JPH05186525A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a polyolefin in high yields with the molecular weight distribution reading controllable by performing the polymerization in the presence of a catalyst comprising a catalyst component comprising a specified transition metal compound and an alkali metal salt of a cyclopentadiene and a specified modified organoaluminum compound. CONSTITUTION:An olefin is (co)polymerized in the presence of a catalyst comprising a catalyst component prepared by bringing compound of the formula: Me<1>R<1>nX<1>4-n (wherein R<1> is a 1-24C hydrocarbon residue; X<1> is halogen; Me is Zr, Ti or Hf; and 0<=n<=4) and an alkali metal salt of a cyclopentadiene into contact with each other and an Al-O-Al-bond-containing modified organoaluminum compound prepared by reacting an organoaluminum compound with water. According to the above process, a polyolefin can be produced in high polymerization activity and the molecular weight distribution of a polyolefin can be reely controlled by suitably selecting the catalyst. Especially a copolymer of a narrow compositional distribution can be obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyolefin using a specific catalyst. More specifically, the present invention is capable of producing a polyolefin with high polymerization activity by polymerizing or copolymerizing an olefin in the presence of a specific catalyst, and moreover, the molecular weight distribution of the obtained polyolefin can be freely controlled. In particular, in the case of copolymerizing ethylene and α-olefin, it relates to a method for producing a polyolefin having excellent characteristics such as a narrow composition distribution.

[0002]

The use of zirconium compounds (typically metallocene compounds) in the production of polyolefins, especially ethylene polymers or ethylene.alpha.-olefin copolymers, is described in US Pat. It is known as disclosed in Japanese Patent Laid-Open No. 58-19309. However, although there is a method for producing an ethylene-based copolymer in a high yield as a technique for a solid catalyst component, the resulting copolymer has the drawbacks of a narrow molecular weight distribution, a narrow composition distribution, and a low molecular weight. Was.

Focusing on the point of 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-63-234005 proposes that the molecular weight of a polymer obtained by using a transition metal compound having a 2,3- and 4-substituted cyclopentadienyl group can be improved. .. Further, JP-A-2-22307 proposes to improve the molecular weight of a polymer by using a hafnium compound having a ligand bonded to at least two conjugated cycloalkadienyl groups which are crosslinked.

However, the synthetic route of the above catalyst components is complicated, the operation is complicated, and the use of hafnium as a transition metal species has a drawback that the yield of the obtained polymer is low.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have mentioned the above-mentioned drawbacks and requirements, namely, simplification of synthesis of catalyst components, high yield, easy control of molecular weight distribution, and compositional distribution. As a result of intensive studies to produce narrow polyolefins, a new specific catalyst system that solves the conventional problems has been found and the present invention has been accomplished.

That is, the present invention includes: a) (1) a compound represented by the general formula Me ¹ R ¹ _n X ¹ _4-n (wherein R ¹ is a hydrocarbon residue having 1 to 24 carbon atoms, X
¹ is a halogen atom, Me is Zr, Ti or Hf, and n is 0 ≦ n ≦ 4. And (2) a catalyst component obtained by bringing alkali metal salts of cyclopentadiene into contact with each other, and b) a modified organoaluminum compound containing an Al—O—Al bond obtained by reacting an organoaluminum compound with water. The present invention relates to a method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst, and the present invention is: a) (1) represented by the general formula Me ¹ R ¹ _n X ¹ _4-n. Compound (wherein R ¹ is a hydrocarbon residue having 1 to 24 carbon atoms, X 1
¹ is a halogen atom, Me is Zr, Ti or Hf, and n is 0 ≦ n ≦ 4. ) (2) Alkali metal salt of cyclopentadiene and (3) compound represented by the general formula Me ² R ² _m X ² _zm (wherein R ² is a hydrocarbon group having 1 to 24 carbon atoms, X ² is an alkoxy group having 1 to 12 carbon atoms or a halogen atom, Me
² represents a Group I to III element of the periodic table, z is the valence of Me ² , and m is 0 ≦ m ≦ 3. Olefins are polymerized in the presence of a catalyst consisting of a catalyst component obtained by bringing them into contact with each other and b) a modified organoaluminum compound containing an Al-O-A1 bond obtained by the reaction of an organoaluminum compound and water. It relates to a method for producing a polyolefin, which is characterized by copolymerization.

The catalyst used in the method of the present invention has high activity per transition metal, and the obtained polyolefin is
The molecular weight distribution can be controlled freely, especially ethylene
The α-olefin copolymer has excellent characteristics such as a narrow composition distribution and extremely low surface tackiness. Further, the effect is particularly remarkable when a compound represented by the general formula Me ² R ² _m X ² _zm is used as a catalyst component.

The present invention will be described in detail below. As described above, the production method of the present invention comprises (1) the general formula Me ¹ R ¹ _n X ¹
A compound represented by _4-n , (2) an alkali metal salt of cyclopentadiene, and optionally (3) a general formula Me.
Modified organoaluminum compound containing a component obtained a compound represented by the _{^{2 R 2 m X 2 z-}} m in contact with each other, Al-O-Al bonds obtained by reacting with water the organic aluminum compound It is characterized in that olefin polymerization or copolymerization is carried out in the presence of a catalyst consisting of.

First, the compound represented by the general formula Me ¹ R ¹ _n X ¹ _4-n will be described. In this equation,
R ¹ represents a hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 and more preferably 1 to 8, and examples of the hydrocarbon residue include a methyl group, an ethyl group, a propyl group and butyl. Group, alkyl group such as pentyl group, hexyl group, octyl group, alkenyl group such as vinyl group and allyl group, aryl group such as phenyl group, tolyl group, xylyl group, benzyl group, phenethyl group, styryl group, neofil group, etc. Aralkyl group, methoxy group, ethoxy group,
Examples thereof include an alkoxy group such as a propoxy group, a butoxy group and a pentyloxy group, an aryloxy group such as a phenoxy group and a tolyloxy group, and an aralkyloxy group such as a benzyloxy group. X ¹ is a halogen atom of fluorine, iodine, chlorine and bromine, and Me ¹ is Zr, Ti or H.
f, preferably Zr. n is 0 ≦ n ≦ 4, preferably 0 <n ≦ 4. As the compounds represented by these general formulas, specifically,

Tetramethylzirconium, tetraethylzirconium, tetrapropylzirconium, tetra-n
-Butyl zirconium, tetrapentyl zirconium,
Tetraphenylzirconium, tetratolylzirconium, tetrabenzylzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetraphenoxyzirconium, tetratolyloxyzirconium, tetrapentyloxyzirconium, tetrabenzyloxyzirconium, tetraallylzirconium , Tetraneofil zirconium, trimethyl monochloro zirconium, triethyl monochloro zirconium, tripropyl monochloro zirconium, tri n-butyl monochloro zirconium, tribenzyl dichloro mono zirconium, dimethyl dichloro zirconium, diethyl dichloro zirconium, di n-butyl dichloro zirconium, dibenz Zirconium dichloride, monomethyl trichloro zirconium, monoethyl trichloro zirconium, mono-n- butyl trichloro zirconium,
Monobenzyltrichlorozirconium, tetrachlorozirconium, trimethoxymonochlorozirconium, dimethoxydichlorozirconium, monomethoxytrichlorozirconium, tetraethoxyzirconium, triethoxymonochlorozirconium, diethoxydichlorozirconium, monoethoxytrichlorozirconium, triisopropoxymonochlorozirconium, diiso Propoxydichlorozirconium, monoisopropoxytrichlorozirconium, tetra-n-butoxyzirconium, tri-n-butoxymonochlorozirconium, di-n-
Butoxydichlorozirconium, mono-n-butoxytrichlorozirconium, tripentoxymonochlorozirconium, dipentoxydichlorozirconium, monopentoxytrichlorozirconium, triphenoxymonochlorozirconium, diphenoxydichlorozirconium, monophenoxytrichlorozirconium, tritolyloxymonochlorozirconium, Ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium, tribenzyloxymonochlorozirconium,
Dibenzyloxydichlorozirconium, monobenzyloxytrichlorozirconium,

Trimethylmonobromozirconium, triethylmonobromozirconium, tripropylmonobromozirconium, tri-n-butylmonobromozirconium, tribenzylmonobromozirconium,

Dimethyldibromozirconium, diethyldibromozirconium, di-n-butyldibromozirconium, dibenzyldibromozirconium, monomethyltribromozirconium, monoethyltribromozirconium, mono-n-butyltribromozirconium, monobenzyltribromozirconium, tetrabromo. zirconium,

Trimethoxymonobromozirconium, dimethoxydibromozirconium, monomethoxytribromozirconium, triethoxymonobromozirconium, diethoxydibromozirconium, monoethoxytribromozirconium, triisopropoxymonobromozirconium, diisopropoxydibromozirconium, mono Isopropoxytribromozirconium,

Tri-n-butoxymonobromozirconium, di-n-butoxydibromozirconium, mono-n-butoxytribromozirconium, tripentoxymonobromozirconium, dipentoxydibromozirconium, monopentoxytribromozirconium, triphenoxymonobromo. zirconium,

Diphenoxydibromozirconium, monophenoxytribromozirconium, tritolyloxymonobromozirconium, ditolyloxydibromozirconium, monotolyloxytribromozirconium,
Tribenzyloxymonobromozirconium, dibenzyloxydibromozirconium, monobenzyloxytribromozirconium,

Trimethyl monoiodo zirconium, triethyl monoiodo zirconium, tripropyl monoiodo zirconium, tri-n-butyl monoiodo zirconium, tribenzyl monoiodo zirconium,

Dimethyldiiodozirconium, diethyldiiodozirconium, di-n-butyldiiodozirconium, dibenzyldiiodozirconium, monomethyltriiodozirconium, monoethyltriiodozirconium, mono-n-butyltriiodozirconium, monobenzyltriiodo. Zirconium, tetraiodozirconium,

Trimethoxy monoiodo zirconium, dimethoxy diiodo zirconium, monomethoxy triiodo zirconium, triethoxy monoiodo zirconium, diethoxy diiodo zirconium, monoethoxy triiodo zirconium, triisopropoxy monoiodo zirconium, diisopropoxy diiodo. Zirconium, monoisopropoxytriiodozirconium,

Tri-n-butoxymonoiodozirconium, di-n-butoxydiiodozirconium, mono-n-
Butoxytriiodozirconium, Tripentoxymonoiodozirconium, Dipentoxydiiodozirconium, Monopentoxytriiodozirconium, Triphenoxymonoiodozirconium, Diphenoxydiiodozirconium, Monophenoxytriiodozirconium, Tritolyloxymonoiodozirconium , Ditolyloxydiiodozirconium, monotolyloxytriiodozirconium, tribenzyloxymonoiodozirconium, dibenzyloxydiiodozirconium,
Monobenzyloxytriiodozirconium,

Tetramethyltitanium, tetraethyltitanium, tetrapropyltitanium, tetra-n-butyltitanium, tetrabenzyltitanium, tetraallyltitanium, tetraneofiltitanium trimethylmonochlorotitanium, triethylmonochlorotitanium, tripropylmonochlorotitanium, trin-butylmonochloro Titanium, tribenzyldimonochlorotitanium, dimethyldichlorotitanium, diethyldichlorotitanium, di-n-butyldichlorotitanium,
Dibenzyldichlorotitanium, monomethyltrichlorotitanium, monoethyltrichlorotitanium, monon
-Butyltrichlorotitanium, monobenzyltrichlorotitanium, tetramethoxytitanium, trimethoxymonochlorotitanium, dimethoxydichlorotitanium, monomethoxytrichlorotitanium, tetraethoxytitanium, triethoxymonochlorotitanium, diethoxydichlorotitanium, monoethoxytrichlorotitanium, tetraisopropoxy Titanium, triisopropoxymonochlorotitanium, diisopropoxydichlorotitanium, monoisopropoxytrichlorotitanium, tetra-n-butoxytitanium, tri-n-butoxymonochlorotitanium, di-n-butoxydichlorotitanium, mono-n-butoxytrichlorotitanium,
Tetrapentoxytitanium, tripentoxymonochlorotitanium, dipentoxydichlorotitanium, monopentoxytrichlorotitanium, tetraphenoxytitanium, triphenoxymonochlorotitanium, diphenoxydichlorotitanium, monophenoxytrichlorotitanium, tetratolyloxytitanium, tritolyloxy Monochlorotitanium, ditolyloxydichlorotitanium, monotolyloxytrichlorotitanium, tetrabenzyloxytitanium, tribenzyloxymonochlorotitanium, dibenzyloxydichlorotitanium, monobenzyloxytrichlorotitanium,

Trimethylmonobromotitanium, triethylmonobromotitanium, tripropylmonobromotitanium, tri-n-butylmonobromotitanium, tribenzylmonobromotitanium,

Dimethyldibromotitanium, diethyldibromotitanium, di-n-butyldibromotitanium, dibenzyldibromotitanium, monomethyltribromotitanium, monoethyltribromotitanium, mono-n-butyltribromotitanium, monobenzyltribromotitanium, tetra Bromotitanium,

Trimethoxymonobromotitanium, dimethoxydibromotitanium, monomethoxytribromotitanium, triethoxymonobromotitanium, diethoxydibromotitanium, monoethoxytribromotitanium, triisopropoxymonobromotitanium, diisopropoxydibromotitanium, mono Isopropoxytribromotitanium,

Tri-n-butoxymonobromotitanium, di-n-butoxydibromotitanium, mono-n-butoxytribromotitanium, tripentoxymonobromotitanium, dipentoxydibromotitanium, monopentoxytribromotitanium, triphenoxymono Bromotitanium,

Diphenoxydibromotitanium, monophenoxytribromotitanium, tritolyloxymonobromotitanium, ditolyloxydibromotitanium, monotolyloxytribromotitanium, tribenzyloxymonobromotitanium, dibenzyloxydibromotitanium, monobenzyloxy Tribromotitanium,

Trimethylmonoiodotitanium, triethylmonoiodotitanium, tripropylmonoiodotitanium, tri-n-butylmonoiodotitanium, tribenzylmonoiodotitanium,

Dimethyldiiodotitanium, diethyldiiodotitanium, di-n-butyldiiodotitanium,
Dibenzyldiiodotitanium, monomethyltriiodotitanium, monoethyltriiodotitanium, monon
-Butyltriiodotitanium, monobenzyltriiodotitanium, tetraiodotitanium,

Trimethoxymonoiodotitanium, dimethoxydiiodotitanium, monomethoxytriiodotitanium, triethoxymonoiodotitanium, diethoxydiiodotitanium, monoethoxytriiodotitanium, triisopropoxymonoiodozirconium,
Diisopropoxyjodotitanium, monoisopropoxytriiodotitanium,

Tri-n-butoxymonoiodotitanium,
Di-n-butoxydiiodotitanium, mono-n-butoxytriiodotitanium, tripentoxymonoiodotitanium, dipentoxydiiodotitanium, monopentoxytriiodotitanium, triphenoxymonoiodotitanium, diphenoxydiiodotitanium, mono Phenoxytriiodotitanium, tritolyloxymonoiodotitanium, ditolyloxydiiodotitanium, monotolyloxytriiodotitanium, tribenzyloxymonoiodotitanium, dibenzyloxydiiodotitanium, monobenzyloxytriiodotitanium,

Tetramethyl hafnium, tetraethyl hafnium, tetrapropyl hafnium, tetra n-butyl hafnium, tetrabenzyl hafnium, tetraallyl hafnium, tetraneophyll hafnium, trimethyl monochloro hafnium, triethyl monochloro hafnium, tripropyl monochloro hafnium, tri n-butyl. Monochlorohafnium, tribenzyldimonochlorohafnium, dimethyldichlorohafnium, diethyldichlorohafnium, di-n-butyldichlorohafnium, dibenzyldichlorohafnium, monomethyltrichlorohafnium, monoethyltrichlorohafnium, mono-n-butyltrichlorohafnium, monobenzyltrichlorohafnium, Tetramethoxy hafnium, trimethoxy monochloroha Chloride, dimethoxy-dichloro hafnium, monomethoxy trichlorosilane hafnium, tetraethoxy hafnium, triethoxy monochlorosilane hafnium, diethoxy dichlorosilane hafnium, monoethoxy trichloro hafnium tetraisopropoxide, hafnium,
Triisopropoxymonochlorohafnium, diisopropoxydichlorohafnium, monoisopropoxytrichlorohafnium, tetra-n-butoxyhafnium, tri-n-butoxymonochlorohafnium, di-n-butoxydichlorohafnium, mono-n-butoxytrichlorohafnium, tetrapentoxyhafnium, Tripentoxymonochlorohafnium, dipentoxydichlorohafnium, monopentoxytrichlorohafnium, tetraphenoxyhafnium, triphenoxymonochlorohafnium, diphenoxydichlorohafnium, monophenoxytrichlorohafnium, tetratolyloxyhafnium, tritolyloxymonochlorohafnium, ditolyl Oxydichlorohafnium, monotolyloxytrichlorohafnium, tetra Emissions Jill oxy hafnium, tri-benzyloxy-monochloro hafnium, di-benzyloxy-dichloro hafnium, mono-benzyloxy-trichloro hafnium

Trimethylmonobromohafnium, triethylmonobromohafnium, tripropylmonobromohafnium, tri-n-butylmonobromohafnium, tribenzylmonobromohafnium,

Dimethyldibromohafnium, diethyldibromohafnium, di-n-butyldibromohafnium,
Dibenzyldibromohafnium, monomethyltribromohafnium, monoethyltribromohafnium, mono-n
-Butyltribromohafnium, monobenzyltribromohafnium, tetrabromohafnium,

Trimethoxymonobromohafnium, dimethoxydibromohafnium, monomethoxytribromohafnium, triethoxymonobromohafnium, diethoxydibromohafnium, monoethoxytribromohafnium, triisopropoxymonobromohafnium, diisopropoxydibromohafnium, mono Isopropoxytribromohafnium,

Tri-n-butoxymonobromohafnium,
Di-n-butoxydibromohafnium, mono-n-butoxytribromohafnium, tripentoxymonobromohafnium, dipentoxydibromohafnium, monopentoxytribromohafnium, triphenoxymonobromohafnium, diphenoxydibromohafnium, monophenoxytribromo Hafnium, tritolyloxymonobromohafnium, ditolyloxydibromohafnium, monotolyloxytribromohafnium, tribenzyloxymonobromohafnium, dibenzyloxydibromohafnium, monobenzyloxytribromohafnium,

Trimethylmonoiodohafnium, triethylmonoiodohafnium, tripropylmonoiodohafnium, tri-n-butylmonoiodohafnium, tribenzylmonoiodohafnium,

Dimethyldiiodohafnium, diethyldiiodohafnium, di-n-butyldiiodohafnium,
Dibenzyldiiodohafnium, monomethyltriiodohafnium, monoethyltriiodohafnium, mono n
-Butyltriiodohafnium, monobenzyltriiodohafnium, tetraiodohafnium,

Trimethoxymonoiodohafnium, dimethoxydiiodohafnium, monomethoxytriiodohafnium, triethoxymonoiodohafnium, diethoxydiiodohafnium, monoethoxytriiodohafnium, triisopropoxymonoiodohafnium, diisopropoxydiiodo Hafnium, monoisopropoxytriiodo hafnium,

Tri-n-butoxymonoiodohafnium,
Di-n-butoxydiiodohafnium, mono-n-butoxytriiodohafnium, tripentoxymonoiodohafnium, dipentoxydiiodohafnium, monopentoxytriiodohafnium, triphenoxymonoiodohafnium, diphenoxydiiodohafnium, mono Phenoxytriiodohafnium, tritolyloxymonoiodohafnium, ditolyloxydiiodohafnium, monotolyloxytriiodohafnium, tribenzyloxymonoiodohafnium, dibenzyloxydiiodohafnium, monobenzyloxytriiodohafnium

Among them, tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium and tetrachlorozirconium are preferable, and more preferable are alkoxy groups such as tetrapropoxyzirconium and tetrabutoxyzirconium. A transition metal compound having is desirable. Moreover, you may use these compounds in mixture of 2 or more types. In particular, the use of the tetraalkoxyzirconium compound has advantages such as good fluidity (large N value) despite the narrow molecular weight distribution of the obtained polymer. Furthermore, compared with the case where a conventional zirconocene or titanocene compound is used as a catalyst constituent, even if the number of comonomer branches per 1000 carbon atoms (1000 C) is small, the density reduction rate is large, for example, ethylene and α-olefin are used. When copolymerizing to produce an ethylene / α-olefin copolymer mainly composed of ethylene, it has an advantage that a low-density copolymer can be produced with a small number of comonomers.

Next, the compound represented by the general formula Me ² R ² _m X ² _zm will be described. In such a compound, R ² is a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group is a methyl group. , Ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group,
Examples thereof include an alkyl group such as a dodecyl group, an alkenyl group such as a vinyl group and an allyl group, an aryl group such as a phenyl group, a tolyl group, and a xylyl group, an aralkyl group such as a benzyl group, a phenethyl group, and a styryl group. X ² is an alkoxy group having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms or a halogen atom of fluorine, iodine, chlorine and bromine. Examples of the alkoxy group include a methoxy group, an ethoxy group,
Examples include propoxy group and butoxy group. Me ² represents a Group I to III element of the periodic table, and examples of such an element include lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum and the like. z represents the valence of Me ² , m is a number in the range of 0 <m ≦ 3, preferably 0 <m <3,
Further, m satisfies m ≦ z. Specific examples of the compound represented by this general formula include methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, t-butyl lithium, pentyl lithium, octyl lithium, phenyl lithium and benzyl. Lithium, dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, di-n-butyl magnesium, di-t-butyl magnesium, dipentyl magnesium, dioctyl magnesium, diphenyl magnesium, dibenzyl magnesium, methyl magnesium chloride,
Ethylmagnesium chloride, isopropylmagnesium chloride, n-propylmagnesium chloride, n-butylmagnesium chloride, t-butylmagnesium chloride, pentylmagnesium chloride, octylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride,
Methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium bromide, ethyl magnesium iodide, isopropyl magnesium bromide, isopropyl magnesium iodide, n
-Propyl magnesium bromide, n-propyl magnesium iodide, n-butyl magnesium bromide, n-butyl magnesium iodide, t-butyl magnesium bromide, t-butyl magnesium iodide, pentyl magnesium bromide, pentyl magnesium iodide, octyl magnesium bromide , Octyl magnesium iodide, phenyl magnesium bromide, phenyl magnesium iodide, benzyl magnesium bromide, benzyl magnesium iodide, dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-
Butylzinc, di-t-butylzinc, dipentylzinc, dioctylzinc, diphenylzinc, dibenzylzinc, trimethylboron, triethylboron, tri-n-propylboron, triisopropylboron, tri-n-butylboron,
Tri-t-butylboron, tripentylboron, trioctylboron, triphenylboron, tribenzylboron

Trimethyl aluminum, triethyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum fluoride,
Diethylaluminum iodide, ethylaluminum dichloride, ethylaluminum dibromide, ethylaluminum difluoride, ethylaluminum ciseiodide, tripropyroaluminum, dipropylaluminium chloride, diprobylaluminum bromide, diprobylaluminum fluoride, dipropylaluminum iodide. , Propyl aluminum dichloride, propyro aluminum dibromide, propyl aluminum difluoride, propyl aluminum diiodide, triisopropyl aluminum, diisopropyl aluminum chloride, diisopropyl aluminum bromide, diisopropyl aluminum fluoride, diisopropyl aluminum diiodide, ethyl aluminum sesquichloride,
Ethyl aluminum sesquibromide, propyl aluminum sesquibromide, propl aluminum sesquibromide, n-butyl aluminum sesquichloride, n-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, dibutyl aluminum iodide, butyl aluminum dichloride, butyrialuminium dibromide, butyl aluminum difluoride, butyl aluminum diiodide, trisec-butyl aluminum, di sec-Butyl aluminum chloride , Di-sec- butyl aluminum bromide, di-sec- butyl aluminum fluoride,
Disec-butyl aluminum iodide, sec-butyl aluminum dichloride, sec-butyl aluminum dibromide, sec-butyl aluminum difluoride, sec-butyl aluminum diiodide, tri te.
rt-butylaluminum, ditert-butylaluminum chloride, ditert-butylaluminum bromide, ditert-butylaluminum fluoride, dit
tert-butyl aluminum iodide, tert-butyl aluminum dichloride, tert-butyl aluminum dibromide, tert-butyl aluminum difluoride, tert-butyl aluminum diiodide, triisobutyl aluminum, diisobutyl aluminum chloride, diisobutyl aluminum bromide, diisobutyryl Aluminum fluoride, diisobutyl aluminum iodide, isobutyl aluminum dichloride, isobutyl aluminum dibromide, isobutyl aluminum difluoride, isobutyl aluminum diiodide, trihexyl aluminum, dihexyl aluminum chloride, dihexyl aluminum bromide, dihexyl aluminum fluoride, dihexyl aluminum iodide Hexyl aluminum Umujikurorido, hexyl aluminum dibromide, hexyl aluminum difluoride,
Hexyl aluminum diiodide, tripentyl 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 propoxide,
Examples thereof include dipropyl aluminum butoxide, butyl aluminum methoxide, butyl aluminum ethoxide, butyl aluminum propoxide, butyl aluminum butoxide, butyl aluminum methoxide, dibutyl aluminum ethoxide, dibutyl aluminum propoxide, dibutyl aluminum butoxide.

The cyclopentadiene in the alkali metal salt of cyclopentadiene used in the present invention includes cyclopentadiene, a substituted cyclopentadiene partially substituted with a hydrocarbon group, and an organic compound containing a cyclopentadienyl group. Silicon compound, and carbon number 1
A compound having a cyclopentadienyl group or a substituted cyclopentadienyl group such as an organosilicon compound having a substituted cyclopentadienyl group partially substituted with a hydrocarbon group of -12.

The substituted cyclopentadiene or the substituted cyclopentadienyl group has 1 to 12 carbon atoms as a substituent.
Preferably, 1 to 6 are preferable, and specifically, a methyl group, an ethyl group, a propyl group, an iso-propyl group,
Examples thereof include an alkyl group such as a butyl group, a t-butyl group, a hexyl group, and an octyl group, an aryl group such as a phenyl group, and an aralkyl group such as a benzyl group.

Examples of such organosilicon compounds include compounds represented by the general formula (Cp) _L SiR ³ _4-L , in which Cp is a cyclopentadiene group and / or a substituted cyclopentadiene group (substituents are as described above. showed similar), ^{R 3} is 1 to 24 carbon atoms, preferably 1 to 12 hydrocarbon residue (e.g., a methyl group, an ethyl group, a propyl group, iso- propyl, butyl, t- butyl group, Alkyl group such as hexyl group and octyl group, methoxy group,
Examples thereof include an ethoxy group, a propoxy group, an alkoxy group such as butoxy group, an aryl group such as phenyl group, an aryloxy group such as phenoxy group, an aralkyl group such as benzyl group), or a hydrogen atom, and L is 1 ≦ L
≦ 4, preferably 1 ≦ L ≦ 3. Examples of the alkali metal salt of these cyclopentadiene include sodium salt and lithium salt.

Specific examples of these alkali metal salts of cyclopentadiene include cyclopentadiene sodium salt, cyclopentadiene lithium salt, methylcyclopentadiene sodium salt, methylcyclopentadiene lithium salt, ethylcyclopentadiene sodium salt,
Ethylenecyclopentadiene lithium salt, t-butylcyclopentadiene sodium salt, t-butylcyclopentadiene lithium salt, hexylcyclopentadiene sodium salt, hexylcyclopentadiene lithium salt, octylcyclopentadiene sodium salt, octylcyclopentadiene lithium salt, 1,2- Dimethylcyclopentadiene sodium salt, 1,2-dimethylcyclopentadiene lithium salt, 1,3-dimethylcyclopentadiene sodium salt, 1,3-dimethylcyclopentadiene lithium salt, 1,2,4-trimethylcyclopentadiene sodium salt, 1, 2,4-Trimethylcyclopentadiene lithium salt, 1,2,3,4-tetramethylcyclopentadiene nantrium salt, 1,2,3,4-tetramethylcyclo Lithium salt, pentamethylcyclopentadiene sodium salt, pentamethylcyclopentadiene lithium salt, monophenylcyclopentadiene sodium salt, monophenylcyclopentadiene lithium salt, benzylcyclopentadiene sodium salt, benzylcyclopentadiene lithium salt, monocyclopentadienyl Silane sodium salt, monocyclopentadienylsilane lithium salt, dicyclopentadienylsilane lithium salt, dicyclopentadienylsilane sodium salt, tricyclopentadienylsilane sodium salt, tricyclopentadienylsilane lithium salt, tetra Cyclopentadienylsilane sodium salt, tetracyclopentadienylsilane lithium salt, monocyclopentadienylmonomethylsilane sodium Salt, monocyclopentadienyl monomethyl silane lithium salt, monocyclopentadienyl monoethyl silane sodium salt, monocyclopentadienyl monoethyl silane lithium salt, monocyclopentadienyl dimethylsilane sodium salt,
Monocyclopentadienyldimethylsilane lithium salt,
Monocyclopentadienyldiethylsilane sodium salt, monocyclopentadienyldiethylsilane lithium salt, monocyclopentadienyltrimethylsilane sodium salt, monocyclopentadienyltrimethylsilane lithium salt, monocyclopentadienyltriethylsilane sodium salt, Monocyclopentadienyl triethylsilane lithium salt, monocyclopentadienyl monomethoxysilane sodium salt, monocyclopentadienyl monomethoxysilane lithium salt, monocyclopentadienyl monoethoxysilane sodium salt, monocyclopentadienyl monoethoxy Silane lithium salt, monocyclopentadienyl monophenoxysilane sodium salt, monocyclopentadienyl monophenoxysilane lithium salt,

Dicyclopentadienyl monomethylsilane sodium salt, dicyclopentadienyl monomethylsilane lithium salt, dicyclopentadienyl monoethylsilane sodium salt, dicyclopentadienyl monoethylsilane lithium salt, dicyclopentadienyl Dimethylsilane sodium salt, dicyclopentadienyldimethylsilane lithium salt, dicyclopentadienyldiethylsilane sodium salt, dicyclopentadienyldiethylsilane lithium salt, dicyclopentadienylmethylethylsilane sodium salt, dicyclopentadiene Lithium phenylmethylethylsilane, sodium dicyclopentadienyldipropylsilane, lithium lithium dicyclopentadienyldipropylsilane, dicyclopentadienylethylpropylsilane nato Umium salt, dicyclopentadienylethylpropylsilane lithium salt, dicyclopentadienyldiphenylsilane sodium salt, dicyclopentadienyldiphenylsilane lithium salt, dicyclopentadienylphenylmethylsilane sodium salt, dicyclopentadienyl Phenylmethylsilane lithium salt, dicyclopentadienyl monomethoxysilane sodium salt, dicyclopentadienyl monomethoxysilane lithium salt, dicyclopentadienyl monoethoxysilane sodium salt, dicyclopentadienyl monoethoxysilane lithium salt,

Tricyclopentadienyl monomethylsilane sodium salt, tricyclopentadienyl monomethylsilane lithium salt, tricyclopentadienyl monoethylsilane sodium salt, tricyclopentadienyl monoethylsilane lithium salt, tricyclopentadienyl Monomethoxysilane sodium salt, tricyclopentadienyl monomethoxysilane lithium salt, tricyclopentadienyl monoethoxysilane sodium salt, tricyclopentadienyl monoethoxysilane lithium salt, 3-methylcyclopentadienylsilane sodium salt, 3-Methylcyclopentadienylsilane lithium salt, bis 3-
Methylcyclopentadienylsilane sodium salt, bis-3-methylcyclopentadienylsilane lithium salt, 3
-Methylcyclopentadienylmethylsilane sodium salt, 3-methylcyclopentadienylmethylsilane lithium salt, 1,2-dimethylcyclopentadienylsilane sodium salt, 1,2-dimethylcyclopentadienylsilane lithium salt, 1 , 3-dimethylcyclopentadienylsilane sodium salt, 1,3-dimethylcyclopentadienylsilane lithium salt, 1,2,4-trimethylcyclopentadienylsilane sodium salt, 1,2,4
-Trimethylcyclopentadienylsilane lithium salt,
1,2,3,4-Tetramethylcyclopentadienylsilane sodium salt, 1,2,3,4-tetramethylcyclopentadienylsilane lithium salt, pentamethylcyclopentadienylsilane sodium salt, pentamethylcyclopenta Examples thereof include dienylsilane lithium salt.

The method for producing these alkali metal salts of cyclopentadiene is not particularly limited. For example, it can be easily carried out by contacting cyclopentadiene with metal sodium or lithium in a polar solvent such as ether or tetrahydrofuran. And the like.

As described above, one component of the catalyst used in the production method of the present invention is (1) the general formula Me ¹ R ¹ _n X ¹
A compound represented by _4-n (component (1)) and an alkali metal salt of (3) cyclopentadiene (component (3)),
Further optionally (2) the general formula _{^{Me 2 R 2 m X 2 z}} -m
The compound (component (2)) represented by is contacted with each other, and the order of contacting these components is not particularly limited. Therefore, regarding the contact method of the above components (1) to (3), first, when only the component (1) and the component (3) are used, a method of contacting each component at the same time,
Examples of the method include adding and contacting the component (3) with the component (1) and the component (1) with the component (3). When the components (1) to (3) are used, the component (1) is used. ~ (3)
At the same time, components (1) and (2) are contacted first, then components (3) are contacted, components (1) and (3) are contacted first, then component (2)
And the components (2) and (3) are first contacted, and then the component (1) is contacted, and a part of the component (3) is contacted with the component (1). The rest of 3) and the component (2) may be brought into contact with each other.

The method of contacting these two or three components is not particularly limited, and is generally an aromatic hydrocarbon such as benzene, toluene, xylene and ethylbenzene (usually having a carbon number of 1 to 3) in an inert atmosphere such as nitrogen or argon. 6-12), heptane, hexane, decane, dodecane, cyclohexane and other aliphatic or alicyclic hydrocarbons (usually having 5 to 12 carbon atoms) in the presence of a liquid inert hydrocarbon, with or without stirring. And a method of contacting. Moreover, the conditions at this time are normally -100 degreeC-2.
At a temperature of 00 ° C, preferably -50 ° C to 100 ° C,
It is desirable that the time is 30 minutes to 50 hours, preferably 1 hour to 24 hours.

When the components are brought into contact with each other in an inert hydrocarbon solvent, they may be directly subjected to the polymerization in a solution state after the completion of all the catalytic reactions, or they may be once prepared as solid catalyst components by a means such as precipitation and drying. After taking out, it may be used for polymerization. Of course, the contact reaction of each component may be performed multiple times. The usage ratio of these three components is usually 0.01 to 100 mol, preferably 0.1 to 10 mol, more preferably 1 to 5 mol, of the component (2) per 1 mol of the component (1).
It is desirable to prepare the component (3) in an amount of usually 0.01 to 100 mol, preferably 0.1 to 10 mol, and more preferably 0.5 to 2 mol.

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

The above-mentioned organoaluminum compounds are represented by the general formula R _n AlX _3-n (R is a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group or an aralkyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, X represents a hydrogen atom or a halogen atom, and n represents a compound represented by 1 ≦ n ≦ 3), and preferably trialkylaluminum is used. The alkyl group of trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. Is particularly preferable.

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

According to the present invention, the olefin is polymerized or copolymerized in the presence of the catalyst composed of the above-mentioned catalyst component and the modified organoaluminum compound. The catalyst component and the modified organoaluminum compound are separately or premixed. Then, it can be supplied into the polymerization reaction system. In any case, the proportion of the catalyst component and the modified organoaluminum compound used is such that the atomic ratio of aluminum in the modified organoaluminum compound to the transition metal in the catalyst component is 1 to 10.
It is selected to be in the range of 10,000, preferably 5 to 1,000.

The method of the present invention can be applied to the production of various olefin polymers and olefin copolymers. Among them, α-olefins having 2 to 12 carbon atoms, for example, ethylene, propylene and 1-butene. When homopolymerizing α-olefins such as 1, 1-hexene and 4-methylpentene-1, ethylene and propylene, ethylene and 1
-Butene, ethylene and 1-hexene, ethylene and 4-methylpentene-1, etc., ethylene and 3 to 1 carbon atoms
It is preferably used when copolymerizing two α-olefins, when copolymerizing propylene and 1-butene, and when copolymerizing ethylene and two or more other α-olefins.

For the purpose of modifying the olefin polymer, a diene compound such as butadiene, 1,4-hexadiene, ethylidene norbornene or dicyclopentadiene may be used as a copolymerization component. The method of the invention can be applied.

When the copolymerization is carried out, the comonomer content can be arbitrarily selected, but ethylene and α having 3 to 12 carbon atoms are used.
-When copolymerizing with an olefin, the α-olefin content in the ethylene / α-olefin copolymer is 40 mol% or less, preferably 30 mol% or less, and more preferably 20 mol% or less. It is desirable to do.

The polymerization reaction can be carried out by slurry polymerization, solution polymerization or gas phase polymerization in the presence of the above-mentioned specific catalyst. In particular, slurry polymerization or gas phase polymerization is preferable, and in a state where oxygen, water, etc. are substantially cut off, hexane,
Olefin in the presence or absence of an inert hydrocarbon solvent selected from aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane. Polymerize. The polymerization conditions at this time are 20 ° C to 200 ° C.
℃, preferably 50 ℃ ~ 100 ℃, pressure normal pressure ~ 70kg
/ Cm ² G, preferably atmospheric pressure to 20 kg / cm ² G, and the polymerization time is usually 5 minutes to 10 hours, preferably 5 minutes to 5 hours.

The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the addition of hydrogen to the polymerization reaction system allows the molecular weight to be adjusted more effectively. It can be carried out. Further, the method of the present invention can be applied to a multi-stage polymerization system of two or more stages having different hydrogen concentrations and polymerization temperatures without any trouble.

[0062]

EXAMPLES The present invention will be specifically described below 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 Index (MI) ASTM D 1238-57T 190 ° C, 2.16
It was measured based on the kg load. Density Measured according to ASTM D 1505-68.

Melting point measurement by differential scanning calorimeter (DSC) Using a DSC-20 type melting point measuring device manufactured by Seiko Denshi, the sample (5 mg) was kept at 180 ° C. for 3 minutes, and then at 10 ° C./minute to 0 ° C. The mixture was cooled to 0 ° C., held at 0 ° C. for 10 minutes, and then heated at 10 ° C./minute to measure the melting point.

Measurement of Mw / Mn Using a 150C GPC apparatus manufactured by Waters Co., a column Toyo Soda GMH-6, a solvent 0-dichlorobenzene, a temperature of 135 ° C., and a flow rate of 1.0 ml / min were measured. , Mw / Mn were determined.

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

Preparation of Modified Organoaluminum Compound The modified organoaluminum compound (methylalumoxane: MAO) used in the following Examples and Comparative Examples was prepared as follows. 13 g of copper sulfate pentahydrate was placed in a three-necked flask with a capacity of 300 ml equipped with an electromagnetic induction stirrer, and toluene 5 was added.
Suspended with 0 ml. Then, 150 ml of a solution of trimethylaluminum having a concentration of 1 mmol / ml was added dropwise to the above suspension at a temperature of 0 ° C. over 2 hours.
The temperature was raised to ° C and the reaction was carried out at that temperature for 24 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 (1) Preparation of Na Salt of Cyclopentadiene 50 ml of purified tetrahydrofuran (THF) was added to a 300 ml three-necked flask, then 11 g of cyclopentadiene and 4 g of metallic Na were added, and refluxed 4
Reacted for hours. After the reaction, unreacted Na is removed, and then 2
Prepared as a mol / 1 THF solution. (2) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then tetrapropoxy zirconium (Zr (O
Pr) ₄ ) 1.6 g and cyclopentadiene sodium salt (2 mol / liter, THF solution) 5 mL were added,
The mixture was stirred at room temperature for 30 minutes. Then, to this solution was added a separately prepared toluene solution of triethylaluminum (TEA) (solution in which 2.8 mL of TEA was dissolved in 47 mL of toluene) at room temperature over 30 minutes, and the mixture was further stirred for 1 hour to prepare a solution. A catalyst component A was obtained. All the operations were performed under a nitrogen atmosphere. (3) Gas Phase Polymerization A 3 L stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and 200 g of dried salt was added, and further 1.3 mg of a catalyst component A as a zirconium atom, a methylalumoxane (MAO) solution (1 mmol / mL) 1
4 mL was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) was continuously supplied and the total pressure was maintained at 9 kgf / cm ² to carry out polymerization for 2 hours. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 127 g of a white polymer. The produced ethylene / butene-1 copolymer has a melt index (MI) of 25 and a density of 0.9187 g / cm.
³ , Mw / Mn4.5, degree of branching 17.5 pieces / 1000C
The composition distribution was narrow, the melting point was 103.0 ° C., and the catalyst efficiency was 98,000 g copolymer / gZr.

Example 2 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then tetrapropoxy zirconium (Zr (O
Pr) ₄ ) 1.6 g and cyclopentadiene sodium salt (2 mol / liter, THF solution) 5 mL were added,
The mixture was stirred at room temperature for 30 minutes. Then, to this solution was added TH of separately prepared ethylmagnesium chloride (EtMgCl).
A mixed solution of 10 mL of F solution (2 mol / liter THF) and 40 mL of toluene was added at room temperature over 30 minutes, and the mixture was further stirred for 1 hour to obtain a solution-like catalyst component B. In addition,
All operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization Except that 1.4 mg of zirconium atom was added as the catalyst component B in place of the catalyst component A in Example 1 (however, the amount of MAO was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 134 g of a white polymer. Generated ethylene
Butene-1 copolymer has MI30 and a density of 0.9219 g.
/ Cm ³ , Mw / Mn 4.3, melting point 105.1 ° C., branching degree 16/1000 C, catalyst efficiency was 96000 g copolymer / gZr.

Example 3 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then tetrachlorozirconium (ZrCl ₄ ) was added.
1.2 g and cyclopentadiene sodium salt (2 mol / liter, THF solution) 7.5 mL were added, and the mixture was stirred at room temperature for 30 minutes. Next, 15 mL of a separately prepared THF solution of ethylmagnesium chloride (EtMgCl) (2 mol / liter THF) and 40 m of toluene were added to this solution.
The mixed solution with L was added at room temperature over 30 minutes, and further 1
After stirring for a time, a solution-like catalyst component C was obtained. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In Example 1, except that 1.4 mg of zirconium atom was added as the catalyst component C in place of the catalyst component A (however, the amount of MAO was changed to Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 66 g of a white polymer. The produced ethylene / butene-1 copolymer has MI100 and a density of 0.9225 g.
/ Cm ³ , Mw / Mn3.1, melting point 105.8 ° C, catalyst efficiency was 47,000 g copolymer / gZr.

Example 4 (1) Synthesis of tetrabenzylzirconium 5 g of zirconium tetrachloride was reacted with 12.9 g of benzylmagnesium chloride in ether and stirred at a temperature of 20 ° C. for 2 hours and then at room temperature for another hour. . Magnesium chloride that precipitated in the reaction was filtered to leave a yellow ether solution, and a tetrabenzylzirconium ether solution was obtained. 200 ml of this solution contained 5.1 g of tetrabenzylzirconium. (2) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then tetrabenzyl zirconium (ZrB
z ₄ ) 2.3 g of the above ether solution and cyclopentadiene lithium salt (2 mol / l, THF
Solution) (7.5 mL) was added, and the mixture was stirred at room temperature for 30 minutes. Then, to this solution was added a separately prepared solution of ethylmagnesium chloride (EtMgCl) in THF (2 mol / liter T).
A mixed solution of 15 mL of HF) and 40 mL of toluene was added at room temperature over 30 minutes, and the mixture was further stirred for 1 hour to obtain a catalyst component D in the form of a solution. All the operations were performed under a nitrogen atmosphere. (3) Gas Phase Polymerization In place of catalyst component A in Example 1, except that 1.6 mg of zirconium atom was added as catalyst component D (however,
The amount of MAO was changed so that Al / Zr = 2000), and vapor phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 118 g of a white polymer. Generated ethylene
The butene-1 copolymer has MI21 and a density of 0.9227 g.
/ Cm ³ , Mw / Mn 4.2, melting point 106.1 ° C, catalyst efficiency was 74000 g copolymer / gZr.

Example 5 (1) Preparation of 1,2,4-trimethylcyclopentadiene sodium salt 50 mL of THF produced was added to a 100 mL three-necked flask, and then 1,2,4-trimethylcyclopentadiene 20 g and metallic sodium 4 g were added. Under reflux 4
Reacted for hours. After completion of the reaction, unreacted sodium was removed to prepare a solution having a 1,2,4-trimethylcyclopentadiene sodium salt concentration of 2 mol / liter THF. (2) Preparation of catalyst component To a 300 mL three-necked flask was added 43 mL of purified toluene, and then 1.6 g of Zr (OPr) ₄ and 1,
5 mL of 2,4-trimethylcyclopentadiene sodium salt (2 mol / liter, THF solution) was added, and the mixture was stirred at room temperature for 30 minutes. Then, a mixed solution of 25 mL of a separately prepared toluene solution of trimethylaluminum (2 mol / liter THF) and 30 mL of toluene was added to this solution at room temperature over 30 minutes, and the mixture was further stirred for 1 hour to prepare a solution-like catalyst component E. Got All the operations were performed under a nitrogen atmosphere. (3) Gas Phase Polymerization Instead of the catalyst component A in Example 1, 1.5 mg of the catalyst component E was added as a zirconium atom (however,
The amount of MAO was changed so that Al / Zr = 500)
Was subjected to gas phase polymerization in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 98 g of a white polymer. Produced ethylene butene-1
The copolymer is MI8, density 0.9213 g / cm ³ , M
w / Mn 8.7, melting point 104.8 ° C., catalyst efficiency 650
It was 00 g copolymer / g Zr.

Example 6 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then 1.6 g of Zr (OPr) ₄ and cyclopentadienyltrimethylsilane sodium salt (2 mol / l, tetrahydro). Furan (THF) solution) 5
mL was added, and the mixture was stirred at room temperature for 30 minutes. This solution was then added to a separately prepared toluene solution of triethylaluminum (TEA) (47 mL of toluene, 5.6 mL of TEA).
Was added at room temperature over 30 minutes, and the mixture was further stirred for 1 hour to obtain a catalyst component F in the form of a solution.
All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In Example 1, except that 1.3 mg of zirconium atom was added as the catalyst component F instead of the catalyst component A (however, the MAO amount was changed to Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 66 g of a white polymer. The produced ethylene / butene-1 copolymer has MI11 and a density of 0.9110 g /
cm ³ , Mw / Mn 5.2, melting point 98.5 ° C., catalyst efficiency was 103000 g copolymer / g Zr.

Example 7 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then 1.2 g of ZrCl ₄ and cyclopentadiene sodium salt (2 mol / liter, THF solution).
5 mL was added, and the mixture was stirred at room temperature for 30 minutes. Then, to this solution, a toluene solution of methyllithium in which 2.8 mL of methyllithium was dissolved in 47 mL of toluene was separately prepared, and the whole amount thereof was added at room temperature over 30 minutes, followed by stirring for 1 hour to prepare a solution-form catalyst. Component G was obtained. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In Example 1, except that 1.4 mg of the catalyst component G was used as the zirconium atom in place of the catalyst component A (however, the MAO amount was changed to Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 69 g of a white polymer. The produced ethylene / butene-1 copolymer had MI98 and a density of 0.9223 g /
cm ³ , Mw / Mn 3.3, melting point 106.5 ° C., catalyst efficiency was 49000 g copolymer / g Zr.

Example 8 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, 1.9 g of tetrabutoxyzirconium and 5 mL of cyclopentadiene sodium salt (2 mol / liter, THF solution) were added, and the mixture was allowed to stand at room temperature. Stir for 30 minutes below. Then, 25 mL of a separately prepared THF solution of butyllithium (2 mol / L) was added to this solution at room temperature over 30 minutes, and the mixture was further stirred for 1 hour to obtain a solution-like catalyst component H. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In Example 1, except that the catalyst component H was replaced with 1.3 mg of zirconium atom as the catalyst component H (however, the MAO amount was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 66 g of a white polymer. The produced ethylene / butene-1 copolymer had MI33 and a density of 0.9253 g /
cm ³ , Mw / Mn 4.7, melting point 106.8 ° C., catalyst efficiency was 51000 g copolymer / g Zr.

Example 9 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then 1.4 g of Zr (OPr) ₂ Cl ₂ and cyclopentadienylmethylsilane sodium salt (2 mol / liter, (THF solution) (10 mL) was added, and the mixture was stirred at room temperature for 3
Stir for 0 minutes. Then, to this solution, a toluene solution of diethylaluminum ethoxide in which 6.1 mL of diethylaluminum ethoxide was dissolved in 47 mL of toluene was separately prepared, and the whole amount thereof was added at room temperature over 30 minutes, and the mixture was further stirred for 1 hour, A catalyst component I in solution was obtained. In addition,
All operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In Example 1, except that 1.3 mg of zirconium atom was added as the catalyst component I in place of the catalyst component A (however, the MAO amount was changed to Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 44 g of a white polymer. The ethylene / butene-1 copolymer produced had MI23 and a density of 0.9210 g /
cm ³ , Mw / Mn 5.9, melting point 104.5 ° C., catalyst efficiency 57,000 g copolymer / g Zr.

Example 10 (1) Gas Phase Polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added, and 1.2 mg of the catalyst component A used in Example 1 as a zirconium atom was added. , MAO solution (1 mmol / mL) 1
4 mL was added and heated to 60 ° C. with stirring. Then, ethylene gas was introduced so as to be 9 kgf / cm ^2, and the polymerization was started. While continuously supplying ethylene gas, the total pressure was maintained at 9 kgf / cm ^2, and the polymerization was carried out for 2 hours. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 139 g of a white polymer. The produced ethylene polymer had MI15 and a density of 0.9495 g / c.
m ³ , Mw / Mn 4.8, melting point 132.3 ° C., catalyst efficiency was 108000 g copolymer / g Zr.

Example 11 (1) Preparation of catalyst component To a 300 mL three-necked flask was added 43 mL of purified toluene, and then 1.6 g of Zr (OPr) ₄ and bis (monomethylcyclopentadienyl) dimethylsilane sodium salt (2 mol / mol). Liter, 5 mL of THF solution) were added, and the mixture was stirred at room temperature for 30 minutes. Then add 47 to this solution.
A toluene solution of triethylaluminum in which 2.8 mL of triethylaluminum was dissolved in mL toluene was separately prepared, and the whole amount thereof was added at room temperature over 30 minutes, followed by stirring for 1 hour to obtain a solution-like catalyst component J. .. All the operations were performed under a nitrogen atmosphere. (2) Gas phase polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added, and 1.2 mg of a catalyst component J was used as a zirconium atom, MA.
14 mL of O solution (1 mmol / mL) was added and heated to 60 ° C. with stirring. Then, 9 kgf of propylene gas
/ Cm ² to start polymerization, and continuously supply propylene gas while maintaining a total pressure of 9 kgf / cm 2.
^It was maintained at 2 and polymerized for 2 hours. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 36 g of a white polymer. The produced propylene polymer is M
I29, density 0.9007 g / cm ³ , Mw / Mn 4.
3, the melting point was 85.3 ° C., and the catalyst efficiency was 21000 g copolymer / g Zr.

Example 12 (1) Preparation of catalyst component To a 300 mL three-necked flask was added 43 mL of purified toluene, and then 1.7 g of tetrabutoxytitanium and cyclopentadiene sodium salt (2 mol / liter, TH
(F solution) (5 mL) was added, and the mixture was stirred at room temperature for 30 minutes. Then, to this solution was separately prepared a toluene solution of tributylaluminum in which 5.0 mL of tributylaluminum was dissolved in 47 mL of toluene, and the whole amount thereof was added at room temperature over 30 minutes, followed by stirring for 1 hour to prepare a solution-form catalyst. Ingredient K
Got All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization Instead of the catalyst component A in Example 1, 1.6 mg of the catalyst component K was added as a titanium atom (provided that MAO was used).
The amount was changed so that Al / Ti = 1000), and vapor phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 13 g of a white polymer. The produced ethylene / butene-1 copolymer had MI11, a density of 0.9235 g / cm ³ , and a Mw.
/ Mn 4.1, melting point 105.1 ° C., catalyst efficiency 2100
It was 0 g copolymer / g Zr.

Example 13 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, then 2.1 g of tetrapropoxy hafnium and 5 mL of cyclopentadiene sodium salt (2 mol / liter, THF solution) were added, and the mixture was allowed to stand at room temperature. Stir for 30 minutes below. Then add 2.0 mL of 47 mL toluene to this solution.
Was prepared separately for each toluene solution of trimethylaluminum, and the whole amount thereof was added at room temperature over 30 minutes, followed by stirring for 1 hour to obtain a solution-like catalyst component L. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In place of the catalyst component A in Example 1, 2.1 mg of the catalyst component L was added as a hafnium atom (however, M
AO amount was changed so that Al / Hf = 1000)
Was subjected to gas phase polymerization in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 66 g of a white polymer. Produced ethylene butene-1
The copolymer has MI21, a density of 0.9219 g / cm ³ ,
Mw / Mn 2.9, melting point 104.6 ° C, catalyst efficiency 32
It was 000 g copolymer / g Zr.

Example 14 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then tetrapropoxy zirconium (Zr (O
Pr) ₄ ) 1.6 g and cyclopentadiene sodium salt (2 mol / liter, THF solution) 5 mL were added,
The mixture was stirred at room temperature for 30 minutes and further stirred for 1 hour to obtain a catalyst component M in the form of a solution. All the operations were performed under a nitrogen atmosphere. (2) Gas phase polymerization In place of the catalyst component A in Example 1, except that 2.5 mg of the catalyst component M was added as a zirconium atom (however,
The amount of MAO was changed so that Al / Zr = 1000), and vapor phase polymerization was performed in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 30 g of a white polymer. The ethylene / butene-1 copolymer produced had MI9 and a density of 0.9215 g / c.
m ³ , Mw / Mn 4.2, melting point 104.2 ° C., catalyst efficiency was 29000 g copolymer / g Zr.

Example 15 (1) Liquid Phase Polymerization A 3 L stainless steel autoclave equipped with a stirrer was replaced with nitrogen, 500 ml of toluene was added, and then the catalyst component F used in Example 6 was 0.6 mg as zirconium atom, MAO. Solution (1 mmol / ml) 3.
Add 3 ml, then add 60 ml of hexene, 60
Polymerization was carried out for 2 hours while heating to 0 ° C. and continuously supplying ethylene gas while maintaining the total pressure at 9 kgf / cm ² .
After the completion of the polymerization, excess gas was discharged, ethanol was added to deactivate the catalyst, and the mixture was dried to obtain 66 g of an ethylene / hexene-1 copolymer. The produced ethylene polymer is MI
2.7, density 0.9196 g / cm ³ , Mw / Mn =
3.6, melting point 101.3 ° C, catalyst efficiency 110000g
It was a copolymer / gZr.

Comparative Example 1 (1) Preparation of catalyst component 100 mL of purified toluene in a 300 mL three-necked flask
Was added, and then 4.2 g of Zr (OPr) ₄ was added and stirred at room temperature to obtain a catalyst component A ′. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization Instead of the catalyst component A in Example 1, 1.3 mg of the catalyst component A ′ was added as a zirconium atom (however, the MAO amount was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1, but no polymer was produced.

Comparative Example 2 (1) Preparation of catalyst component 100 mL of purified toluene in a 300 mL three-necked flask
Was added, and then 4.2 g of tetrabenzyl zirconium was added and stirred at room temperature to obtain a catalyst component B ′. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In Example 1, except that the catalyst component B ′ was replaced by 1.5 mg of zirconium atom instead of the catalyst component A (however, the amount of MAO was changed to Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1, but no polymer was produced.

Comparative Example 3 (1) Preparation of catalyst component 100 mL of purified toluene in a 300 mL three-necked flask
Was added, and then 4.2 g of tetrachlorozirconium was added and stirred at room temperature to obtain a catalyst component C ′. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In Example 1, except that 1.4 mg of the catalyst component C ′ was added as a zirconium atom instead of the catalyst component A (however, the MAO amount was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1, but no polymer was produced.

Comparative Example 4 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, then 1.6 g of Zr (OPr) ₄ was added, and the mixture was stirred at room temperature for 30 minutes. This solution was then added to a separately prepared toluene solution of triethylaluminum (TEA) (47
(solution of 2.8 mL TEA dissolved in mL toluene)
Was added over 30 minutes at room temperature, and the mixture was further stirred for 1 hour to obtain a solution-form catalyst component D ′. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In Example 1, except that 1.5 mg of the catalyst component D ′ was added as the zirconium atom instead of the catalyst component A (however, the MAO amount was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1, but no polymer was produced.

Comparative Example 5 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, then 1.6 g of tetrabenzylzirconium was added, and the mixture was stirred at room temperature for 30 minutes. Then, a separately prepared toluene solution of triethylaluminum (TEA) (a solution prepared by dissolving 2.8 mL TEA in 47 mL toluene) was added to this solution at room temperature over 30 minutes, and further 1
After stirring for a period of time, a solution of catalyst component E ′ was obtained. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In place of the catalyst component A in Example 1, except that 1.3 mg of the catalyst component E ′ was added as a zirconium atom (however, the MAO amount was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 8 g of a white polymer. The produced ethylene / butene-1 copolymer had MI1.3 and a density of 0.9254 g /
cm ³ , Mw / Mn 5.1, melting point 117.3 ° C., catalyst efficiency was 6000 g copolymer / gZr, catalyst efficiency was low, and only a polymer having poor physical properties was obtained.

Comparative Example 6 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, 1.6 g of tetrachlorozirconium was added, and the mixture was stirred at room temperature for 30 minutes. Then, a separately prepared toluene solution of triethylaluminum (TEA) (a solution prepared by dissolving 2.8 mL TEA in 47 mL toluene) was added to this solution at room temperature over 30 minutes, and further 1
After stirring for a time, a solution of catalyst component F ′ was obtained. All the operations were performed under a nitrogen atmosphere. (2) Gas phase polymerization In place of the catalyst component A in Example 1, 1.5 mg of the catalyst component F ′ was added as a zirconium atom (however, the amount of MAO was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1, but no polymer was produced.

Comparative Example 7 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, then 1.9 g of tetrabutoxyzirconium was added, and the mixture was stirred at room temperature for 30 minutes. Then, a solution of butyllithium in THF (2 mol / L) 25 prepared separately was added to this solution.
mL was added at room temperature over 30 minutes, and the mixture was further stirred for 1 hour to obtain a solution-form catalyst component G ′. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization Except that 1.6 mg of the catalyst component G ′ was added as a zirconium atom instead of the catalyst component A in Example 1 (however, the MAO amount was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1, but no polymer was produced.

Comparative Example 8 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then tetrabenzylzirconium (ZrB
The above ether solution corresponding to 2.3 g of z ₄ ) was added, and the mixture was stirred at room temperature for 30 minutes. Then, to this solution was added a separately prepared solution of methyllithium in THF (2 mol / liter TH
F) A mixed solution of 15 mL and 40 mL of toluene was added at room temperature over 30 minutes, and the mixture was further stirred for 1 hour to obtain a catalyst component H ′ in the form of a solution. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization Instead of the catalyst component A in Example 1, 1.5 mg of the catalyst component H ′ was added as a zirconium atom (however, the amount of MAO was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 12 g of a white polymer. The ethylene / butene-1 copolymer produced had MI 1.9 and a density of 0.9221 g.
/ Cm ³ , Mw / Mn 5.3, melting point 116.3 ° C., catalyst efficiency is 8000 g copolymer / g Zr, and catalyst efficiency is low.
Moreover, only a polymer having poor physical properties was obtained.

Comparative Example 9 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, then 1.2 g of ZrCl ₄ was added, and the mixture was stirred at room temperature for 30 minutes.
It was stirred for a minute. Then, 5 mL of a separately prepared solution of methyllithium in THF (2 mol / L) was added to this solution at room temperature for 3 times.
The mixture was added over 0 minutes and further stirred for 1 hour to obtain a catalyst component I ′ in the form of a solution. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In place of the catalyst component A in Example 1, except that 1.4 mg of the catalyst component I ′ was added as a zirconium atom (however, the MAO amount was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1, but no polymer was produced.

Comparative Example 10 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, then 1.6 g of Zr (OPr) ₄ was added, and the mixture was stirred at room temperature for 30 minutes. Then, 10 mL of a separately prepared THF solution of ethylmagnesium chloride (EtMgCl) (2 mol / liter THF) and 40 parts of toluene were added to this solution.
The mixed solution with mL was added at room temperature over 30 minutes, and the mixture was further stirred for 1 hour to obtain a solution-like catalyst component J ′. All the operations were performed under a nitrogen atmosphere. (2) Gas phase polymerization In place of the catalyst component A in Example 1, except that 1.6 mg of the catalyst component J ′ was added as a zirconium atom (however, the MAO amount was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1, but no polymer was produced.

Comparative Example 11 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then tetrabenzylzirconium (ZrB
The above ether solution corresponding to 2.3 g of z ₄ ) was added, and the mixture was stirred at room temperature for 30 minutes. Then, to this solution was added separately prepared ethylmagnesium chloride (EtMgCl) in THF.
15 mL of solution (2 mol / liter THF) and toluene 4
A mixed solution with 0 mL was added at room temperature over 30 minutes, and the mixture was further stirred for 1 hour to obtain a catalyst component K ′ in the form of a solution. In addition,
All operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization In place of the catalyst component A in Example 1, except that 1.7 mg of the catalyst component K ′ was added as a zirconium atom (however, the amount of MAO was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1. After the polymerization was completed, the excess mixed gas was discharged and cooled, and the contents were taken out to obtain 26 g of a white polymer. The produced ethylene / butene-1 copolymer had MI2.1 and a density of 0.9219 g.
/ Cm ³ , Mw / Mn 5.2, melting point 114.9 ° C., catalyst efficiency was 15000 g copolymer / gZr, and only a polymer having poor physical properties was obtained.

Comparative Example 12 (1) Preparation of catalyst component 43 mL of purified toluene was added to a 300 mL three-necked flask, and then tetrachlorozirconium (ZrCl ₄ ) was added.
1.2 g was added, and the mixture was stirred at room temperature for 30 minutes. This solution was then added to a separately prepared ethylmagnesium chloride (Et
MgCl) in THF (2 mol / liter THF) 1
30 mL of a mixed solution of 5 mL and 40 mL of toluene at room temperature
The mixture was added over a period of minutes, and the mixture was further stirred for 1 hour to obtain a solution-form catalyst component L ′. All the operations were performed under a nitrogen atmosphere. (2) Gas Phase Polymerization Instead of the catalyst component A in Example 1, 1.4 mg of the catalyst component L ′ was added as a zirconium atom (however, the MAO amount was changed so that Al / Zr = 1000). Gas phase polymerization was carried out in the same manner as in Example 1, but no polymer was produced.

Comparative Example 13 (1) Preparation of Catalyst Component 3.8 ml of zirconocene chloride was dissolved in 13 ml of a toluene solution of MAO (1 mmol / ml) at room temperature. The mixture was stirred at room temperature for 30 minutes and then subjected to polymerization. All operations were performed under a nitrogen atmosphere. (2) Gas phase polymerization A 3 L stainless steel autoclave equipped with a stirrer was replaced with nitrogen, the catalyst and dried salt 200
g, and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / Ethylene molar ratio of 0.05) was continuously supplied and the total pressure was maintained at 9 kgf / cm ² to carry out polymerization for 2 hours. After the polymerization is completed, the excess mixed gas is discharged and cooled,
The content was taken out to obtain 127 g of a white polymer. The produced ethylene-butene-1 copolymer has a melt index (MI) of 25, a density of 0.9102 g / cm ³ , and a Mw.
/ Mn 7.9, branching degree 32.4 pieces / 1000C, melting point 9
At 7.8 ° C., the catalyst efficiency was 64000 g copolymer / g Zr.

[0095]

Industrial Applicability The production method of the present invention can produce a polyolefin with high activity, and can control the molecular weight distribution of the obtained polyolefin by appropriately selecting a catalyst, especially in the case of a copolymer. Has a narrow composition distribution. Moreover, the catalyst used in the present invention has excellent characteristics such as easy preparation.

[Brief description of drawings]

FIG. 1 is a flow chart showing the steps for preparing a catalyst used in the present invention.

Claims (2)

[Claims] 1. a) (1) General formula Me ¹ R ¹ _n X ¹
A compound represented by _4-n (in the formula, R ¹ has 1 to 24 carbon atoms)
Hydrocarbon residue, X ¹ is a halogen atom, Me is Zr, T
i or Hf is shown, and n is 0 ≦ n ≦ 4. ) And (2) a catalyst component obtained by bringing alkali metal salts of cyclopentadiene into contact with each other, and b) a modified organoaluminum compound containing an Al—O—Al bond obtained by reacting an organoaluminum compound with water. A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst. 2. a) (1) The general formula Me ¹ R ¹ _n X ¹
A compound represented by _4-n (in the formula, R ¹ has 1 to 24 carbon atoms)
Hydrocarbon residue, X ¹ is a halogen atom, Me is Zr, T
i or Hf is shown, and n is 0 ≦ n ≦ 4. ) (2) Alkali metal salt of cyclopentadiene and (3) compound represented by the general formula Me ² R ² _m X ² _zm (wherein R ² is a hydrocarbon group having 1 to 24 carbon atoms, X ² is an alkoxy group having 1 to 12 carbon atoms or a halogen atom, Me
² represents a Group I to III element of the periodic table, z is the valence of Me ² , and m is 0 ≦ m ≦ 3. Olefins are polymerized in the presence of a catalyst consisting of a catalyst component obtained by bringing them into contact with each other and b) a modified organoaluminum compound containing an Al-O-Al bond obtained by a reaction of an organoaluminum compound and water. A method for producing a polyolefin, which comprises copolymerizing.