JPH0859728A - Catalyst for polymerizing olefins and production of polyolefin using the same - Google Patents

Abstract

PURPOSE: To obtain a catalyst for producing a polyolefin having relatively wide molecular weight distribution, good particle properties or an olefin-based copolymer having narrow composition distribution, high molecular weight and hardly causing tackiness. CONSTITUTION: This catalyst is obtained by carrying out preliminary polymerization of olefins on a catalyst component obtained by bringing (l) a compound expressed by the general formula, Me<1> R<1> p (OR<2> )q X<1> 4-p-q ) (Me<1> is Zr, Ti or Hf; R<1> an R<2> are each a 1-24C hydrocarbon group; X is a halogen atom), (2) a compound expressed by the general formula, Me<2> R<3> m (OR<4> )n X<2> z-m-n (Me<2> is an element of a group I to III of the periodic table; R<3> and R<4> are each 1-24C hydrocarbon group; X<2> is a halogen atom or hydrogen atom (with the proviso that when X<2> is hydrogen atom, Me<2> is an element of a group III of the periodic table), (3) an organic cyclic compound having a conjugated double bond, (4) a modified organoaluminum compound containing Al-O-Al bond and (5) an inorganic support and/or a particulate polymer support, into contact with each other.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for polymerizing olefins and a method for producing a polyolefin using the same, and more particularly, to a copolymer having a relatively wide molecular weight distribution, good particle properties, and copolymerization. The present invention relates to a catalyst capable of producing an excellent polyolefin having a narrow composition distribution, a high molecular weight and a low tackiness, and a method for producing a polyolefin using the catalyst.

[0002]

2. Description of the Related Art In the production of polyolefins, particularly ethylene polymers or ethylene / .alpha.-olefin copolymers, it is known to use a catalyst composed of a zirconium compound (typically a metallocene compound) and an aluminoxane. No. 58-19309.
This technique has an advantage that an ethylene-based copolymer can be produced in a high yield, but has the disadvantage that the copolymer has a narrow molecular weight distribution, a narrow composition distribution, and a low molecular weight.

Focusing only on increasing the molecular weight of the produced polymer, it is possible to increase the molecular weight to some extent by selecting a metallocene transition metal compound which is one component of the catalyst. For example, JP-A-63-23400
No. 5, using a transition metal compound having 2,3 and 4-substituted cyclopentadienyl groups, and JP-A-2-22
No. 307 proposes using a hafnium compound having a ligand bonded to at least two bridged conjugated cycloalkadienyls to increase the molecular weight of the resulting polymer. However, the catalyst components as described above have complicated synthesis routes and complicated operations,
Further, when hafnium is used as the transition metal species, there is a drawback that the yield of the obtained polymer (yield per catalyst) decreases. Furthermore, the conventional catalyst systems exemplified above are often soluble in the reaction system, and the polymer produced when used in slurry polymerization or gas phase polymerization has a very low bulk density, resulting in poor particle properties. was there.

[0004]

SUMMARY OF THE INVENTION In order to solve the above-mentioned drawbacks of the prior art, the present inventors have used a novel catalyst system having a completely different structure from the conventional catalyst system, and It has been found that a polyolefin suitable for the purpose, that is, a polyolefin having a high molecular weight, a relatively wide molecular weight distribution, a narrow composition distribution, and excellent particle properties can be produced in a high yield (JP-A-5-132518). As a result of further improvements, the inventors of the present invention further studied the above problems, found a specific prepolymerization catalyst, and by using such a catalyst, the polymerization activity was higher than that in the conventional method, and thus obtained. The polymer has a high bulk density and is excellent in particle properties, etc., of course, there is no fouling in the polymerization reactor, and there is virtually no adhesion of the polymer to the stirrer in the polymerization reactor or the inner wall of the reactor. Found. Further, they have found that the catalyst of the present invention has a high initial polymerization activity and is extremely advantageous from the viewpoint of industrial productivity.

[0005]

That is, the present invention is
(1) General formula ^{_{Me 1 R 1 p (OR 2}} ) q X 1 4-p-q
(Wherein Me ¹ is Zr, Ti or H)
f, R ¹ and R ² each represent a hydrocarbon group having 1 to 24 carbon atoms, X ¹ represents a halogen atom, p and q
Are integers respectively satisfying the ranges of 0 ≦ p <4, 0 ≦ q <4, 0 ≦ p + q ≦ 4), and (2) the general formula Me ² R ³ _m (O
R ⁴ ) _n X ² _z-m-n A compound represented by the formula (in the formula, Me
² is an element of groups I to III of the periodic table, R ³ and R ⁴ are each a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom (provided that X ² is a hydrogen atom, Me ² represents a group III element of the periodic table)
z represents the valence of Me ² , and m and n are each 0 ≦ m ≦.
z, an integer satisfying the range of 0 ≦ n ≦ z, and 0 ≦ m
+ N ≦ z), (3) an organic cyclic compound having a conjugated double bond, (4) a modified organoaluminum compound containing an Al—O—Al bond, and (5) an inorganic carrier and / or a particulate polymer carrier. The present invention relates to an olefin polymerization catalyst, which is formed by prepolymerizing olefins with catalyst components obtained by bringing them into contact with each other.
The present invention also relates to a method for producing a polyolefin, which comprises polymerizing or copolymerizing olefins in the presence of such a catalyst.

The catalyst of the present invention is relatively easy to synthesize, has a high activity per transition metal, and is capable of producing a polyolefin with high efficiency. Further, the obtained polyolefin has a high molecular weight and a high molecular weight. The distribution is relatively wide, especially for ethylene / α-olefin copolymers, the composition distribution is narrow, the surface tackiness is extremely low, and the bulk density is high and the powder properties are good. It has many industrial advantages such as high-efficiency production of polyolefin without fouling.

The present invention will be described in more detail below. As described above, the catalyst of the present invention has the following general formula (1): Me ¹ R ¹ _p (OR ² ) _q X ¹
_4-p-q in the compound represented by the component (2) the general formula _{^{Me 2 R 3 m (OR 4}} ) n X 2
Compound represented by _z-mn Component (3) Organic cyclic compound having conjugated double bond, Component (4) Modified organoaluminum compound containing Al-O-Al bond, and Component (5) Inorganic carrier and / or Alternatively, it is formed by prepolymerizing olefins with a catalyst component obtained by bringing the particulate polymer supports into contact with each other.

First, the general formula of component (1), Me ¹ R ¹ _p (O
The compound represented by R ² ) _q X ¹ _4-pq will be described. In the formula, R ¹ and R ² have 1 to 24 carbon atoms,
It preferably represents a hydrocarbon group of 1 to 12, and more preferably 1 to 8, and examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group and an isobutyl group. , Tert-butyl group, cyclobutyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group,
Alkyl groups such as isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, dodecyl group; alkenyl groups such as vinyl group, allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, naphthyl group, etc. And an aralkyl group such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, phenylpropyl group, and neophyll group. These may have branches. X ¹ is a halogen atom of fluorine, iodine, chlorine and bromine, Me ¹ is Zr, Ti or Hf, and preferably Zr. p and q are 0 ≦ p ≦ 4 and 0 ≦ q, respectively.
≤4, 0≤p + q≤4, preferably 0 <p
It is an integer of + q ≦ 4.

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

Trimethyl monochloro zirconium, triethyl monochloro zirconium, tripropyl monochloro zirconium, tri n-butyl monochloro zirconium, tripentyl monochloro zirconium, triphenyl monochloro zirconium, tritolyl monochloro zirconium, tribenzyl monochloro zirconium, triallyl monochloro zirconium, trineo. Phil monochlorozirconium, dimethyldichlorozirconium, diethyldichlorozirconium, dipropyldichlorozirconium, di-n-butyldichlorozirconium, dipentyldichlorozirconium, diphenyldichlorozirconium, ditolyldichlorozirconium, dibenzyldichlorozirconium, diallyldichlorozirconium,
Dineofildichlorozirconium, monomethyltrichlorozirconium, monoethyltrichlorozirconium, monopropyltrichlorozirconium, mono-n-butyltrichlorozirconium, monopentyltrichlorozirconium, monophenyltrichlorozirconium,
Monotolyltrichlorozirconium, monobenzyltrichlorozirconium, monoallyltrichlorozirconium, mononeophyltrichlorozirconium,

Tetrachlorozirconium, trimethoxymonochlorozirconium, dimethoxydichlorozirconium, monomethoxytrichlorozirconium, triethoxymonochlorozirconium, diethoxydichlorozirconium, monoethoxytrichlorozirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, monopropoxytrichlorozirconium. , Tri-n-butoxymonochlorozirconium, di-n
-Butoxydichlorozirconium, mono-n-butoxytrichlorozirconium, tripentyloxymonochlorozirconium, dipentyloxydichlorozirconium, monopentyloxytrichlorozirconium, triphenoxymonochlorozirconium, diphenoxydichlorozirconium, monophenoxytrichlorozirconium, tritolyloxymonochlorozirconium, Ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium, tribenzyloxymonochlorozirconium, dibenzyloxydichlorozirconium, monobenzyloxytrichlorozirconium, triallyloxymonochlorozirconium, diallyloxydichlorozirconium, monoallyloxytrichlorozirconium, trineo I oxy monochloro zirconium, di neophyl oxy zirconium dichloride, mono neophyl oxy trichloro zirconium,

Tetrabromozirconium, trimethylmonobromozirconium, triethylmonobromozirconium, tripropylmonobromozirconium, tri-n-
Butylmonobromozirconium, tripentylmonobromozirconium, triphenylmonobromozirconium, tritolylmonobromozirconium, tribenzylmonobromozirconium, triallylmonobromozirconium, 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,

Trimethoxy monoiodo zirconium, dimethoxy diiodo zirconium, monomethoxy triiodo zirconium, triethoxy monoiodo zirconium, diethoxy diiodo zirconium, monoethoxy triiodo zirconium, tripropoxy monoiodo zirconium, dipropoxy diiodo zirconium, 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, dineofiloxydiiodozirconium, 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 neofiltitanium, tetramethoxy titanium, tetra Ethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentyloxytitanium, tetraphenoxytitanium, tetratolyloxytitanium, tetrabenzyloxytitanium, tetraallyloxytitanium, tetraneophyloxytitanium,

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

Dibenzyloxydichlorotitanium, monobenzyloxytrichlorotitanium, tetrabromotitanium, trimethylmonobromotitanium, triethylmonobromotitanium, tripropylmonobromotitanium, tri-n-butylmonobromotitanium, tribenzylmonobromotitanium, dimethyl Dibromotitanium, diethyldibromotitanium, di-n-butyldibromotitanium, dibenzyldibromotitanium, monomethyltribromotitanium, monoethyltribromotitanium, mono-n-butyltribromotitanium, monobenzyltribromotitanium, 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, tri-n-butoxymonochlorohafnium, di-n-butoxydichloro. Hafnium, mono-n-butoxytrichlorohafnium, tripentyloxymonochlorohafnium, dipentyloxydichlorohafnium, monopentyloxytrichlorohafnium, triphenoxymonochlorohafnium, diphenoxydichlorohafnium, monophenoxytrichlorohafnium, tritolyloxymonochlorohafnium, ditolyloxy. Dichlorohafnium,
Monotolyloxytrichlorohafnium, tribenzyloxymonochlorohafnium, dibenzyloxydichlorohafnium, monobenzyloxytrichlorohafnium, tetrabromohafnium, trimethylmonobromohafnium, triethylmonobromohafnium, tripropylmonobromohafnium, tri-n-butylmonobromo Hafnium, tribenzylmonobromohafnium, dimethyldibromohafnium, diethyldibromohafnium,

Di-n-butyldibromohafnium, dibenzyldibromohafnium, monomethyltribromohafnium, monoethyltribromohafnium, mono-n-butyltribromohafnium, monobenzyltribromohafnium, 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,
Mononeophyll triethoxy hafnium, mononeophyll tripropoxy hafnium, mononeophyll tributoxy hafnium, mononeophyll triphenoxy hafnium, and the like. Of course, in these compounds listed as specific examples of the above component (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.
r (OR) ₄ compound. These compounds can be used as a mixture of two or more kinds.

The component (2) is a compound represented by the following general formula. Me in ^{_{2 R 3 m (OR 4)}} n X 2 z-m-n type, Me ² represents one of the periodic table I~III group element, this lithium, sodium, potassium, magnesium, calcium , Zinc, boron, aluminum and the like. R ³ and R ⁴ represent a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 and more preferably 1 to 8 carbon atoms, which include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, Alkyl group such as butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, dodecyl group; vinyl group , Alkenyl groups such as allyl groups, phenyl groups, tolyl groups, xylyl groups, mesityl groups, indenyl groups, naphthyl groups and other aryl groups; benzyl groups, trityl groups, phenethyl groups, styryl groups, benzhydryl groups, phenylbutyl groups, phenylpropyi groups. And aralkyl groups such as ru group and neophyll group. These may have branches. X ² represents halogen such as fluorine, iodine, chlorine or bromine or represents a hydrogen atom. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. z represents the valence of Me ² . m is a number satisfying 0 ≦ m ≦ z, n is 0 ≦ n ≦ z, and 0 <m + n ≦ z, and preferably m and n are integers.

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

Dimethyl zinc, diethyl zinc, dipropyl zinc, diisopropyl zinc, di-n-butyl zinc, di-t-
Butyl zinc, dipentyl zinc, dioctyl zinc, diphenyl zinc, dibenzyl zinc, trimethylboron, triethylboron, tripropylboron, triisopropylboron, tributylboron, tri-t-butylboron, tripentylboron, trioctylboron, triphenylboron, tri Benzylboron, trimethylaluminum,
Triethyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum fluoride, diethyl aluminum iodide, ethyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum difluoride, ethyl aluminum diiodide, tripropyl aluminum, dipropyl aluminum chloride , Dipropyl aluminum bromide, dipropyl aluminum fluoride, dipropyl aluminum iodide,

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

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

Ethyl aluminum diethoxide, ethyl aluminum dipropoxide, ethyl aluminum dibutoxide, diethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum propoxide, diethyl aluminum butoxide, propyl aluminum dimethoxide, propyl aluminum diethoxide, Propyl aluminum dipropoxide, propyl aluminum dibutoxide, dipropyl aluminum methoxide, dipropyl aluminum ethoxide, dipropyl aluminum propoxide, dipropyl aluminum butoxide, butyl aluminum dimethoxide, butyl aluminum diethoxide, butyl aluminum dipropoxide , Butyl aluminum dibutoxide, dibutyl aluminum Tokishido, dibutyl aluminum ethoxide, dibutyl aluminum propoxide, dibutyl aluminum butoxide

Aluminum hydride, dimethyl aluminum hydride, diethyl aluminum hydride,
Dipropyl aluminum hydride, diisopropyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, methyl aluminum dihydride, ethyl aluminum dihydride, propyl aluminum dihydride, isopropyl aluminum dihydride, butyl aluminum dihydride, Isobutyl aluminum dihydride, hexyl aluminum dihydride, cyclohexyl aluminum dihydride, borane, dimethylboron hydride, diethylboron hydride, methylboron dihydride, ethylboron dihydride, diborane, etc. can be mentioned. That.

As the component (3), a cyclic organic compound having two or more conjugated double bonds is used. Ingredient (3)
Includes two or more, preferably 2 to 4 conjugated double bonds,
More preferably, a cyclic hydrocarbon compound having 1 or 2 or more rings having 2 to 3 and having a total carbon number of 4 to 24, preferably 4 to 12; and the cyclic hydrocarbon compound is partially 1 to 6 Hydrocarbon residues (typically having 1 to 1 carbon atoms)
A cyclic hydrocarbon compound substituted with 12 alkyl groups or aralkyl groups); having 1 or 2 or more rings having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds. , The total carbon number is 4 to 24, preferably 4
An organosilicon compound having a cyclic hydrocarbon group of 1 to 12; an organosilicon compound in which the cyclic hydrocarbon group is partially substituted with 1 to 6 hydrocarbon residues or an alkali metal salt (sodium salt or lithium salt). Is included. Particularly preferably, one having a cyclopentadiene structure in any of the molecules is desirable. Incidentally, as a suitable example of the cyclic hydrocarbon compound, a compound represented by the following general formula can be given.

[0037]

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In the chemical formula 1, R ¹ , R ² , R ³ , R
⁴ is hydrogen or a hydrocarbon residue 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, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, an alkyl group such as an octyl group, an aryl group such as a phenyl group, a methoxy group, an 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, and any two of them jointly form a cyclic hydrocarbon group, Examples thereof include heptatriene, aryl and condensed rings thereof. Suitable examples of the compound represented by Chemical formula 1 include cyclopentadiene, indene, azulene, and their alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives. Further, a compound in which the compound represented by Chemical formula 1 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.

The organic cyclic hydrocarbon compounds usable as the component (3) will be briefly described below. Cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene,
t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene,
1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-dimethylindene, 4,5,
Cyclohexyl having 7 to 24 carbon atoms such as 6,7-tetrahydroindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, methylcyclooctatetraene, azulene, methylazulene, ethylazulene, fluorene and methylfluorene. Polyene or substituted cyclopolyene,

Monocyclopentadienylsilane, biscyclopentadienylsilane, triscyclopentadienylsilane, tetrakiscyclopentadienylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadienylmonoethylsilane, monocyclo Pentadienyldimethylsilane, Monocyclopentadienyldiethylsilane, Monocyclopentadienyltrimethylsilane, Monocyclopentadienyltriethylsilane, Monocyclopentadienylmonomethoxysilane, Monocyclopentadienylmonoethoxysilane, Monocyclo Pentadienylmonophenoxysilane,

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

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

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

Further, any one of the above-mentioned compounds may 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.

As the component (4) of the present invention, Al-O-
Modified organoaluminum compounds containing Al bonds are used. Such a modified organoaluminum compound is usually 1 to 100, preferably 1 to 50 Al-OA in a molecule.
It contains an l-bond and is usually obtained by reacting an organoaluminum compound with water. The modified organoaluminum may be linear or cyclic.

The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon. The inert hydrocarbon is preferably an aliphatic, alicyclic or aromatic hydrocarbon such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene.

These organoaluminum compounds are represented by the general formula R _n AlX _3-n (wherein R is a C 1-18, preferably C 1-12 alkyl group, alkenyl group, aryl group, aralkyl group, etc.). Represents a chain or branched hydrocarbon group, X represents a hydrogen atom or a halogen atom, and n is 1 ≦
Indicates an integer in the range of n ≦ 3. ) Is desirable, and trialkylaluminum is particularly preferably used. Examples of the alkyl group in the trialkylaluminum include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. A methyl group is preferred. Also, a plurality of types can be used in combination.

The reaction ratio (water / Al (molar ratio)) between water and an organic alkyl group compound is usually 0.25 / 1 to 1.2 /.
It is desirable that it is 1, preferably 0.5 / 1 to 1/1. The reaction temperature is generally -70 ° C to 100 ° C, preferably-
It is in the range of 20 ° C to 20 ° C. The reaction time is not particularly limited, but is usually 5 minutes to 24 hours, preferably 10 minutes to 5
Selected in a time range. As water required for the reaction, not only water itself but also crystal water contained in copper sulfate hydrate, aluminum sulfate hydrate, and the like can be used.

By reacting alkylaluminum with water, a modified organoaluminum usually called aluminoxane can be obtained. Of course, it is also possible to use a combination of two or more modified organoaluminum compounds in the present invention.

As the component (5) of the present invention, an inorganic carrier and / or a particulate polymer carrier is used. The inorganic carrier may be in any shape such as powder, granules, flakes, foil or fibrous as long as it retains its original shape in the step of preparing the catalyst of the present invention. Even in the shape of, the maximum length is usually 5 to 2
A range of 00 μm, preferably 10 to 100 μm is suitable. The inorganic carrier is preferably porous, and usually has a surface area of 50 to 1000 m ² / g.
The pore volume is in the range of 0.05 to ³ cm ³ . As the inorganic carrier of the present invention, a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate, or a mixture thereof can be used, and these are usually in the air at 200 to 900 ° C. or in the air, such as nitrogen and argon. Used by firing in an inert gas.

Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like. Further, as the metal oxide, the periodic table I to V is used.
Group III single oxides or complex oxides may be mentioned, for example SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ ,
TiO ₂ , ZrO ₂ , Fe ₂ O ₃ , SiO ₂ · Al ₂ O
₃ , Al ₂ O ₃ · MgO, Al ₂ O ₃ · CaO, Al ₂
O ₃ · MgO · CaO, Al ₂ O ₃ · MgO · Si
O ₂ , Al ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ ,
Examples thereof include Al ₂ O ₃ .NiO and SiO ₂ .MgO. In addition, the above formula represented by an oxide is not a molecular formula but represents only a composition, that is, the structure and the component ratio of the multiple oxide used in the present invention are not particularly limited. The metal oxide used in the present invention may adsorb a small amount of water, or may contain a small amount of impurities.

As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable. The metal carbonate is preferably an alkali metal or alkaline earth metal carbonate, and specific examples thereof include magnesium carbonate, calcium carbonate and barium carbonate. Examples of the carbonaceous material include carbon black and activated carbon. Any of the above inorganic carriers can be preferably used in the present invention, but the use of metal oxides such as silica and alumina is particularly preferable.

On the other hand, as the particulate polymer carrier, either a thermoplastic resin or a thermosetting resin can be used as long as it does not melt and remains solid during catalyst preparation and polymerization reaction. The particle size is usually 5-2000μ
m, preferably in the range of 10 to 100 μm. The molecular weight of these polymer carriers is not particularly limited as long as the polymer can exist as a solid substance at the time of catalyst preparation and polymerization reaction, and can be arbitrarily selected from low molecular weight to ultra high molecular weight. It can be used. Specifically, various polyolefins (preferably having 2 to 12 carbon atoms) represented by particulate ethylene polymers, ethylene / α-olefin copolymers, propylene polymers or copolymers, poly-1-butene, and the like, Polyester, polyamide, polyvinyl chloride, polymethyl methacrylate, polymethyl acrylate, polystyrene, polynorbornene, as well as various natural polymers and mixtures thereof can be used as polymer carriers.

Of course, the above-mentioned inorganic carrier and particulate polymer carrier can be used as they are as the component (5) of the present invention, but as a pretreatment, these carriers are used as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-aluminum. An organic aluminum compound such as hexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylmonoethoxyaluminum, triethoxyaluminum, etc. Or Al-O-Al
It can also be used as the component (5) after contact treatment with a modified organoaluminum compound containing a bond (this compound will be described later) or a silane compound.

Further, regarding the inorganic carrier, it may be an alcohol, an active hydrogen-containing compound such as an aldehyde, an electron-donating compound such as an ester or an ether, an alkoxide group such as a tetraalkoxysilicate, a trialkoxyaluminum or a transition metal tetraalkoxide. A method of contacting a compound or the like in advance and then using it as the component (5) is also preferably used.

The contact treatment method is usually an aromatic hydrocarbon (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, etc. in an inert atmosphere such as nitrogen or argon. Method of contacting a carrier with a pretreatment compound in the presence of liquid inert hydrocarbon such as aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as dodecane and cyclohexane with or without stirring Is mentioned. This contact is usually from -100 ° C to 200 ° C, preferably from -50 ° C.
30 minutes to 50 hours at a temperature of 100 ° C., preferably 1
It is desirable to carry out for 24 hours.

The catalytic reaction is carried out in a solvent in which the above-mentioned pretreatment compound is soluble, that is, benzene, toluene,
It is preferable to carry out in an aromatic hydrocarbon such as xylene or ethylbenzene (usually having a carbon number of 6 to 12). In this case, after the catalytic reaction, this is used as it is without preparing the solvent to prepare the catalyst component of the present invention. Can be used for Further, in the contact reaction product concerned, a liquid inert hydrocarbon in which the pretreatment compound is insoluble or sparingly soluble (for example, when the pretreatment compound is a modified organoaluminum compound, pentane, hexane, decane, dodecane, cyclohexane). (Aliphatic or alicyclic hydrocarbon, etc.) is added and component (5) is precipitated as a solid component and dried, or part or all of the aromatic hydrocarbon that is the solvent during the pretreatment is dried. After removal by means such as the above, the component (5) can be taken out as a solid component.

The ratio of the inorganic carrier and / or particulate polymer carrier to be subjected to the pretreatment and the pretreatment compound is
There is no particular limitation as long as the object of the present invention is not impaired, but it is usually selected within the range of 1 to 10000 mmol, preferably 5 to 1500 mmol (however, Al atom concentration in modified aluminum compound) per 100 g of carrier. .

The catalyst components before the prepolymerization used in the present invention are, as described above, [Component-1] to [Component-5].
Are prepared by bringing them into contact with each other, but the order of contacting these components is not particularly limited, but the preferred contacting method is (A) [component-1] to [component-5] at the same time. Method of contacting (B) [Component-1], [Component-2], [Component-3],
Method of sequentially contacting [Component-4] and [Component-5] (C) [Component-1], [Component-3], [Component-2],
Method of sequentially contacting [Component-4] and [Component-5] (D) [Component-1], [Component-5], [Component-2],
Method of sequentially contacting [Component-3] and [Component-4] (E) [Component-4], [Component-5], [Component-2],
Method of sequentially contacting [Component-3] and [Component-1] (F) [Component-4], [Component-5], [Component-1],
Method of sequentially contacting [Component-2] and [Component-3] (G) [Component-1], [Component-2], [Component-3],
Method of contacting [Component-4] simultaneously and then contacting [Component-5] (H) [Component-1], [Component-2] and [Component-3] are simultaneously contacted, and then [Component-4] ] After contacting [component-
(I) [Component-1], [Component-2] and [Component-3] are brought into contact with each other at the same time, and then [Component-5] is brought into contact with [Component-
(J) [Component-1], [Component-2], [Component-3] are brought into contact with each other at the same time, and they are then brought into contact with [Component-4] and [Component-5]. Method of contacting (K) [Component-1], [Component-5], and then sequentially contacting [Component-3], [Component-4], [Component-5] (L) [Component -2], [Component-5], and then sequentially contacting [Component-3], [Component-1], and [Component-5] (M) [Component-1], [Component-5] Is preferably contacted with, and then contacted with what is contacted with [Component-2], [Component-3], and [Component-4].

The method of contacting these five components is not particularly limited, but usually, in an inert atmosphere such as nitrogen or argon,
Generally, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene (usually having 6 to 12 carbon atoms), butane, pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, methylcyclopentane, and other aliphatic hydrocarbons. Alternatively, a method of contacting each component with or without stirring in a liquid inert hydrocarbon medium such as an alicyclic hydrocarbon (usually having a carbon number of 4 to 12) or kerosene is preferably adopted. Of course, the media may or may not be removed at each contact step. This contact is usually -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C.
It is desirable to carry out at the temperature of 10 minutes to 50 hours, preferably 30 minutes to 24 hours. When a particulate polymer carrier is used as the component (5), it is desirable that the catalytic reaction is carried out under the condition that the polymer carrier remains substantially solid.

When the components (1) to (5) are brought into contact with each other, as described above, an aromatic hydrocarbon solvent in which a certain component is soluble and an aliphatic or fat in which a certain component is insoluble or sparingly soluble are used. Although any of the aromatic hydrocarbon solvents can be used, it is particularly preferable to use an aromatic hydrocarbon in which the components (1) to (4) are soluble as the solvent. Further, in the case where the catalytic reaction of each component is carried out stepwise, the soluble aromatic hydrocarbon solvent used in the preceding stage may be used as it is as a solvent for the catalytic reaction in the subsequent stage without removing it. . Further, after the first contact using a soluble solvent, a liquid inert hydrocarbon in which a certain component is insoluble or sparingly soluble (for example, pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, methylcyclopentane). Or other aliphatic or alicyclic hydrocarbon) to recover the desired product as a solid, or once the aromatic hydrocarbon solvent is partially or wholly removed by a method such as drying to produce the desired product. After removal of the product as a solid, the subsequent catalytic reaction of the desired product can also be carried out using any of the inert hydrocarbon solvents described above. Further, in the present invention, it is possible to carry out the catalytic reaction of each component a plurality of times. After contacting each component in each inert hydrocarbon medium, the solvent can be directly subjected to prepolymerization without removing the solvent, and the contact reaction product can be subjected to any means such as reduced pressure or inert gas blowing. The catalyst component of the invention can be taken out in substantially solid form before it is subjected to prepolymerization.

The proportions of the components (1) to (5) used in the present invention are the same as those of the component (1) and the component (2).
The component (2) is usually 0.01 to 100 mol per mol,
Preferably 0.1 to 50 mol, more preferably 1 to 2
The range of 0 mol is desirable, and the components (1) and (3)
As for the component (3), the amount of the component (3) is usually 0.01 to 100 mol, preferably 0.1 to 50 mol, and more preferably 0.1 to 20 mol. Regarding 1) and component (4), the atomic ratio of aluminum in the modified organoaluminum compound to the transition metal (Ti, Zr, Hf) in the catalyst component is usually 1 to 10.
The range of 000 mol, preferably 10 to 1000 mol is desirable. As for the component (1) and the component (5), the component (1) was added to the transition metal (Ti,
Zr, Hf) is usually 0.01 to 1000 mmol, preferably 0.1 to 500 mmol, more preferably 0.1.
It is desirable to use in the range of 5 to 100 mmol.

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

The following combinations are mentioned as one of the other suitable combinations. Tetraalkyltitanium compounds such as tetramethyltitanium among the components (1); tetraalkoxytitanium compounds such as tetranormalbutoxytitanium or tetraisopropoxytitanium or tetraaralkyltitanium compounds such as tetrabenzyltitanium; trimethylaluminum among the components (2) A trialkylaluminum compound such as triethylaluminum, triisobutylaluminum, trihexylaluminum or tridecylaluminum or a halogen-containing alkylaluminum compound such as diethylaluminum chloride or ethylaluminum dichloride, a hydride such as diisobutylaluminum hydride, a component (3) Of which, indene; methylindene or trimethylsilylindene Which indene derivative; cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene, etc. cyclopentadiene derivative; Bonded compounds or dimethylsilylbiscyclopentadiene and other compounds of the general formula A _L SiR
A compound represented by _4-L , methylaluminoxane among the components (4), and silica, alumina, silica-alumina, silica-titania among the components (5).

The following combinations are mentioned as one of the other suitable combinations. A tetraalkoxyzirconium compound such as tetranormal butoxyzirconium or tetraisopropoxyzirconium among the components (1),
Of the component (2), a trialkylaluminum compound such as triethylaluminum, triisobutylaluminum, trihexylaluminum or tridecylaluminum or an alkylaluminum alkoxide compound such as diethylaluminum butoxide, ethyldibutoxyaluminum or diethylethoxyaluminum. , Hydrides such as diisobutylaluminum hydride, indene of component (3); indene derivatives such as methylindene or trimethylsilylindene; cyclopentadiene derivatives such as cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene ; Bisindenylethane or isopropylbissik Indene derivatives or compounds cyclopentadiene derivative are bonded via an alkylene group or the formula A _L SiR compound represented by the _4-L, such as dimethylsilyl bis cyclopentadiene such as pentadiene, methylaluminoxane and of the components (4) Of the components (5), silica, alumina, silica-alumina, silica-titania.

The following combinations are mentioned as one of other suitable combinations. Of the component (1), a zirconium chloride compound such as zirconium tetrachloride, phenoxyzirconium chloride, trichloride isopropoxyzirconium or benzylzirconium trichloride, and an alkyllithium compound such as butyllithium or methyllithium or dibutylmagnesium in the component (2). , An alkyl magnesium compound such as ethyl magnesium bromide or butyl magnesium chloride, indene of component (3); an indene derivative such as methyl indene or trimethylsilyl indene; cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene Derivatives such as cyclopentadiene; bisindenylethane or isopropylbisshi Compound indene derivative or cyclopentadiene derivative such as Ropentajien are bonded through an alkylene group or the formula A _L SiR compound represented by the _4-L, such as dimethylsilyl bis cyclopentadiene, methylaluminoxane of the components (4) And silica among the components (5),
Alumina, silica-alumina, silica-titania.

The following combinations are mentioned as one of other suitable combinations. A tetraalkoxyzirconium compound such as tetranormal butoxyzirconium or tetraisopropoxyzirconium among the components (1),
Of the component (2), a trialkylaluminum compound such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum or tridecylaluminum, or a halogen-containing alkylaluminum compound such as diethylaluminum chloride or ethylaluminum dichloride, the component (3) Among them, indene; indene derivatives such as methylindene or trimethylsilylindene; cyclopentadiene derivatives such as cyclopentadiene, methylcyclopentadiene, dimethylcyclopentadiene, trimethylcyclopentadiene or trimethylsilylcyclopentadiene; indene derivatives such as bisindenylethane or isopropylbiscyclopentadiene Or cyclopentadiene Compound conductor is represented by the general formula A _L SiR _4-L, such as a compound or dimethylsilyl bis cyclopentadiene bonded through an alkylene group, the silica of methylaluminoxane and components of the components (4) (5), Alumina, silica-alumina, silica-titania.

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

The catalyst of the present invention can be obtained by prepolymerizing olefins with the catalyst components obtained by bringing the components (1) to (5) into contact with each other. The olefins used in the prepolymerization 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 specific examples thereof include ethylene, propylene, butene-1, hexene-1, 4-methylpentene-1. To be done. In the prepolymerization, these olefins can be homopolymerized, and also two or more kinds of α-olefins can be copolymerized, and the copolymerization can be any of alternating copolymerization, random copolymerization and block copolymerization. It does not matter if there is.

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 that 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%.

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

The olefin used in the prepolymerization may be the same as or different from that used in the main polymerization. In the present invention, the olefin is prepolymerized to the catalyst component obtained by bringing the components (1) to (5) into contact with each other. Further, in addition to the catalyst component, the prepolymerization is performed in the coexistence of the organoaluminum compound. be able to.

As such an organoaluminum compound,
For example, the general formula R _n AlX _3-n (wherein R is a carbon number 1 to
18, preferably 1 to 12 straight-chain or branched hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups and aralkyl groups, alkoxy groups or aryloxy groups, X represents a hydrogen atom or a halogen atom, and n is 1 A range of ≦ n ≦ 3 is shown. The compound represented by () is mentioned as a suitable thing. Examples of the alkyl group in the formula include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and the like. Groups are preferred. Examples of the organoaluminum compound represented by the general formula include trimethylaluminum, triethylaluminum, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum fluoride, diethylaluminum iodide, ethylaluminum dichloride, ethylaluminum dibromide, and ethylaluminum difluoride. Ride, ethyl aluminum diiodide, tripropyl aluminum, dipropyl aluminum chloride, dipropyl aluminum bromide, dipropyl aluminum fluoride, dipropyl aluminum iodide,

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

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

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

The organoaluminum compound can be used as a mixture or an addition compound of an organoaluminum compound represented by the general formula and an organic acid ester. Examples of organic acid esters include methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, butyl benzoate, and hexyl benzoate. , Cyclopentyl benzoate, cyclohexyl benzoate, methyl p-toluate, ethyl p-toluate, phenyl p-toluate,
Examples thereof include ethyl o-toluate and the like, preferably benzoic acid, o- or p-toluic acid or an alkyl ester of anisic acid, and particularly preferably methyl ester or ethyl ester thereof.

Further, as such organic aluminum,
Other suitable examples include so-called modified organoaluminum compounds containing an Al-O-Al bond obtained by reacting an organoaluminum compound with water. In addition,
Examples of the compound include the same as the component (4) used in the preparation of the catalyst component.

Of course, a plurality of kinds of organic aluminum compounds may be used in combination, and specifically, a compound represented by the general formula R _n AlX _3-n may be used in combination with a modified organic aluminum compound. The compounds represented by the formula R _n AlX _3-n or different modified organoaluminum compounds may be used. As the organoaluminum compound, trialkylaluminum is particularly preferable, and among them, triethylaluminum, triisobutylaluminum and tri-n-hexylaluminum are preferable.

When the organoaluminum compound is used in the prepolymerization, the ratio of its use is based on the transition metal (Me ¹ ) in the catalyst component obtained by bringing the components (1) to (5) into contact with each other. The atomic ratio of aluminum in the organic aluminum compound is usually 1000 or less, preferably 0.0
It is desirable to select in the range of 01 to 1000, more preferably 0.01 to 500. As a specific embodiment, a method of prepolymerizing in the absence of a solvent in the presence of a trace amount of an organoaluminum compound that reacts with impurities in a polymerization reaction container and impurities in a raw material is preferable.

The prepolymerization for obtaining the catalyst of the present invention can be carried out by solution polymerization, slurry polymerization, or substantially solvent-free gas phase polymerization, and can be carried out in an inert hydrocarbon medium or in the absence of a medium. Be seen. Examples of the inert medium include aromatic hydrocarbons (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, and ethylbenzene, butane, pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, Examples thereof include aliphatic or alicyclic hydrocarbons (usually having 4 to 12 carbon atoms) such as methylcyclopentane, and kerosene.

Preliminary polymerization may be carried out batchwise or continuously, and may be carried out by any of reduced pressure, normal pressure and increased pressure. Suitable polymerization conditions include a temperature of usually -10 ° C to 200 ° C., preferably 0 ° C. to 150 ° C., more preferably 20 ° C. to 100 ° C., the pressure is usually normal pressure to 70 kg / cm ² G, preferably normal pressure to 20 k.
g / cm ² G is desirable, is not particularly restricted but the polymerization time (residence time) is usually 3 minutes to 5 hours, preferably is desirably 15 minutes to 2 hours. Also, a molecular weight modifier such as hydrogen may be used.

The olefin polymerization catalyst of the present invention obtained by such prepolymerization contains 0.01 to 100 g of olefin per 1 g of catalyst component obtained by contacting components (1) to (5) with each other. , Preferably 0.1-5
It is desirable to obtain it by polymerizing or copolymerizing 0 g, particularly preferably 0.5 to 10 g of olefin.
Incidentally, the main polymerization may be carried out continuously with the preliminary polymerization, or the main polymerization may be carried out after the polymerization reaction is once completed, or may be once taken out as a solid catalyst and then subjected to the main polymerization. .

Thus, the olefin polymerization catalyst of the present invention is obtained, and in the present invention, a polyolefin can be produced by polymerizing or copolymerizing olefins in the presence of such a catalyst. Examples of the olefins preferably used in the method for producing a polyolefin of the present invention include the same olefins as those exemplified as those already used in the prepolymerization. Further, the catalyst or the production method of the present invention is also suitably used when the obtained polyolefin is further polymerized with a polar monomer for modification. Examples of the polar monomer include methyl acrylate, methyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, monomethyl maleate, diethyl fumarate, and dimethyl itaconate. At this time, the content of the polar monomer in the modified polyolefin is usually 0.1 to 10 mol%, preferably 0.2 to 2 mol%.

The main polymerization reaction can be carried out in the presence of the above-mentioned catalyst by slurry polymerization, solution polymerization or substantially solvent-free gas phase polymerization, preferably slurry polymerization, gas phase polymerization, and more preferably Slurry polymerization is desirable, and it is effective in preventing fouling of the polymer onto the wall of the polymerization reactor and the stirring blade. The forms of the prepolymerization and the main polymerization may be the same or different. For example, the prepolymerization is a slurry and the main polymerization is a gas phase polymerization, the prepolymerization is a slurry polymerization and the main polymerization is a slurry polymerization, and the prepolymerization is a gas phase polymerization. The polymerization may be slurry polymerization, the preliminary polymerization may be gas phase polymerization, and the main polymerization may be gas phase polymerization.

The polymerization reaction is carried out in a state where oxygen, water, etc. are substantially cut off, and in the case of slurry or solution polymerization, it is carried out in an inert hydrocarbon medium. As the inert medium, benzene, toluene are generally used. , Aromatic hydrocarbons such as xylene and ethylbenzene (usually having 6 to 12 carbon atoms), butane, pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, methylcyclopentane and other aliphatic or alicyclic compounds Examples include hydrocarbons (usually having 4 to 12 carbon atoms) and kerosene. It is possible to carry out the polymerization in the presence of an organoaluminum compound. In addition,
Examples of the organoaluminum compound include those similar to the organoaluminum compounds exemplified as those used in the prepolymerization, that is, the general formula R _n AlX.
Examples thereof include a compound represented by _3-n and a modified organoaluminum compound having an Al-O-Al bond, and the amount used is not particularly limited, but a transition metal (Me ¹ ) in a normal catalyst is used.
The atomic ratio of aluminum in the organoaluminum compound to 1000 is usually 1000 or less, preferably 0.001 to 10
00, more preferably 0.01 to 500 is desirable.

The polymerization conditions are such that the temperature is usually from 20 ° C to 200 ° C.
℃, preferably 50 ℃ ~ 100 ℃ is desirable, the pressure is usually atmospheric pressure ~ 70kg / cm ² G, preferably atmospheric pressure ~ 20k.
g / cm ² G is desirable, and the polymerization time (residence time) is not particularly limited, but is usually 3 minutes to 10 hours, preferably 15 minutes to 5 hours. The molecular weight of the resulting polymer is
It can be adjusted to some extent by appropriately selecting conditions such as the polymerization temperature, the amount of the catalyst used, the composition ratio of the catalyst raw material, and the polymerization conditions, but the molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system. be able to. Further, the method of the present invention can be applied without problems to multi-stage polymerization of two or more stages in which the hydrogen concentration, the polymerization temperature, the amount of catalyst, and the polymerization form (slurry polymerization and gas phase polymerization) are different from each other.

[0091]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples. The physical properties of the polymers obtained in Examples and Comparative Examples were measured by the following methods. -Melt flow rate (MFR) It measured based on ASTM D 1238-57T.
(190 ℃, 2.16kg load) ・ Flow ratio MFR10kg load (190 ℃) and MFR2.16kg
The melt index ratio (10 kg load / 2.16 kg load) of the load (190 ° C.) was calculated. This was used as a measure of the molecular weight distribution. -Amount of n-hexane extracted Sheet pressed (150 mm x 40 m)
m, thickness 0.2 mm) was extracted for 5 hours at the boiling point of hexane. -Density It measured based on ASTM D 1505-68.

The modified organoaluminum compound (methylalumoxane) used in Examples and Comparative Examples was prepared as follows. That is, 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 in 50 ml of toluene. Then 1m concentration
mol / ml trimethylaluminum solution 150m
1 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.
Allowed to react for hours. 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.

Example 1 (Preparation of catalyst component) 100 ml of purified toluene was added to a 300 ml three-necked flask and cooled to -20 ° C. Next, zirconium tetrapropoxide (Zr (OPr) ₄ )
0.25g was added, then triethylaluminum 0.7
g and 0.7 g of indene were added. After the addition is complete, -20 ° C
After stirring for 1 hour, heat gradually while stirring,
The temperature was raised to 20 ° C. over 2 hours, and the reaction was further stirred at 45 ° C. for 3 hours. The solution was lowered to 25 ° C and then 4
SiO ₂ baked at 00 ° C. for 5 hours (manufactured by Fuji Devison,
# 952) (15 g) was added, and the mixture was kept at 25 ° C. and stirred for 2 hours. Then, a toluene solution of methylalumoxane (concentration: A
100 ml of 1 mmol / ml (1 atom) was added.
After the addition was completed, the mixture was reacted with stirring at 25 ° C for 3 hours. Then, the solvent was removed under a nitrogen blow and under reduced pressure to obtain 22 g of a solid catalyst component.

(Preparation of Gas-Phase Prepolymerization Catalyst) To a 500 ml autoclave equipped with a stirrer, which had been dried under heating under reduced pressure, 2 g of the above solid catalyst component was added at room temperature under a nitrogen atmosphere, and then 65 ° C.
The temperature was raised to 1, and prepolymerization of a butene-1 / ethylene (molar ratio 0.04) mixed gas was performed at 0.5 kgf / cm ² · G for 10 minutes. After the prepolymerization, 4 g of a gas phase prepolymerized catalyst having good fluidity was obtained. This was a polymer 1 g / g solid catalyst.

(Ethylene / Butene-1 Copolymerization / Slurry Polymerization) 1000 ml of hexane and 1 mmol of triethylaluminum and 1 mmol of triethylaluminum were added to a sufficiently dried 2 L autoclave at room temperature under a nitrogen atmosphere, and then the above preliminary gas phase polymerization catalyst 2 was added.
After the addition of 00 mg, the temperature was raised to 80 ° C., 30 g of butene-1 was injected with ethylene, and the total pressure was 10 kgf / cm ^2.
Keeping at G, polymerization was carried out for 2 hours. After the polymerization, it was air-dried as it was to obtain 65 g of butene-1 / ethylene copolymer having a bulk density of 0.45. The inner wall of the 2 L autoclave and the stirring blade were very clean without polymer adhesion. The physical properties of the obtained polymer are shown in Table 1.

Comparative Example 1 In the slurry polymerization ethylene / butene-1 copolymerization of Example 1, except that 200 mg of the gas phase prepolymerization catalyst was replaced by 100 mg of the catalyst component before the gas phase prepolymerization catalyst was used. The same procedure as 1 was performed. After polymerization, air-dried as it was, 60 g of butene-1 having a bulk density of 0.28.
/ Ethylene copolymer was obtained. The adhesion of the polymer to the inner wall of the 2 L autoclave and the stirring blade was very large. The physical properties of the obtained polymer are shown in Table 1.

Example 2 (Ethylene / butene-1 Copolymerization / Gas Phase Polymerization) Using the gas phase prepolymerization catalyst obtained in Example 1, ethylene and butene-1 were copolymerized by a gas phase polymerization method. In a 2 L autoclave equipped with a sufficiently dried stirrer, 1 mmol of triethylaluminum and 200 mg of a gas phase prepolymerization catalyst component were added at room temperature under a nitrogen atmosphere, and the mixture was heated to 80 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.12) was introduced so as to be 9 kgf / cm ² · G to start polymerization, and ethylene and butene-1 was added.
1 mixed gas (butene-1 / ethylene molar ratio 0.0
5) continuous supply, total pressure 9kgf / cm ² · G
Polymerization was carried out for 2 hours while maintaining After polymerization, the bulk density is 0.
70 g of butene-1 / ethylene copolymer with 48 were obtained. No polymer adhered to the inner wall of the 2 L autoclave and the stirring blade. The polymerization results are shown in Table 1.

Example 3 (Preparation of catalyst component) 100 ml of purified toluene was added to a 300 ml three-necked flask, 0.25 g of zirconium tetrabutoxide (Zr (OBu) ₄ ) was added, and then 1.7 g of triethylaluminum. Indene 0.7g
Was added to raise the temperature and the reaction was carried out with stirring at 120 ° C. for 2 hours. After the reaction, the mixture was cooled to 25 ° C., and a toluene solution of methylalumoxane (concentration; Al atom was 1 mmol /
100 ml) was added. After the addition was completed, the mixture was reacted with stirring at 25 ° C for 3 hours. 15 g of SiO ₂ (manufactured by Fuji Devison Co., Ltd., # 952) which was calcined at 400 ° C. for 5 hours in this reaction solution
Was added to raise the temperature to 40 ° C., and the mixture was reacted with stirring at 40 ° C. for 2 hours. Then, the solvent was removed under a nitrogen blow and reduced pressure to obtain 24 g of a solid catalyst component.

(Preparation of Gas Phase Prepolymerization Catalyst) To a 500 ml autoclave equipped with a stirrer, which had been dried under heating and reduced pressure, 1 mmol of triethylaluminum and 2 g of the above solid catalyst component were added at room temperature under a nitrogen atmosphere, and then the temperature was raised to 65 ° C. to reduce ethylene to 0. Polymerization was performed at 0.5 kgf / cm ² · G for 15 minutes.
After the polymerization, 4 g of a gas phase prepolymerization catalyst having good fluidity was obtained.
This was a polymer 1 g / g solid catalyst.

(Ethylene / Butene-1 Copolymerization / Slurry Polymerization) To a sufficiently dried 2 L autoclave, 1000 ml of hexane and 200 mg of the above gas phase prepolymerization catalyst were added at room temperature under a nitrogen atmosphere, and the temperature was raised to 80 ° C. to 30 g. Butene-1 of No.1 is press-fitted with ethylene and the total pressure is 10 kgf / cm.
Maintained at ² · G, it was carried out for 2 hours polymerization. After the polymerization, it was air-dried as it was to obtain 63 g of butene-1 / ethylene copolymer having a bulk density of 0.45. The inner wall of the 2 L autoclave and the stirring blade were very clean without polymer adhesion. The polymerization results are shown in Table 1.

Example 4 A slurry prepolymerized catalyst was prepared using the catalyst component prepared in Example 3. (Preparation of slurry prepolymerization catalyst) In a 500 ml three-necked flask equipped with a sufficiently dried stirrer, 200 ml of hexane and 1 m of triethylaluminum at room temperature under a nitrogen atmosphere.
mol and 1 g of the catalyst component prepared in Example 3 were added. After the addition, the temperature is raised to 30 ° C., and the mixture gas of ethylene and butene-1 is added under stirring and normal pressure (molar ratio of butene-1 / ethylene of 0.
05) was continuously fed to carry out prepolymerization for 45 minutes.
After prepolymerization, the supernatant hexane was drawn off, and then washed twice with 100 ml of hexane. After washing, nitrogen blowing and vacuum drying were performed to obtain 2 g of a slurry prepolymerization catalyst.

(Ethylene / Butene-1 Copolymerization / Slurry Polymerization) 1000 ml of hexane and 200 mg of the above slurry prepolymerization catalyst were added to a sufficiently dried 2 L autoclave at room temperature under a nitrogen atmosphere and then the temperature was raised to 80 ° C. to 30 g.
Butene-1 is press-fitted with ethylene to give a total pressure of 10 kgf / c
Polymerization was carried out for 2 hours while maintaining m ² · G. After the polymerization, it was air-dried as it was to obtain 45 g of butene-1 / ethylene copolymer having a bulk density of 0.48. The inner wall of the 2 L autoclave and the stirring blade were very clean without polymer adhesion. The polymerization results are shown in Table 1.

Example 5 Gas phase polymerization was carried out using the slurry prepolymerization catalyst prepared in Example 4. (Ethylene / Butene-1 Copolymerization / Gas Phase Polymerization) A fully dried 2 L autoclave equipped with a stirrer was charged with 200 mg of the slurry prepolymerization catalyst component at room temperature under a nitrogen atmosphere and heated to 80 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.
11) was charged so as to be 9 kgf / cm ² · G to start polymerization, and while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05), Polymerization was carried out for 2 hours while maintaining the total pressure at 9 kgf / cm ² · G. After the polymerization, 40 g of butene-1 / ethylene copolymer having a bulk density of 0.47 was obtained. No polymer adhered to the inner wall of the 2 L autoclave and the stirring blade. The polymerization results are shown in Table 1.

Example 6 (Preparation of catalyst component) 100 ml of purified toluene was added to a 300 ml three-necked flask, and then alumina Al ₂ O ₃ was added.
(Catalyst Kasei, surface area 300 m ² / g, average particle size 60μ
m) and 0.58 g of zirconium tetrabutoxide (Zr (OBu) ₄ ) dissolved in 50 ml of toluene were added, and the mixture was stirred and reacted at 40 ° C. for 2 hours. To this reaction solution, 0.86 g of biscyclopentaenylmethylsilane and then 2.38 g of triisobutylaluminum were added to raise the temperature, and the mixture was reacted with stirring at 120 ° C. for 2 hours. After the reaction, 25 ℃
It was cooled to 150 m, and a toluene solution of methylalumoxane (concentration; 1 mmol / ml in terms of Al atom) was added to 150 m.
1 was added. After the addition was completed, the mixture was reacted with stirring at 25 ° C for 3 hours. Then, the solvent was removed under a nitrogen blow and reduced pressure to obtain 27 g of a solid catalyst component.

(Preparation of Gas Phase Prepolymerization Catalyst) 1 mmol of triethylaluminum and 2 g of the above solid catalyst component were added at room temperature under a nitrogen atmosphere to a 500 m autoclave equipped with a stirrer which had been dried under heating under reduced pressure, and the temperature was raised to 65 ° C.
0.25k of 1 / ethylene (molar ratio 0.04) mixed gas
Prepolymerization was carried out at gf / cm ² · G for 10 minutes. After the prepolymerization, 3 g of a gas phase prepolymerized catalyst having good fluidity was obtained. This was a polymer 0.5 g / g solid catalyst.

(Ethylene / Butene-1 Copolymerization / Slurry Polymerization) 1000 ml of hexane and 200 mg of the above gas phase prepolymerization catalyst were added to a sufficiently dried 2 L autoclave at room temperature under a nitrogen atmosphere, and then the temperature was raised to 80 ° C. to 30 g. Butene-1 of No. 1 was press-fitted with ethylene, and the total pressure was 10 kgf / cm ^2.
-Kept at G and polymerized for 2 hours. After the polymerization, it was air-dried as it was to obtain 150 g of butene-1 / ethylene copolymer having a bulk density of 0.45. The inner wall of the 2 L autoclave and the stirring blade were very clean without polymer adhesion. The polymerization results are shown in Table 1.

Example 7 (Preparation of catalyst component) 100 ml of purified toluene was added to a 300 ml three-necked flask, and then 1.2 g of diethylaluminum chloride and 1.
6 g and 0.21 g of zirconium tetraethoxide (Zr (OEt) ₄ ) dissolved in 50 ml of toluene were added to increase the temperature, and the mixture was reacted with stirring at 120 ° C. for 2 hours. After the reaction,
The mixture was cooled to 25 ° C., and a toluene solution of methylalumoxane (concentration; Al atom was 1 mmol / ml) was added thereto 15
0 ml was added. After completion of the addition, the mixture was reacted with stirring at 25 ° C. for 3 hours. To this reaction solution, 15 g of Ligner Rhodensity polyethylene powder dried under reduced pressure at 80 ° C. for 5 hours was added, and the temperature was raised to 40 ° C. to carry out stirring reaction at 40 ° C. for 2 hours. Then, the solvent was removed under a nitrogen blow and reduced pressure to obtain 26 g of a solid catalyst component.

(Preparation of Gas-Phase Prepolymerization Catalyst) To a 500 m autoclave equipped with a stirrer, which had been dried under heating and reduced pressure, 1 mmol of triethylaluminum and 2 g of the above solid catalyst component were added at room temperature under a nitrogen atmosphere, and the temperature was raised to 65 ° C.
0.5 kg of 1 / ethylene (molar ratio 0.04) mixed gas
Polymerization was carried out at f / cm ² · G for 30 minutes. After the polymerization, 6 g of a gas phase prepolymerization catalyst having good fluidity was obtained. This was a polymer 2 g / g solid catalyst.

(Ethylene / Butene-1 Copolymerization / Slurry Polymerization) To a sufficiently dried 2 L autoclave, 1,000 ml of hexane and 300 mg of the above gas phase prepolymerization catalyst were added at room temperature under a nitrogen atmosphere, and then the temperature was raised to 80 ° C. to obtain 30 g. Butene-1 was press-fitted with ethylene to give a total pressure of 10 kgf / cm ^2.
-Kept at G and polymerized for 2 hours. After the polymerization, it was air-dried as it was to obtain 53 g of butene-1 / ethylene copolymer having a bulk density of 0.45. The inner wall of the 2 L autoclave and the stirring blade were very clean without polymer adhesion. The polymerization results are shown in Table 1.

Example 8 In Example 3, 15 g of Mg (CO ₃ ) ₂ powder dried at 150 ° C. for 2 hours was used instead of silica, 1.45 g of cyclopentadiene instead of it and indene, and trihexyl aluminum 1. The same procedure as in Example 3 was carried out except that 2.8 g was used instead of 7 g. The polymerization results are shown in Table 1.
It was shown to.

Example 9 (Preparation of catalyst component) (Preparation of silica) 100 ml of purified hexane was added to a 300 ml three-necked flask, and then 4
SiO ₂ baked at 00 ° C. for 5 hours (manufactured by Fuji Devison,
# 952) (15 g) was added, then triethylaluminum (1.7 g) was added, and the mixture was stirred at 40 ° C. for 2 hr.
After the reaction, vacuum drying was carried out to prepare triethylaluminum-treated silica. To a 300 ml three-necked flask, 100 ml of purified toluene was added, and then 2.8 g of trihexylaluminum, 1.2 g of indene, and 0.25 g of zirconium tributoxide monochloride (Zr (OBu) ₃ Cl) dissolved in 50 ml of toluene were added. The temperature was raised and the reaction was carried out with stirring at 120 ° C. for 2 hours. After the reaction, 25 ℃
To 80 ml of a toluene solution of methylalumoxane (concentration; 1 mmol / ml in terms of Al atom).
added. After the addition was completed, the mixture was reacted with stirring at 25 ° C for 3 hours.
15 g of the above-mentioned silica treated with triethylaluminum was added to this reaction solution, the temperature was raised to 40 ° C., and the reaction was performed with stirring at 40 ° C. for 2 hours. Then, the solvent was removed under a nitrogen blow and under reduced pressure to obtain 22 g of a solid catalyst component.

(Preparation of Gas-Phase Prepolymerization Catalyst) To a 500 m autoclave equipped with a stirrer, which had been dried under heating under reduced pressure, 2 g of the above solid catalyst component was added at room temperature under a nitrogen atmosphere and then the temperature was raised to 65 ° C. to obtain butene-1 / ethylene (mol Ratio 0.02) The mixed gas was prepolymerized at 0.25 kgf / cm ² · G for 15 minutes. After the prepolymerization, 3 g of a gas phase prepolymerized catalyst having good fluidity was obtained. This was a polymer 0.5 g / g solid catalyst.

(Ethylene / Butene-1 Copolymerization / Gas Phase Polymerization) In a 2 L autoclave equipped with a sufficiently dried stirrer, 200 mg of a gas phase prepolymerization catalyst component at room temperature under a nitrogen atmosphere.
Was added and heated to 80 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (a molar ratio of butene-1 / ethylene of 0.11) was charged so as to be 9 kgf / cm ² · G to start polymerization, and a mixed gas of ethylene and butene-1 ( Polymerization was carried out for 2 hours while continuously supplying a butene-1 / ethylene molar ratio of 0.05) and maintaining the total pressure at 9 kgf / cm ² · G. 80 with a bulk density of 0.47 after polymerization
g of butene-1 / ethylene copolymer was obtained. No polymer adhered to the inner wall of the 2 L autoclave and the stirring blade. The polymerization results are shown in Table 1.

Example 10 Gas phase polymerization was carried out using the gas phase prepolymerization catalyst prepared in Example 3. (Ethylene / Hexene-1 Copolymerization / Gas Phase Polymerization) To a 2 L autoclave equipped with a sufficiently stirrer was added 200 mg of the gas phase prepolymerization catalyst component at room temperature under a nitrogen atmosphere, and the mixture was heated to 80 ° C. with stirring. Then ethylene and hexene-1
Mixed gas (molar ratio of hexene-1 / ethylene of 0.0
8) was charged so as to be 9 kgf / cm ² · G to start the polymerization, and while continuously supplying a mixed gas of ethylene and hexene-1 (hexene-1 / ethylene molar ratio 0.04), Polymerization was carried out for 2 hours while maintaining the total pressure at 9 kgf / cm ² · G. After the polymerization, 55 g of hexene-1 / ethylene copolymer having a bulk density of 0.48 was obtained. No polymer adhered to the inner wall of the 2 L autoclave and the stirring blade, and it was very clean. The physical properties of the obtained polymer are shown in Table 1.

Example 11 (Preparation of catalyst component) To a 300 ml three-necked flask was added 100 ml of purified toluene, then 3.06 g of titanium tetrabutoxide (Ti (OBu) ₄ ) and then 5.6 g of trihexylaluminum and indene. The temperature was raised by adding 3.6 g and the reaction was carried out at 120 ° C. for 2 hours with stirring. After the reaction, the mixture was cooled to 25 ° C., and 200 ml of a toluene solution of methylalumoxane (concentration; 1 mmol / ml in terms of Al atom) was added thereto. After the addition was completed, the mixture was reacted with stirring at 25 ° C for 3 hours. This reaction solution was baked at 400 ° C. for 5 hours.
15 g of io ₂ (# 952, manufactured by Fuji Devison Co., Ltd.) was added and the temperature was raised to 40 ° C., and the mixture was stirred and reacted at 40 ° C. for 2 hours. Then, the solvent was removed under a nitrogen blow and under reduced pressure to obtain 39 g of a solid catalyst component.

(Preparation of Gas Phase Prepolymerization Catalyst) To a 500 m autoclave equipped with a stirrer, which had been dried under heating and reduced pressure, 0.5 mmol of triethylaluminum and 2 g of the above catalyst component were added at room temperature under a nitrogen atmosphere, and the temperature was raised to 65 ° C.
0.3 kg of 1 / ethylene (molar ratio 0.05) mixed gas
Prepolymerization was carried out at f / cm ² · G for 10 minutes. After the prepolymerization, 4 g of a gas phase prepolymerized catalyst having good fluidity was obtained. This was a polymer 1 g / g solid catalyst.

(Ethylene / Butene-1 Copolymerization / Slurry Polymerization) 1000 ml of hexane and 200 mg of the above gas phase prepolymerization catalyst were added to a well-dried 2 L autoclave at room temperature under a nitrogen atmosphere and then the temperature was raised to 80 ° C. to obtain 20 g. Butene-1 was press-fitted with ethylene to give a total pressure of 10 kgf / cm ^2.
-Kept at G and polymerized for 3 hours. After the polymerization, it was air-dried as it was to obtain 110 g of butene-1 / ethylene copolymer having a bulk density of 0.45. The inner wall of the 2 L autoclave and the stirring blade were very clean without any polymer adhesion. The physical properties of the obtained polymer are shown in Table 1.

Example 12 (Preparation of catalyst component) 100 ml of purified toluene was added to a 300 ml three-necked flask, then 0.17 g of titanium tetrabutoxide (Ti (OBu) ₄ ), then 1.7 g of trihexylaluminum and indene. 1.8 g was added to raise the temperature, and the mixture was reacted with stirring at 120 ° C. for 2 hours. After the reaction, the mixture was cooled to 25 ° C., and 100 ml of a toluene solution of methylalumoxane (concentration; Al atom: 1 mmol / ml) was added thereto. After the addition was completed, the mixture was reacted with stirring at 25 ° C for 3 hours. This reaction solution was baked at 400 ° C. for 5 hours.
15 g of io ₂ (# 952, manufactured by Fuji Devison Co., Ltd.) was added and the temperature was raised to 40 ° C., and the mixture was stirred and reacted at 40 ° C. for 2 hours. Then, the solvent was removed under a nitrogen blow and reduced pressure to obtain 24 g of a solid catalyst component.

(Preparation of Gas-Phase Prepolymerization Catalyst) To a 500 m autoclave equipped with a stirrer, which had been dried under heating and reduced pressure, 0.5 mmol of triethylaluminum and 2 g of the above catalyst component were added at room temperature under a nitrogen atmosphere, and the temperature was raised to 65 ° C.
1.3 kg of 1 / ethylene (molar ratio 0.05) mixed gas
Prepolymerization was carried out at f / cm ² · G for 15 minutes. After the prepolymerization, 4 g of a gas phase prepolymerized catalyst having good fluidity was obtained. This was a polymer 1 g / g solid catalyst.

(Ethylene / Butene-1 Copolymerization / Slurry Polymerization) 1000 ml of hexane and 200 mg of the above gas phase prepolymerization catalyst were added to a sufficiently dried 2 L autoclave at room temperature under a nitrogen atmosphere and then the temperature was raised to 80 ° C. to 20 g. Butene-1 of No. 1 was press-fitted with ethylene to give a total pressure of 10 kgf / cm ^2.
-Kept at G and polymerized for 3 hours. After the polymerization, it was air-dried as it was to obtain 20 g of butene-1 / ethylene copolymer having a bulk density of 0.45. The inner wall of the 2 L autoclave and the stirring blade were very clean without any polymer adhesion. The physical properties of the obtained polymer are shown in Table 1.

Example 13 (Preparation of catalyst component) First, tetrabenzyl hafnium (HfBz ₄ ) was prepared as follows. 3 g of hafnium tetrachloride was added to an ether solution of benzylmagnesium chloride and maintained at -20 ° C for 2 hours, and then reacted by stirring at room temperature for 2 hours. After removing MgCl ₂ produced as a by-product, the ether solution was concentrated and further cooled to −20 ° C. to obtain crystals. To a 300 ml three-necked flask, 100 ml of purified toluene was added, then 0.97 g of tetrabenzyl hafnium (HfBz ₄ ), 1.7 g of trihexylaluminum and 0.7 g of indene were added, and the temperature was raised to 120 ° C. for 2 hours. The reaction was carried out with stirring. After the reaction, the mixture was cooled to 25 ° C., and 100 ml of a toluene solution of methylalumoxane (concentration; Al atom: 1 mmol / ml) was added thereto. After the addition was completed, the mixture was reacted with stirring at 25 ° C for 3 hours. To this reaction solution, 15 g of SiO ₂ (manufactured by Fuji Devison Co., Ltd., # 952) which had been calcined at 400 ° C. for 5 hours was added, and the temperature was raised to 40 ° C. and reacted with stirring at 40 ° C. for 2 hours. Then, the solvent was removed under a nitrogen blow and reduced pressure to obtain 24 g of a solid catalyst component.

(Preparation of Gas Phase Prepolymerization Catalyst) 0.5 mmol of triethylaluminum and 2 g of the above catalyst component were added at room temperature under a nitrogen atmosphere to a 500 m autoclave equipped with a stirrer which had been dried under heating and reduced pressure, and the temperature was raised to 65 ° C.
0.8 kg of 1 / ethylene (molar ratio 0.05) mixed gas
Prepolymerization was carried out at f / cm ² · G for 30 minutes. After the prepolymerization, 4 g of a gas phase prepolymerized catalyst having good fluidity was obtained. This was a polymer 1 g / g solid catalyst.

(Ethylene / Butene-1 Copolymerization / Slurry Polymerization) 1000 ml of hexane and 200 mg of the above gas phase prepolymerization catalyst were added to a sufficiently dried 2 L autoclave at room temperature under a nitrogen atmosphere and then the temperature was raised to 80 ° C. to obtain 20 g. Butene-1 was press-fitted with ethylene to give a total pressure of 10 kgf / cm ^2.
-Kept in G and polymerized for 5 hours. After the polymerization, it was air-dried as it was to obtain 150 g of butene-1 / ethylene copolymer having a bulk density of 0.45. The inner wall of the 2 L autoclave and the stirring blade were very clean without any polymer adhesion. The physical properties of the obtained polymer are shown in Table 1.

Comparative Example 2 (Preparation of catalyst component) To a 300 ml three-necked flask was added 100 ml of purified toluene, then 0.90 g of bis (cyclopentaenyl) zirconium dichloride, and then a toluene solution of methylalumoxane (concentration; 200 ml of Al atom (1 mmol / ml) was added and the temperature was raised to carry out stirring reaction at 60 ° C. for 2 hours. After the reaction, it was cooled to 25 ° C. This reaction solution was baked at 400 ° C. for 5 hours SiO ₂
(Fuji Davison Co., # 952) Add 15g and 40 ℃
To 40 ° C. and reacted for 2 hours with stirring. Then, the solvent was removed under a nitrogen blow and reduced pressure to obtain a solid catalyst component 2
8 g was obtained. The amount of Zr supported in the catalyst component is 1.00 wt%
Met.

(Preparation of Gas-Phase Prepolymerization Catalyst) 0.5 mmol of triethylaluminum and 2 g of the above catalyst component were added at room temperature under a nitrogen atmosphere to a 500 m autoclave equipped with a stirrer which had been dried under heating and reduced pressure, and the temperature was raised to 65 ° C.
0.8 kg of 1 / ethylene (molar ratio 0.02) mixed gas
Prepolymerization was carried out at f / cm ² · G for 30 minutes. After the prepolymerization, 4 g of a gas phase prepolymerization catalyst having poor fluidity was obtained. This was a polymer 1 g / g solid catalyst.

(Ethylene / Butene-1 Copolymerization / Slurry Polymerization) 1000 ml of hexane and 200 mg of the above gas phase prepolymerization catalyst were added to a well-dried 2 L autoclave at room temperature under a nitrogen atmosphere and then the temperature was raised to 80 ° C. to obtain 15 g. Butene-1 was press-fitted with ethylene to give a total pressure of 10 kgf / cm ^2.
-Kept at G and polymerized for 3 hours. After the polymerization, it was air-dried as it was to obtain 175 g of butene-1 / ethylene copolymer having a bulk density of 0.28. A large amount of polymer adhered to the inner wall of the 2 L autoclave and the stirring blade. The physical properties of the obtained polymer are shown in Table 1.

[Brief description of drawings]

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

[Table 1]

Claims (2)

[Claims] 1. A general formula Me ¹ R ¹ _p (OR ² ) _q.
A compound represented by X ¹ _4-pq (wherein Me ¹ is Z
r, Ti or Hf, R ¹ and R ² each represent a hydrocarbon group having 1 to 24 carbon atoms, X ¹ represents a halogen atom, and p and q each represent 0 ≦ p <4 and 0 ≦ q < 4, 0 ≦
p is an integer satisfying the range of + q ≦ 4), (2 ) the general formula _{^{Me 2 R 3 m (OR 4}} ) n X 2 z-m-n compound represented by (wherein, Me ² is a periodic table Group I-III elements, R
³ and R ⁴ each represent a hydrocarbon group having 1 to 24 carbon atoms, X ² represents a halogen atom or a hydrogen atom (provided that X ²
Is a hydrogen atom, Me ² represents a group III element of the periodic table), z represents the valence of Me ² , and m and n are 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively. An integer satisfying the range and 0 ≦ m + n ≦ z), (3) an organic cyclic compound having a conjugated double bond, (4) a modified organoaluminum compound containing an Al—O—Al bond, and (5) An olefin polymerization catalyst, which is formed by prepolymerizing an olefin with a catalyst component obtained by bringing an inorganic carrier and / or a particulate polymer carrier into contact with each other. 2. (1) The general formula Me ¹ R ¹ _p (OR ² ) _q.
A compound represented by X ¹ _4-pq (wherein Me ¹ is Z
r, Ti or Hf, R ¹ and R ² each represent a hydrocarbon group having 1 to 24 carbon atoms, X ¹ represents a halogen atom, and p and q each represent 0 ≦ p <4 and 0 ≦ q < 4, 0 ≦
p is an integer satisfying the range of + q ≦ 4), (2 ) the general formula _{^{Me 2 R 3 m (OR 4}} ) n X 2 z-m-n compound represented by (wherein, Me ² is a periodic table Group I-III elements, R
³ and R ⁴ each represent a hydrocarbon group having 1 to 24 carbon atoms, X ² represents a halogen atom, z represents the valence of Me ² , and m and n each represent 0 ≦ m ≦ z and 0 ≦ n. An integer satisfying the range of ≦ z, and 0 ≦ m + n ≦ z),
(3) Organic cyclic compound having conjugated double bond, (4) Al
-O-Al bond-containing modified organoaluminum compound, and (5) the presence of a catalyst formed by prepolymerizing olefins with a catalyst component obtained by bringing an inorganic carrier and / or a particulate polymer carrier into contact with each other. under,
A method for producing a polyolefin, which comprises polymerizing or copolymerizing olefins.