate 1.0 ml / min. , Mw / Mn were determined.

Temperature rising elution fractionation (Temperature
e Rising Elution Fractiona
(hereinafter referred to as TREF)): The obtained olefin (co) polymer was dissolved in o-dichlorobenzene and then cooled to form a polymer layer on diatomaceous earth, and then the temperature was continuously raised. The eluted components were continuously detected.

Measurement of degree of branching Using a JEOL NMR apparatus, 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 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxyzirconium (0.11 g), diisobutylaluminum hydride (0.69 ml), 1,2-bisindenylethane (0.1 g), 2,2,2-trifluoroethyltriphenylsilyl ether (5.0 × 10
^-4 mol) was dissolved in 13 ml of toluene to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst.
This catalyst solution was introduced into a 2 L autoclave and the total pressure was maintained at 9 atm while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.3) at 60 ° C.
Polymerization was carried out for 2 hours. Catalyst efficiency is 220kg / gZ
r, density 0.9100 g / cm ³ , MFR 2.0
g / 10min (190 ° C), melting point 113.5 ° C, M
It was w / Mn = 8.6. The TREF peak was sharp and it was found that the composition distribution was very narrow.

Example 2 200 g of sea sand that had been heat treated at 300 ° C. after acid cleaning was 2 L
It was introduced into an autoclave and dried sufficiently. Tetrabutoxyzirconium (0.22 g), aluminum hydride (0.09 g), indene (0.23 ml), hexafluorobenzene (4.4 × 10 ⁻⁵ mol) were added to toluene 1
It was suspended in 3 ml to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst. This catalyst solution was introduced into a 2 L autoclave, and ethylene and 1-butene (butene / butene /
While continuously supplying a mixed gas of ethylene = 0.2),
Polymerization was carried out at 60 ° C for 2 hours while maintaining the total pressure at 9 atm. The catalyst efficiency is 130 kg / gZr and the density is 0.92.
00g / cm ³ , MFR 1.4g / 10min (19
0 ° C.), the melting point was 118.0 ° C., and Mw / Mn = 9.1.

Example 3 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tributoxy monochlorozirconium (0.26 g), lithium aluminum hydride (0.10 g), indene (0.28 ml) and perfluoromethylcyclohexane (4.4 × 10 ⁻⁵ mol) were suspended in toluene (17 ml) to prepare a catalyst component. Obtained. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component suspension (Al / Z
(r = 100 (molar ratio)), and stirred at room temperature for 30 minutes to obtain a target catalyst. This catalyst solution was introduced into a 2 L autoclave, and ethylene and 1-butene (butene / ethylene =
Polymerization was carried out at 60 ° C. for 2 hours while continuously supplying the mixed gas of 0.2) and maintaining the total pressure at 9 atm. The catalyst efficiency is 23 kg / gZr and the density is 0.9250 g / c.
m ³ and MFR were 1.0 g / 10 min (190 ° C.), the melting point was 117.7 ° C., and Mw / Mn = 9.7.

Example 4 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Dibutoxydichlorozirconium (0.26 g), lithium aluminum triethoxy hydride (0.80 g), indene (0.28 ml) and 2,2,2-trifluoroethyltrityl ether (4.4 × 10 ⁻⁵ mol) were added. It was dissolved in 17 ml of toluene to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst. This catalyst solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and the temperature was 60 ° C. for 2 hours. Polymerization was carried out. The catalyst efficiency is 38 kg / gZr and the density is 0.91.
80 g / cm ³ , MFR 0.4 g / 10 min (19
0 ° C.), the melting point was 115.2 ° C., and Mw / Mn = 6.7.

Example 5 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxytitanium (0.13 g), lithium aluminum tri-tert-butoxy hydride (0.60 g),
Indene (0.35 ml), 2,2-dimethoxy-1,
1,1,3,3,3-hexafluoropropane (4.2
(× 10 ⁻⁵ mol) was dissolved in 17 ml of toluene to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Ti = 1000
(Molar ratio)), and stirred at room temperature for 30 minutes to obtain a target catalyst. This catalyst solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and the temperature was 60 ° C. for 2 hours. Polymerization was carried out. Catalyst efficiency is 45 kg /
gTi, density 0.9100 g / cm ³ , MFR 1.3 g / 10 min (190 ° C.), melting point 111.2
C., Mw / Mn = 8.5.

Example 6 2 L of 200 g of sea sand heat treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrapropoxy hafnium (0.23 g), diisobutylaluminum hydride (0.38 ml), indene (0.
23 ml), 1,1,1-tris- (2 ', 2', 2 '
-Trifluoroethoxy) -ethane (1.3 x 10 ^-5
(Mol) was dissolved in 25 ml of toluene to obtain a catalyst component.
Furthermore, a toluene solution of methylaluminoxane (Al / H
f = 500 (molar ratio)), and stirred at room temperature for 30 minutes,
The target catalyst was obtained. This catalyst solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and the temperature was 60 ° C. for 2 hours. Polymerization was carried out. The catalyst efficiency is 45 kg / gHf and the density is 0.9200 g / c.
m ³ and MFR were 1.2 g / 10 min (190 ° C.), the melting point was 115.0 ° C., and Mw / Mn = 7.7.

Example 7 500 ml of purified toluene was introduced into a sufficiently dried 2 L autoclave. Tetrabutoxy zirconium (0.11 g), di-isobutylaluminum hydride (0.69 ml), 1,2,4-trimethylcyclopentadiene (0.31 g), 1,1,1-trimethoxy-2,2,2- Trifluoroethane (4.4 x 10
^-5 mol) was dissolved in 13 ml of toluene to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 600 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst.
This catalyst solution was introduced into a 2 L autoclave, and propylene gas was continuously supplied, while maintaining the total pressure at 9 atm to carry out polymerization at 60 ° C. for 2 hours. Catalyst efficiency is 220 kg
/ GZr, Mw = 16000, and Mw / Mn = 3.9.

Example 8 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrapropoxyzirconium (0.29g), catecholborane (0.12g), 1,3-dimethylcyclopentadiene (0.08g), 2,2-bis- (2 ', 2', 2'-
Trifluoroethoxy) -propane (4.4 × 10 ⁻⁵
Mol) was dissolved in 40 ml of toluene. This solution 0.5
Toluene solution of methylaluminoxane was added to ml (A
1 / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave and the total pressure was maintained at 9 atm while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2) at 60 ° C.
Polymerization was carried out for 2 hours. Catalyst efficiency is 60kg / gZr
And the density is 0.9200 g / cm ³ , and the MFR is 0.6 g.
/ 10 min (190 ° C), melting point 116.5 ° C, Mw
/Mn=5.5.

Example 9 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrapropoxyzirconium (0.29 g), sodium borohydride (0.05 g), 1,3-dimethylcyclopentadiene (0.08 g), 3-perfluorohexyl-1,2-epoxypropane (4.3 × 10 ^{−). 5} mol)
Was suspended in 40 ml of toluene. 0.5 ml of this suspension
To this, add a toluene solution of methylaluminoxane (Al /
Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and while continuously supplying ethylene gas, polymerization was carried out at 60 ° C. for 2 hours while maintaining the total pressure at 9 atm. Catalyst efficiency is 30kg / gZr
And has a density of 0.9650 g / cm ³ and an MFR of 0.6 g
/ 10 min (190 ° C.), melting point 137.0 ° C., Mw
/Mn=5.2.

Example 10 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabenzyl zirconium (0.29 g), zinc polo hydride (0.04 g), indene (0.41 ml), 3-
(2,2,3,3-tetrafluoropropoxy) -1,
2-Epoxy propane (4.4 × 10 ⁻⁵ mol) was suspended in 40 ml of toluene. Toluene solution of methylaluminoxane was added to 0.5 ml of this suspension (Al / Zr =
100 (molar ratio)) and stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and polymerization was performed at 60 ° C for 2 hours. I went. The catalyst efficiency is 22 kg / gZr, the density is 0.9180 g / cm ³ , and the MFR is 0.9 g / 10 mi.
n (190 ° C.), melting point 117.2 ° C., Mw / Mn =
It was 7.6.

Example 11 2 L of 200 g of sea sand heat treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrachlorozirconium (0.19 g), potassium triisobutylborohydride (8.2 × 10 ⁻⁵ mol), indene (0.41 ml), 2-trifluoromethylfuran (3.2 ×× 10 ⁻⁵ mol) Was suspended in 40 ml of toluene. A toluene solution of methylaluminoxane was added to 0.5 ml of this solution (Al / Zr = 100 (molar ratio)),
The mixture was stirred at room temperature for 30 minutes. This solution was introduced into a 2 L autoclave, and ethylene and 1-butene (butene / ethylene =
Polymerization was carried out at 60 ° C. for 2 hours while continuously supplying the mixed gas of 0.2) and maintaining the total pressure at 9 atm. The catalyst efficiency is 21 kg / gZr and the density is 0.9220 g / c.
m ³ and MFR were 0.5 g / 10 min (190 ° C.), the melting point was 117.2 ° C., and Mw / Mn = 5.3.

Example 12 2 L of 200 g of sea sand that had been heat treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxyzirconium (0.11 g), diisobutylaluminum hydride (0.69 ml), 1,2-bisindenylethane (0.1 g), 2-trifluoromethyltetrahydrofuran (4.4 × 10 ⁻⁵ mol) in toluene It was dissolved in 13 ml to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst. This catalyst solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and the temperature was 60 ° C. for 2 hours. Polymerization was carried out. The catalyst efficiency is 200 kg / gZr and the density is 0.9.
200 g / cm ³ , MFR 1.1 g / 10 min (1
90 ° C.), the melting point was 115.0 ° C., and Mw / Mn = 7.9. The TREF peak was sharp and it was found that the composition distribution was very narrow.

Example 13 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tetrabutoxy zirconium (0.22 g), aluminum hydride (0.09 g), indene (0.23 ml), 2-trifluoromethyltetrahydropyran (4.4 × 10 ⁻⁵⁾
(Mol) was suspended in 13 ml of toluene to obtain a catalyst component.
A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst.
This catalyst solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and 60 ° C.
Polymerization was carried out for 2 hours. Catalyst efficiency is 100 kg / gZ
r, density 0.9250 g / cm ³ , MFR 1.3
g / 10 min (190 ° C.), melting point 116.3 ° C., M
It was w / Mn = 9.1.

Example 14 2 L of 200 g of sea sand heat-treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Tributoxy monochloro zirconium (0.26 g), lithium aluminum hydride (0.10 g), indene (0.28 ml), 2- (2 ', 2', 2'-trifluoroethoxy) -tetrahydrofuran (2.2 x 10).
^-5 mol) was suspended in 17 ml of toluene to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component suspension (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain the target catalyst.
This catalyst solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and 60 ° C.
Polymerization was carried out for 2 hours. Catalyst efficiency is 19kg / gZr
With a density of 0.9190 g / cm ³ and an MFR of 0.4 g
/ 10 min (190 ° C), melting point 116.3 ° C, Mw
/Mn=9.8.

Example 15 2 L of 200 g of sea sand that had been heat treated at 300 ° C. after acid cleaning
It was introduced into an autoclave and dried sufficiently. Dibutoxydichlorozirconium (0.26 g), lithium aluminum triethoxyhydride (0.80 g), indene (0.28 ml), 2- (2 ′, 2 ′, 2′-trifluoroethoxy) -tetrahydropyran (2. 2 x 1
0 ^-5 mol) was dissolved in toluene 17 ml, to obtain a catalyst component. A toluene solution of methylaluminoxane was added to 0.5 ml of this catalyst component solution (Al / Zr = 100 (molar ratio)), and the mixture was stirred at room temperature for 30 minutes to obtain a target catalyst.
This catalyst solution was introduced into a 2 L autoclave, and while continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was maintained at 9 atm and 60 ° C.
Polymerization was carried out for 2 hours. Catalyst efficiency is 37kg / gZr
And has a density of 0.9250 g / cm ³ and an MFR of 0.2 g
/ 10 min (190 ° C.), melting point 119.3 ° C., Mw
/Mn=6.7.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that 2,2,2-trifluoroethyltriphenylsilyl ether was not used. The catalyst efficiency is 150 kg / gZr and the density is 0.
9150g / cm ³ , MFR is 3.0g / 10min
(190 ° C.), melting point 113.0 ° C., Mw / Mn = 6.
It was 5.

Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 except that diisobutylaluminum hydride was not used. No polymer was obtained.

Comparative Example 3 Example 1 except that no bisindenylethane was used.
Polymerization was carried out in the same manner as in. Catalyst efficiency is 0.001kg / g
It was Zr. It was found that the TREF peak was very broad and the composition distribution was wide.

[Brief description of drawings]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-7-173214 (JP, A) JP-A-7-292030 (JP, A) JP-A-8-34811 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (2)

(57) [Claims] 1. A general formula MeR _p (OR ′) _q X.
A compound represented by _4-pq (wherein R and R ′ are independently a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom, Me is Zr, Ti or Hf, and p and q are 0 respectively. ≤p
≦ 4, 0 ≦ q ≦ 4, 0 ≦ p + q ≦ 4), (2) at least one metal hydride compound selected from the following general formulas 1 to 3 general formula 1: MeH _m R _3-m general formula 2 : Me _{'[MeH p R q (OR) 4} -pq ] _z formula 3: [formula 1] (In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, Me is an element of Group 13 of the periodic table, and Me 'is an element of Group 1, 2, or 12 of the periodic table, When R is 2 or more, R may be the same or different, z is the valence of Me ′, and m, n, p and q are 0 <m ≦ 3,
0 ≦ n ≦ 4, 1 ≦ p ≦ 4, 0 ≦ q ≦ 3, and 1 ≦ p
+ Q ≦ 4. ), (3) An organic compound having a cyclopentadiene structure , and (4) a catalyst component for olefin polymerization obtained by bringing a compound containing a carbon-halogen bond into contact with each other. 2. (1) The general formula MeR _p (OR ′) _q X
A compound represented by _4-pq (wherein R and R ′ are independently a hydrocarbon group having 1 to 24 carbon atoms, X is a halogen atom, Me is Zr, Ti or Hf, and p and q are 0 respectively. ≤p
≦ 4, 0 ≦ q ≦ 4, 0 ≦ p + q ≦ 4), (2) at least one metal hydride compound selected from the following general formulas 1 to 3 general formula 1: MeH _m R _3-m general formula 2 : Me _{'[MeH p R q (OR) 4} -pq ] _z formula 3: [formula 2] (In the formula, R is a hydrocarbon group having 1 to 20 carbon atoms, Me is an element of Group 13 of the periodic table, and Me 'is an element of Group 1, 2, or 12 of the periodic table, When R is 2 or more, R may be the same or different, z is the valence of Me ′, and m, n, p and q are 0 <m ≦ 3,
0 ≦ n ≦ 4, 1 ≦ p ≦ 4, 0 ≦ q ≦ 3, and 1 ≦ p
+ Q ≦ 4. ), (3) Organic compound having cyclopentadiene structure , (4) Carbon-halogen containing compound, and (5) Olefin polymerization obtained by bringing modified organoaluminum compound containing Al—O—Al bond into contact with each other. Catalyst.