JPH06199945A - Method for producing polyolefin - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for producing a polyolefin having a high polymerization activity and a relatively wide molecular weight distribution. Structure (1) A compound represented by the general formula MeR ¹ _n X _4-n (wherein R ¹ is a hydrocarbon residue having 1 to 24 carbon atoms,
X represents a halogen atom, Me represents Zr, Ti, or Hf, and n is 0 ≦ n ≦ 4. ), (2) General formula AlR ²
_p X compound represented by _3-p (wherein, ^{R 2} is 1 to the number of carbon atoms
24 hydrocarbon residues, X is a halogen atom, and p is 0
<P ≦ 3. ), (3) an organic cyclic compound having two or more conjugated double bonds, and (4) a general formula R ³ R ⁴ Mg
(Wherein R ³ and R ⁴ have 1 to 24 carbon atoms)
Is a hydrocarbon group. The olefins are polymerized or copolymerized in the presence of a catalyst consisting of

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyolefin using a specific catalyst. More specifically, it relates to a method for producing a polyolefin having a high polymerization activity and a relatively wide molecular weight distribution by polymerizing an olefin in the presence of a specific catalyst.

[0002]

2. Description of the Related Art In producing a polyolefin, particularly an ethylene polymer or an ethylene / α-olefin copolymer, a catalyst comprising, for example, a zirconium compound (typically a zirconocene compound) and an aluminoxane is used. It is used in JP-A-58
It is known as shown in No. 19309. In such a conventional technique, an ethylene-based polymer can be produced in a certain yield, and the obtained copolymer has a narrow molecular weight distribution and a narrow composition distribution.

However, in order to obtain a polymer in a high yield using such a catalyst system, the amount of aluminoxane used as a promoter for the transition metal such as zirconium must be increased. Further, since aluminoxane, especially methylaluminoxane, is expensive, there is a drawback that the cost for producing the catalyst becomes high. From the above, it has been desired to reduce the use ratio of aluminoxane to the catalyst component.

In order to improve this point, JP-A-60-28
No. 0802 and Japanese Patent Laid-Open No. 63-218707 have been proposed, but the effect is not yet sufficient.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have conducted extensive studies to solve the above-mentioned drawbacks of the prior art, and as a result, use a novel catalyst system having a completely different constitution from the conventional catalyst system, We have found a catalyst component that can produce a polyolefin with a high yield, a high molecular weight, and a relatively wide molecular weight distribution without the essential use of aluminoxanes.

That is, the present invention provides (1) the general formula

[0007]

[Chemical 4]

A compound represented by the formula (wherein R ¹ is a carbon number 1
~ 24 hydrocarbon residues, X is a halogen atom, Me is Z
represents r, Ti, or Hf, and n is 0 ≦ n ≦ 4. ), (2) general formula

[0009]

[Chemical 5]

A compound represented by the formula (wherein R ² is 1 carbon atom)
To 24 hydrocarbon residues, X represents a halogen atom, and p is a number of 0 <p ≦ 3. ), (3) an organic cyclic compound having two or more conjugated double bonds, and (4) a general formula

[0011]

[Chemical 6]

The olefins are polymerized or copolymerized in the presence of a catalyst comprising a compound represented by the formula (wherein R ³ and R ⁴ are hydrocarbon groups having 1 to 24 carbon atoms). And a method for producing an olefin polymer.

The catalyst component used in the method of the present invention has a high activity per transition metal without essentially using aluminoxane, and the obtained polyolefin, especially polyethylene, has a high molecular weight and a relatively wide molecular weight distribution. It has the feature that its molecular weight distribution can be controlled freely. Further, by using the catalyst prepared by changing the kind and composition ratio of the catalyst component, the molecular weight of the polymer can be freely controlled without lowering the polymerization activity. Further, the copolymer obtained by copolymerizing α-olefin and ethylene has a high melting point and can be suitably used in a field requiring heat resistance. The catalyst used in the present invention is also characterized in that it can be easily synthesized.

The present invention will be described in detail below.

The olefin polymerization catalyst component of the present invention is
As described above (1) General formula

[0016]

[Chemical 7]

A compound represented by the formula (2): general formula

[0018]

[Chemical 8]

A compound represented by: (3) an organic cyclic compound having two or more conjugated double bonds, and (4) a general formula

[0020]

[Chemical 9]

It is composed of catalyst components obtained by contacting or mixing the compounds represented by the following, and the details are as follows.

First, the general formula of the component (1)

[0023]

[Chemical 10]

The compound represented by will be described. In such formula, R ¹ has 1 to 24 carbon atoms, preferably 1
~ 12, more preferably 1 to 8 hydrocarbon residues, such hydrocarbon residues include a methyl group,
Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, alkenyl groups such as vinyl group, allyl group, aryl groups such as phenyl group, tolyl group, xylyl group, benzyl group, phenethyl group , Hydrocarbon groups exemplified by aralkyl groups such as styryl group and neofil group, and alkoxy groups such as methoxy group, exci group, propoxy group, butoxy group, pentyloxy group, phenoxy group, and aryloxy group such as tolyloxy group. And oxygen-containing hydrocarbon groups such as benzyloxy group and the like aralkyloxy groups. X is a halogen atom of fluorine, iodine, chlorine and bromine, Me is Zr, Ti or Hf, and preferably Zr.
n is 0 ≦ n ≦ 4, preferably 0 <n ≦ 4.

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

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-butyltribromozirconium, monopentyltribromozirconium, monophenyltribromozirconium, monotolyltribromozirconium, monobenzyltribromozirconium, monoallyltribromozirconium, mononeophyltribromozirconium, tetrabromozirconium, trimethoxy Monobromozirconium, dimethoxydibromozirconium, monomethoxytribromozirconium, triethoxymonobromozirconium, diethoxydibromozirconium, monoethoxytribromozirconium, tripropoxymonobromozirconium, dipropoxydibromozirconium, monobropoxytribromozirconium, tri-n -Butoxymonobromozirconium, di-n-butoxydibromozirconium , Mono-n-butoxytribromozirconium, tripentyloxymonobromozirconium, dipentyloxydibromozirconium, monopentyloxytribromozirconium, triphenoxymonobromozirconium, diphenoxydibromozirconium, monophenoxytribromozirconium, tritolyloxymonobromo Zirconium, ditolyloxydibromozirconium, monotolyloxytribromozirconium, tribenzyloxymonobromozirconium, dibenzyloxydibromozirconium, monobenzyloxytribromozirconium, triallyloxymonobromozirconium, diallyloxydibromozirconium, monoallyloxy Tribromozirconium, trineophylloxy monobromozirconi Um, dineofiloxydibromozirconium, mononeophylloxytribromozirconium,

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-Butyltriiodozirconium, monopentyl triiodozirconium, monophenyltriiodozirconium, monotolyltriiodozirconium, monobenzyltriiodozirconium, tetraiodozirconium, trimethoxymonoiodozirconium, dimethoxydiiodozirconium, monomethoxytriiodo Zirconium, triethoxy monoiodo zirconium, diethoxy diiodo zirconium, monoethoxy triiodo zirconium, tripropoxy monoiodo zirconium, dipropoxy diiodo zirconium, monopropoxy triiodo zirconium, tri n-
Butoxymonoiodozirconium, di-n-butoxydiiodozirconium, mono-n-butoxytriiodozirconium, tripentyloxymonoiodozirconium,
Dipentyloxydiiodozirconium, Monopentyloxytriiodozirconium, Triphenoxymonoiodozirconium, Diphenoxydiiodozirconium, Monophenoxytriiodozirconium, Tritolyloxymonoiodozirconium, Ditryloxydiiodozirconium, Monotolyloxytriiodo Zirconium, tribenzyloxymonoiodozirconium,
Dibenzyloxydiiodozirconium, monobenzyloxytriiodozirconium, triallyloxymonoiodozirconium, diallyloxydiiodozirconium, monoallyloxytriiodozirconium, trineophylloxymonoiodozirconium, dineofiloxydiiodozirconium, Mononeophyll oxytriiodozirconium,

Tribenzylmonomethoxyzirconium,
Tribenzyl monoethoxy zirconium, tribenzyl monopropoxy zirconium, tribenzyl monobutoxy zirconium, tribenzyl monopentyloxy zirconium, tribenzyl monophenoxy zirconium,
Tribenzyl monotolyloxy zirconium, tribenzyl monobenzyloxy zirconium, tribenzyl monoallyloxy zirconium, tribenzyl mononeophyloxy zirconium, dibenzyl dimethoxy zirconium, dibenzyl diethoxy zirconium, dibenzyl dipropoxy zirconium, dibenzyl dibutoxy Zirconium, dibenzyldipentyloxyzirconium, dibenzyldiphenoxyzirconium, dibenzylditolyloxyzirconium, dibenzyldibenzyloxyzirconium, dibenzyldiallyloxyzirconium, dibenzyldineophyloxyzirconium, monobenzyltrimethoxyzirconium, monobenzyl Triethoxyzirconium, monobenzyltripropoxyzirconium, mono Benzyltributoxyzirconium, monobenzyltripentyloxyzirconium, monobenzyltriphenoxyzirconium, monobenzyltritolyloxyzirconium, monobenzyltribenzyloxyzirconium, monobenzyltriallyloxyzirconium, monobenzyltrineophylloxyzirconium, trineo Fill monomethoxy zirconium, trineofil monoethoxy zirconium, trineofil monopropoxy zirconium, trineofil monobutoxy zirconium, trineofil monophenoxy zirconium, dineofil dimethoxyzirconium, dineofil diethoxyzirconium, dineofildi Bropoxy zirconium, Dineofil dibutoxy Zirconium, Dineofil diphenoxy Ruconium, mononeophile trimethoxyzirconium, mononeophile triethoxyzirconium, mononeophile tripropoxy zirconium, mononeophyll tributoxy zirconium, mononeophile triphenoxy zirconium, trimethoxy (trimethylsilylmethyl) zirconium, triethoxy (trimethylsilylmethyl) zirconium , Tripropoxy (trimethylsilylmethyl) zirconium, tributoxy (trimethylsilylmethyl) zirconium,

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

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

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

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,

Trimethoxy (trimethylsilylmethyl)
Titanium, triethoxy (trimethylsilylmethyl)
Titanium, tripropoxy (trimethylsilylmethyl) titanium, tributoxy (trimethylsilylmethyl) titanium,

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, tetraneophiloxyhafnium, 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, diben
Zirdibromohafnium, monomethyltribromohafni
Um, monoethyltribromohafnium, mono n-butyl
Lutribromohafnium, monobenzyltribromohaf
Ni, Tetrabromohafnium, Trimethoxymonobu
Lomohafnium, dimethoxydibromohafnium, mono
Methoxytribromohafnium, triethoxy monobrom
Mohafnium, diethoxydibromohafnium, monoe
Toxitribromohafnium, tripropoxy monobrom
Mohafnium, dipropoxydibromohafnium, mono
Propoxytribromohafnium, tri-n-butoximo
Nobromohafnium, di-n-butoxydibromohafnium
System, mono-n-butoxytribromohafnium, tripene
Cyloxymonobromohafnium, dipentyloxydi
Bromohafnium, monopentyloxytribromohaf
Nium, triphenoxymonobromohafnium, diet
Xidibromohafnium, monophenoxytribromoha
Hunium, tritolyloxymonobromohafnium, di
Trilyloxydibromohafnium, monotolyl oxyto
Libromohafnium, tribenzyloxymonobromoha
Hunium, dibenzyloxydibromohafnium, mono
Benzyloxytribromohafnium, tetraiodoha
Hunium, trimethylmonoiodohafnium, triethyl
Rumonoiodohafnium, tripropylmonoiodohaf
Ni, tri-n-butylmonoiodohafnium, tribe
And mono-iodohafnium, dimethyldiiodohafni
Um, diethyldiiodohafnium,

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

Tribenzyl monopropoxy hafnium,
Tribenzyl monobutoxy hafnium, tribenzyl monophenoxy hafnium, dibenzyl dimethoxy hafnium, dibenzyl diethoxy hafnium, dibenzyl dipropoxy hafnium, dibenzyl dibutoxy hafnium, dibenzyl diphenoxy hafnium, monobenzyl trimethoxy hafnium, monobenzyl tri Ethoxy hafnium, monobenzyl tripropoxy hafnium, monobenzyl tributoxy hafnium, monobenzyl triphenoxy hafnium, trineophyll monomethoxy hafnium, trineophyll monoethoxy hafnium, trineophyll monopropoxy hafnium, trineophyll monobutoxy hafnium, tri Neofil monophenoxy hafnium, dineofil dimethoxy hafnium,
Dineofildiethoxyhafnium, Dineofildipropoxyhafnium, Dineofildibutoxyhafnium, Dineofildiphenoxyhafnium, Mononeophile trimethoxyhafnium, Mononeophile triethoxyhafnium, Mononeophile tripropoxyhafnium, Mono Examples are neofil tributoxy hafnium, mononeophyl triphenoxy hafnium, trimethoxy (trimethylsilylmethyl) hafnium, triethoxy (trimethylsilylmethyl) hafnium, tripropoxy (trimethylsilylmethyl) hafnium, tributoxy (trimethylsilylmethyl) hafnium.
Of course, in these compounds listed as the specific examples of the above-mentioned component (2), the R ′ is not only n- but also i.
It also includes cases in which there are various structurally different groups such as so-, s-, t-, and neo-. Among these specific compounds, tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetrabutoxyzirconium, tetrabutoxytitanium and tetrabutoxyhafnium are preferable. Particularly preferred are Zr (OR) ₄ compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium. These compounds can be used as a mixture of two or more kinds.

Next, the general formula of component (2)

[0041]

[Chemical 11]

The compound represented by will be described. In such formula, R ² has 1 to 24 carbon atoms, preferably 1
~ 12, more preferably 1 to 8 hydrocarbon residues, such hydrocarbon residues include a methyl group,
Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, alkenyl groups such as vinyl group, allyl group, aryl groups such as phenyl group, tolyl group, xylyl group, benzyl group, phenethyl group , Hydrocarbon groups exemplified by aralkyl groups such as styryl group and neofil group, and alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, phenoxy group, aryloxy group such as tolyloxy group. , Oxygen-containing hydrocarbon groups exemplified by aralkyloxy groups such as benzyloxy group and the like, and R ² is 2
When one or more are included, they may be the same or different. X represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p is a number of 0 <p ≦ 3. Note that such general formula

[0043]

[Chemical 12]

As the compound represented by the formula (1), those having at least one hydrocarbon group are particularly desirable. Also, this general formula

[0045]

[Chemical 13]

As the compound represented by the formula (1), a compound having at least one halogen atom is particularly desirable, and a compound having at least one halogen atom in at least one aluminum compound is desirable even when a plurality of types of aluminum compounds are used in combination. .

Compounds of this type have the general formula:

[0048]

[Chemical 14]

And

[0050]

[Chemical 15]

Organoaluminum compounds represented by the following are included, and specifically, trimethylaluminum, triethylaluminum, trioctylaluminum, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum fluoride, diethylaluminum iodide, ethylaluminum dichloride, Ethyl aluminum dibromide, ethyl aluminum difluoride, ethyl aluminum diiodide, tripropiroaluminum, dipropyl aluminum chloride, dipropyl aluminum bromide,
Dipropyl aluminum fluoride, dipropyl aluminum 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 iodide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, propyl aluminum sesquichloride,
Propyl 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, butyl aluminum dibromide, butyl aluminum difluoride, butyl aluminum diiodide, tris-butyl aluminum, di s-butyl aluminum chloride, di s-butyl Aluminum bromide, s Butylaluminum fluoride,
Di-s-butyl aluminum iodide, s-butyl aluminum dichloride, s-butyl aluminum dibromide, s-butyl aluminum difluoride, s
-Butyl aluminum diiodide, tri-t-butyl aluminum, di-t-butyl aluminum chloride,
Di-t-butyl aluminum bromide, di-t-butyl aluminum fluoride, di-t-butyl aluminum iodide,

T-butylaluminum dichloride, t
-Butyl aluminum dibromide, t-butyl aluminum difluoride, t-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, trihexyl 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, 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. , Propyl Aluminum Ethoxide, Dipropyl Aluminum Propoxide, Dipropyl Aluminum Ethoxide, Dipropyl Aluminum Propoxide, Dipropyl Aluminum Butoxide, Butyl Aluminum Methoxide, Butyl Aluminum Ethoxide, Butyl Aluminum Propoxide, Butyl Aluminum Butoxide, Dibutyl Aluminum Methoxy And dibutyl aluminum ethoxide, dibutyl aluminum propoxide, dibutyl aluminum butoxide and the like.

Of course, it is preferable to use a plurality of these aluminum compounds in any combination, and in this case, it is desirable that at least one aluminum compound has at least one halogen atom.

As the component (3), an organic cyclic compound having two or more conjugated double bonds is used. The component (3) has a conjugated double bond of 2 or more, preferably 2 to 4, more preferably 2 to 3, and has a total carbon number of 4 to 24, preferably 4 to 12 Hydrogen compound; Cyclic hydrocarbon compound in which the cyclic hydrocarbon compound is partially substituted with a hydrocarbon group of 1 to 6 (typically, an alkyl group having 1 to 12 carbon atoms or an aralkyl group); Two or more bonds, preferably 2 to 4, more preferably 2 to
An organosilicon compound having three cyclic hydrocarbon groups having a total carbon number of 4 to 24, preferably 4 to 12; wherein the ring hydrocarbon group is partially a hydrocarbon residue of 1 to 6; Substituted organosilicon compounds; further included are alkali metal salts (sodium salt, lithium salt, etc.) of these compounds.

Incidentally, the organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.

[0057]

[Chemical 16]

Here, Cp is a cyclopentadienyl group,
R ⁴ represents a substituted cyclopentadienyl group, an indenyl group, and the cyclic hydrocarbon group exemplified by the substituted indenyl group.
Is a methyl group, an ethyl group, a propyl group, an isopropyl group,
Alkyl groups such as butyl group, t-butyl group, pentyl group, hexyl group, octyl group; alkenyl groups such as vinyl group, allyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group; phenyl group, An aryl group such as a tolyl group and a xylyl group; an aryloxy group such as a phenoxy group; a benzyl group, a phenethyl group, a styryl group, an aralkyl group such as a neofil group, and the like, having 1 to 24 carbon atoms, preferably 1 to 12 represents a hydrocarbon residue or hydrogen, and R ⁴ is not only n-, but also iso
It also includes the case of various structural isomer groups such as-, s-, t-, and neo-. X represents a halogen atom such as fluorine, iodine, chlorine or bromine, and r and s are 0 <
It is a number in the range of r ≦ 4 and 0 ≦ s ≦ 3.

Therefore, specific examples of the organic cyclic hydrocarbon compound usable as the component (3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2
-Substituted cyclopentadiene such as dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4- Substituted indene such as methyl-1-indene, 4,7-dimethylindene, 4,5,6,7-tetrahydroindene, cycloheptatriene, substituted cycloheptatriene such as methylcycloheptatriene, cyclooctatetraene, methyl Substituted cyclooctatetraene such as cyclooctatetraene, azulene, methylazulene, ethylazulene, fluorene, substituted fluorene such as methylfluorene, etc. Tajienirushiran, dicyclopentadienyl silane, tri cyclopentadienyl silane,
Tetracyclopentadienylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadienylmonoethylsilane, monocyclopentadienyldimethylsilane, monocyclopentadienyldiethylsilane, monocyclopentadienyltrimethylsilane, monocyclo Pentadienyltriethylsilane, monocyclopentadienylmonomethoxysilane, monocyclopentadienylmonoethoxysilane, monocyclopentadienylmonophenoxysilane,

Monocyclopentadienylmonomethylmonochlorosilane, monocyclopentadienylmonoethylmonochlorosilane, monocyclopentadienylmonomethyldichlorosilane, monocyclopentadienylmonoethyldichlorosilane, monocyclopentadienyltrichlorosilane,

Dicyclopentadienylmonomethylsilane, dicyclopentadienylmonoethylsilane, dicyclopentadienyldimethylsilane, dicyclopentadienyldiethylsilane, dicyclopentadienylmethylethylsilane, dicyclopentadienyl Dipropylsilane, dicyclopentadienylethylpropylsilane, dicyclopentadienyldiphenylsilane, dicyclopentadienylphenylmethylsilane,

Dicyclopentadienylmethylchlorosilane, dicyclopentadienylethylchlorosilane, dicyclopentadienyl rudichlorosilane,

Dicyclopentadienyl monomethoxysilane, dicyclopentadienyl monoethoxysilane,

Dicyclopentadienylmonomethoxymonochlorosilane, dicyclopentadienylmonoethoxymonochlorosilane,

Tricyclopentadienyl monomethylsilane, tricyclopentadienyl monoethylsilane, tricyclopentadienyl monomethoxysilane, tricyclopentadienyl monoethoxysilane, tricyclopentadienyl monochlorosilane,

3-methylcyclopentadienylsilane,
Bis-3-methylcyclopentadienylsilane, 3-methylcyclopentadienylmethylsilane, 1,2-dimethylcyclopentadienylsilane, 1,3-dimethylcyclopentadienylsilane, 1,2,4-trimethylcyclo Pentadienylsilane, 1,2,3,4-tetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsilane, monoindenylsilane, diindenylsilane, triindenylsilane, tetraindenylsilane, mono Indenyl monomethyl silane, mono indenyl monoethyl silane, mono indenyl dimethyl silane, mono indenyl diethyl silane, mono indenyl trimethyl silane, mono indenyl triethyl silane, mono indenyl monomethoxy silane, mono indenyl monoethoxy silane, Mo Indenyl mono phenoxy silane,

Monoindenyl monomethyl monochlorosilane, monoindenyl monoethyl monochlorosilane, monoindenyl monomethyldichlorosilane, monoindenyl monoethyldichlorosilane, monoindenyltrichlorosilane,

Cyindenylmonomethylsilane, diindenylmonoethylsilane, diindenyldimethylsilane,
Diindenyldiethylsilane, diindenylmethylethylsilane, diindenyldipropylsilane, diindenylethylpropylsilane, diindenyldiphenylsilane, diindenylphenylmethylsilane, diindenylmethylchlorosilane, diindenyl Ethylchlorosilane, diindenyldichlorosilane, diindenylmonomethoxysilane, diindenylmonoethoxysilane, diindenylmonomethoxymonochlorosilane, diindenylmonoethoxymonochlorosilane, triindenylmosomethylsilane, triindenylmonosilane Ethylsilane, twainedenyl monomethoxysilane, triindenyl monoethoxysilane, triindenyl monochlorosilane, 3-methylindenylsilane, bis-3-methylindenylsilane, 3-methylethyl De methylpropenylmethyl silane, 1,2-dimethyl-indenyl silane, 1,3-dimethyl-indenyl silane, 1,2,4-trimethyl indenyl silane, 1,
There are 2,3,4-tetramethylindenylsilane, pentamethylindenylsilane and the like. Preferred are cyclopentadiene, substituted cyclopentadinine, indene, substituted indene and the like.

Further, any one of the above-mentioned compounds may have an alkylene group (the carbon number of which is usually 2 to 8, preferably 2 to 8).
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-propanedienylbisindene, 1,
3-propanedienylbis (4,5,6,7-tetrahydro) indene, propylenepis (1-indene),
Isopropyl (1-indenyl) cyclopentadiene,
Examples thereof include diphenylmethylene (9-fluorenyl) cyclopentadiene and isopropylcyclopentadienyl-1-fluorene.

Next, the general formula of component (4)

[0071]

[Chemical 17]

The compound represented by will be described. In the formula, R ³ and R ⁴ each have 1 to 2 carbon atoms.
4, preferably 1 to 12, more preferably 1 to 8 hydrocarbon groups, and examples of such hydrocarbon groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group. Carbon groups such as alkyl groups such as groups, alkenyl groups such as vinyl groups and allyl groups, aryl groups such as phenyl groups, tolyl groups and xylyl groups, aralkyl groups such as benzyl groups, phenethyl groups, styryl groups, and neofil groups, etc. It represents a hydrogen group, and R ³ and R ⁴ may be the same or different.

The compounds represented by these general formulas are as follows:
Specifically, dimethyl magnesium, methyl ethyl magnesium, diethyl magnesium, methyl n-propyl magnesium, ethyl n-propyl magnesium, di n
-Propyl magnesium, methyl n-butyl magnesium, ethyl n-butyl magnesium, n-propyl n-
Butylmagnesium, di-n-butylmagnesium, methylpentylmagnesium, ethylpentylmagnesium, n-propylpentylmagnesium, n-butylpentylmagnesium, dipentylmagnesium, methylhexylmagnesium, ethylhexylmagnesium,
n-propylhexyl magnesium, n-butylhexyl magnesium, pentylhexyl magnesium, dihexyl magnesium, methyl octyl magnesium, ethyl octyl magnesium, n-propyl octyl magnesium, n-butyl octyl magnesium, pentyl octyl magnesium, hexyl octyl magnesium, dioctyl magnesium,

Methylbenzylmagnesium, ethylbenzylmagnesium, n-propylbenzylmagnesium, n-butylbenzylmagnesium, hexylbenzylmagnesium, octylbenzylmagnesium, dibenzylmagnesium, methylphenylmagnesium, ethylphenylmagnesium, n-propylphenylmagnesium, n -Butylphenyl magnesium, pentyl phenyl magnesium, hexyl phenyl magnesium, octyl phenyl magnesium, diphenyl magnesium, etc. are mentioned. Of course, it is also preferable to use a plurality of these magnesium compounds in an arbitrary combination.

The catalyst component used in the production method of the present invention has the general formula (1) as described above.

[0076]

[Chemical 18]

A compound represented by the formula (2)

[0078]

[Chemical 19]

A compound represented by: (3) an organic cyclic compound having two or more conjugated double bonds, and (4) a general formula

[0080]

[Chemical 20]

It is obtained by mutually contacting or mixing the compounds represented by the formula (1), and the order of mixing and contacting these components is not particularly limited.

Contact / Mixing (hereinafter collectively referred to as contact)
As a method,

A method in which the component (1), the component (2), the component (3) and the component (4) are simultaneously contacted,

A method of bringing the component (1), the component (2) and the component (3) into contact with each other, and then bringing the component (4) into contact therewith,

A method in which the component (1), the component (3) and the component (4) are brought into contact with each other and then the component (2) is brought into contact therewith,

A method of bringing the component (2), the component (3) and the component (4) into contact with each other, and then contacting the component (1),

A method in which the component (1), the component (2) and the component (4) are brought into contact with each other, and then the component (3) is brought into contact therewith,

A method in which the component (1), a part of the component (2), the component (3) are brought into contact with each other, and then the rest of the component (2) and the component (4) are brought into contact with each other,

A method in which a part of the component (1), the component (2), the component (3), and the component (4) are brought into contact with each other, and then the rest of the component (4) is brought into contact with them.

A method in which the components (1) and (2) are first brought into contact with each other, and then the components (3) and (4) are brought into contact with each other,

A method in which the components (1) and (3) are first brought into contact with each other, and then the components (2) and (4) are brought into contact with each other,

A method in which the component (1) and the component (4) are first brought into contact with each other, and then the component (2) and the component (3) are brought into contact with each other,

A method in which the component (1), the component (2) and the component (3) are brought into contact with each other, and then the component (2) and the component (4) different from the above are brought into contact with each other,

Examples of the method include contacting the component (1), the component (3) and the component (4), and then contacting the component (2) and the component (4) different from the above.

A method of bringing the component (1), the component (2) and the component (3) into contact with each other, and then bringing the component (4) into contact therewith,

A method in which the component (1), the component (3) and the component (4) are brought into contact with each other, and then the component (2) is brought into contact therewith,

A method in which the component (1), a part of the component (2) and the component (3) are brought into contact with each other, and then the rest of the component (2) and the component (4) are brought into contact with each other;

A method in which the component (1), the component (2) and the component (3) are brought into contact with each other, and then the component (2) and the component (4) different from the above are brought into contact with each other,

A method in which the component (1), the component (3) and the component (4) are brought into contact with each other, and then the component (2) and the component (4) different from the above are brought into contact with each other is preferably used.

The above contact is usually carried out in the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene and xylene, and the contact temperature is usually from -100 ° C to 2 ° C.
00 ° C is preferably selected in the range of -50 ° C to 100 ° C, and the contact time is selected in the range of 30 minutes to 50 hours.

When the four components are brought into contact with each other, the proportion of each component used is generally 1 mol of the component (1) to the component (2).
0.1 to 10000 mol, preferably 1 to 2000 mol, component (3) 0.1 to 1000 mol, preferably 0.5 to 100 mol, component (4) 0.1.
It is in the range of 1 to 10000 mol, preferably 1 to 1000 mol. The proportion of the component (4) used relative to 1 mol of the component (2) is 0.01 to 100 mol, preferably 0.1.
In the range of up to 2 moles.

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 solution 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. Are polymerized or copolymerized. The polymerization conditions at this time are temperature 2
0 ° C to 200 ° C, preferably 50 ° C to 100 ° C, pressure atmospheric pressure to 70 kg / 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 molecular weight can be adjusted more effectively by adding hydrogen to the polymerization reaction system. 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. Further, it is useful as an oligomerization catalyst by selecting the amount ratio of the cyclic conjugated double bond compound. For example, by using ethylene or propylene as a monomer, a dimer to a 20-mer monomer can be synthesized. Further, as described above, in the present invention, the aluminoxane does not have to be used as an essential component, but can be appropriately used if necessary.

[0104]

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) Measured according to ASTM D 1238-57T.

[0107] was measured in accordance with density ASTMD 1505-68.

Melting point measurement by differential scanning calorimeter (DSC)
Using a DSC-20 melting point measuring apparatus manufactured by Seiko Denshi, hold the sample (5 mg) at 180 ° C. for 3 minutes, then cool to 0 ° C. at 10 ° C./minute, hold at 0 ° C. for 10 minutes, and then The melting point was measured by raising the temperature at 10 ° C./min.

Weight average molecular weight / number average molecular weight (Mw / M
n) Mw / Mn is measured by gel permeation chromatography (manufactured by Waters, model type 150-C type is used), orthochlorobenzene is used as a solvent,
The measurement temperature was 135 ° C.

Example 1 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, tetrapropoxyzirconium (hereinafter,
Zr (On-Pr) ₄ ) 3.3 g and indene 9.
After adding 3 g and stirring at room temperature for 30 minutes, 9.1 g of triethylaluminum (hereinafter referred to as AlEt ₃ ) was added dropwise while maintaining the system at 0 ° C. After completion of the addition, the system was brought to room temperature and stirred for 24 hours, A transition metal component was prepared. The concentration of this solution is 0.058 mmol / ml as Zr.

Then, a stainless steel autoclave having a volume of 3 L and equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added thereto to obtain a concentration (1 mmol / m 2).
25 ml of a solution of 1) of diethylaluminum chloride (toluene solution) (the ratio of Zr (On-Pr) ₄ to the metal is Al / Zr = 1500), and 0.3 ml of the above transition metal component. (1.5m as Zr
g), ethylbutylmagnesium EtBuMg (concentration 1
9 ml of a mmol / ml heptane solution (Zr (On-
The amount ratio with Pr) ₄ is Mg / Zr = 50 in terms of the amount ratio of the metal.
0) was added, the system was heated to 60 ° C., and ethylene was added to 9
Kgf / cm ² G was applied so that polymerization was started to start polymerization, and the total pressure was maintained at 9 Kgf / cm ² to carry out polymerization for 2 hours.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 68 g of a white polymer. The obtained polymer has an MFR of 6.7 g / 10 min, Mw /
Mn is 4.9, catalyst efficiency is 45000g / gZr
Met.

Example 2 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.3 g of Zr (On-Pr) ₄ and 9.3 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, and the system was kept at 0 ° C. to maintain diethyl aluminum chloride (hereinafter referred to as AlEt ₂
(Denoted by Cl) 24.1 g was added dropwise, and after completion of the addition, the system was stirred at room temperature for 24 hours to prepare a transition metal component.
The concentration of this solution is 0.054 mmol / ml as Zr
Is.

Next, a 3 L stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added to the autoclave to add a concentration (1 mmol / m 2).
3 ml of diethylaluminum chloride solution (toluene solution) of 1) (the ratio of Zr (On-Pr) ₄ to the amount of metal is Al / Zr = 150) was added, and 0.37 ml of the above transition metal component was added. (1.8 mg as Zr),
5 ml of EtBuMg (concentration 1 mmol / ml heptane solution) (the ratio of Zr (On-Pr) ₄ to Mg was Mg / Zr = 250) was added, and the system was heated to 60 ° C. Polymerization was initiated by injecting ethylene to 9 Kgf / cm ² G, and the total pressure was maintained at 9 Kgf / cm ² G to carry out polymerization for 2 hours.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 41 g of a white polymer. The polymer obtained has an MFR of 10.3 g / 10 min, Mw
/ Mn is 5.0 and the catalyst efficiency is 23000 g / gZ
It was r.

Example 3 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 0.33 g of Zr (On-Pr) ₄ and 0.9 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, then, the system was kept at 0 ° C., 24.1 g of AlEt ₂ Cl was added dropwise, and after the addition was completed. The system was brought to room temperature and stirred for 24 hours to prepare a transition metal component. The concentration of this solution is 0.0054 mm as Zr
ol / ml.

Next, a 3 L stainless steel autoclave equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added thereto, and further 6.0 ml of the above transition metal component (3.0 mg as Zr) and EtBuMg were added.
6.6 ml of (concentration 1 mmol / ml heptane solution)
(The quantitative ratio with Zr (On-Pr) ₄ is M in terms of the metallic ratio.
g / Zr = 200) was added, while maintaining the heated then ethylene. to 60 ° C. to initiate polymerization at Harikon so that 9 Kgf / cm ² G, the total pressure 9 Kgf / cm ² G Polymerization was carried out for 2 hours.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 87 g of a white polymer. The obtained polymer has an MFR of 23.3 g / 10 min, Mw
/ Mn is 5.2 and the catalyst efficiency is 29000 g / gZ.
It was r.

Example 4 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.8 g of Zr (On-Bu) ₄ and 2.6 g of cyclopentadiene were added, and the mixture was stirred at room temperature for 30 minutes, and then at 0 ° C.
While maintaining the system, 0.5 ml of EtBuMg (concentration 1 mmol / ml heptane solution) was added dropwise, and after completion of the addition, the mixture was stirred at room temperature for 24 hours to prepare a transition metal component. The concentration of this solution is 0.064 mmol / ml as Zr.

Then, a stainless steel autoclave having a volume of 3 L and equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added thereto to obtain a concentration (1 mmol / m 2).
38 ml of a solution (toluene solution) of diethylaluminum bromide of 1) (the ratio of Zr (On-Bu) ₄ is Al / Zr = 1000 in terms of metal ratio), and 0.59 ml of the above transition metal component. (3.5m as Zr
g) was added, the system was heated to 80 ° C., and ethylene was added to 1
0 kgf / cm ² to initiate polymerization at Harikon as a G, polymerization was conducted for 2 hours while maintaining the total pressure at 10 Kgf / cm ² G.

After the polymerization was completed, the excess gas was discharged and the contents were taken out by cooling to obtain 130 g of a white polymer. The obtained polymer has an MFR of 110 g / 10 min, Mw
/ Mn is 6.8 and the catalyst efficiency is 37,000 g / gZ.
It was r.

Example 5 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.8 g of Zr (On-Bu) ₄ and 11 g of cyclopentadienyltrimethylsilane were added, and the mixture was added at room temperature to 3
After stirring for 0 minutes, the system was kept at 0 ° C. and the concentration (1 mmol / m 2
l) A solution of diethylaluminum chloride (toluene solution) 0.2 was added dropwise, and after the addition was completed, the system was brought to room temperature and 1
The transition metal component was prepared by stirring for 6 hours. The concentration of this solution is 0.061 mmol / ml as Zr.

Next, the autoclave made of stainless steel having a capacity of 3 L and equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added thereto, and the concentration (1 mmol / m 2
11 ml of a solution of ethylaluminum sesquichloride (toluene solution) (the ratio of Zr (On-Bu) ₄ to Al / Zr = 500 in terms of metal ratio) was added, and the transition metal component 0. 37ml (2.1m as Zr
g) was added and diethyl magnesium (hereinafter Et ₂ M
(represented by g) (concentration 1 mmol / ml heptane solution) of 2.3 ml (the ratio of Zr (On-Bu) ₄ is Mg / Zr = 100 in terms of the amount of metal), and the system was heated at 80 ° C. Then, the temperature was raised to 10 Kgf / cm ² and ethylene was added thereto to start polymerization, and the total pressure was changed to 10 Kgf / cm ^2.
While maintaining at G, polymerization was carried out for 2 hours.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 39 g of a white polymer. The obtained polymer has an MFR of 5.3 g / 10 min, Mw /
Mn is 4.5, catalyst efficiency is 19000g / gZr
Met.

Example 6 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 0.38 g of Zr (On-Bu) ₄ and 2.1 g of ethylenebisindenylethane were added, and the mixture was stirred at room temperature for 30 minutes, and then the system was kept at 0 ° C to give a concentration (1 mmol / ml).
0.2 ml of a solution of diethylaluminum chloride (toluene solution) was added dropwise, and after completion of the addition, the temperature of the system was raised to room temperature.
The transition metal component was prepared by stirring for 6 hours. The concentration of this solution is 0.0066 mmol / ml as Zr.

Next, a 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, and 1 liter of purified toluene was added thereto, and further 4.2 ml of the above transition metal component (2.5 mg as Zr) and EtBuMg were added.
8.1 ml of (concentration 1 mmol / ml heptane solution)
(The amount ratio with Zr (On-Bu) ₄ is M in terms of amount ratio of metal.
g / Zr = 300 was heated and then ethylene. to 80 ° C. was added to) to initiate polymerization at Harikon so that 10Kgf / cm ² G, to maintain the total pressure at 10 Kgf / cm ² G Polymerization was carried out for 2 hours.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 91 g of a white polymer. The obtained polymer has an MFR of 4.2 g / 10 min, Mw /
Mn is 4.7, catalyst efficiency is 36000 g / gZr
Met.

Example 7 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.8 g of Zr (On-Bu) ₄ and 2.6 g of cyclopentadiene were added, and the mixture was stirred at room temperature for 30 minutes, and then at 0 ° C.
While maintaining the system, 0.2 ml of Bu ₂ Mg (concentration 1 mmol / ml heptane solution) was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 24 hours to prepare a transition metal component. The concentration of this solution is 0.064 mmol / ml as Zr.

Then, a stainless steel autoclave having a volume of 3 L and equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added to the autoclave to give a concentration (1 mmol / m 2).
1) A solution of diethylaluminum chloride (toluene solution) (4.4 ml) was added (Al / Zr = 200 in terms of the amount ratio to Zr (On-Bu) ₄ in terms of metal amount), and the system was heated to 60 ° C. Heat and further 0.34 ml of the above transition metal component
(2.0 mg as Zr), and 1.1 ml of EtBuMg (concentration 1 mmol / ml heptane solution) (Zr
The amount ratio with (On-Bu) ₄ is Mg / Z in terms of the metal amount ratio.
r = 50), and then ethylene was added at 10 Kgf / c
m 2 to initiate polymerization at Harikon As will be ^G, the total pressure 1
Polymerization was carried out for 2 hours while maintaining the pressure at 0 Kgf / cm ² G.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 53 g of a white polymer. The obtained polymer has an MFR of 99 g / 10 min, Mw / M
n was 6.8 and the catalyst efficiency was 27,000 g / gZr.

Example 8 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.0 g of tripropoxymonochlorozirconium Zr (On-Pr) ₃ Cl and 6.6 g of cyclopentadiene were added, and after stirring at room temperature for 30 minutes, the system was kept at 0 ° C. and 34.2 g of AlEt ₃ was added dropwise. After completion of the dropping, the system was brought to room temperature and stirred for 24 hours to prepare a transition metal component. The concentration of this solution is Zr 0.052 mmol /
ml.

Next, the autoclave made of stainless steel having a volume of 3 L and equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added thereto, and the concentration (1 mmol / m 2
2.3 ml of a solution of 1) diethylaluminum chloride (toluene solution) (the ratio of Zr (On-Pr) ₃ Cl is Al / Zr = 100 in terms of metal ratio),
The temperature of the system is raised to 60 ° C., and the transition metal component is 0.44 m
l (2.1 mg as Zr), and 6.9 ml (Zr of EtBuMg (concentration 1 mmol / ml heptane solution)).
The amount ratio with (On-Pr) ₃ Cl is the amount ratio of the metal and Mg.
/ Zr = 300), and then add 10 kg of ethylene.
Polymerization was started by injecting so as to be f / cm ² G, and the total pressure was maintained at 10 Kgf / cm ² G to carry out polymerization for 2 hours.

After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 65 g of a white polymer. The obtained polymer has an MFR of 120 g / 10 min, Mw /
Mn is 5.9, catalyst efficiency is 31000 g / gZr
Met.

Example 9 150 ml of purified toluene in a 300 ml flask under nitrogen
And then tetra-n-butoxytitanium (hereinafter,
Ti (On-Bu) ₄ ) 3.4 g and indene 1
After 1.6 g was added and the mixture was stirred at room temperature for 30 minutes, 11.4 g of AlEt ₃ was added dropwise while maintaining the system at 0 ° C. After completion of the addition, the system was brought to room temperature and stirred for 24 hours to prepare a transition metal component. .
The concentration of this solution is 0.056 mmol / ml as Ti
Is.

Next, the autoclave made of stainless steel having a capacity of 3 L and equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added thereto, and the concentration (1 mmol / m 2
2) Diethylaluminum chloride solution (toluene solution) of 26.2 ml (Ti (On-Bu) ₄ in terms of the amount ratio of metal is Al / Ti = 1200),
Furthermore, 0.39 ml of the above transition metal component (1.1 as Ti
mg), EtBuMg (concentration 1 mmol / ml heptane solution), 6.6 ml (Ti (On-Bu) ₄ quantitative ratio Mg / Ti = 300 as metal ratio), and the system was added at 60 ° C. The temperature was raised to 9 Kgf / cm ² G and ethylene was introduced to start the polymerization, and the total pressure was changed to 9 Kgf / cm ^2.
Polymerization was carried out for 2 hours while maintaining cm ² G.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 16 g of a white polymer. The polymer obtained has an MFR of 53 g / 10 min, Mw / M
n was 6.5 and the catalyst efficiency was 15000 g / gTi.

Example 10 150 ml of purified toluene in a 300 ml flask under nitrogen
And then tetrapropoxy hafnium (hereinafter H
f (On-Pr) ₄ ) 4.1 g and indene 11.
After adding 6 g and stirring at room temperature for 30 minutes, the system was kept at 0 ° C.
11.4 g of lEt ₃ was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 24 hours to prepare a transition metal component. The concentration of this solution is 0.057 mmol / ml as Hf.

Next, the autoclave made of stainless steel having a capacity of 3 L and equipped with a stirrer was purged with nitrogen, and 1 liter of purified toluene was added thereto to obtain a concentration (1 mmol / m 2).
1) 25.2 ml of a solution of diethylaluminum chloride (toluene solution) (amount ratio of Hf (On-Pr) ₄ is Al / Hf = 1200 in terms of metal ratio),
Further, 0.37 ml of the above transition metal component (3.7 as Hf)
mg) and EtBuMg (concentration 1 mmol / ml heptane solution) of 6.3 ml (the amount ratio with Hf (On-Pr) ₄ is Mg / Hf = 300 in terms of metal amount ratio), and the system was heated at 60 ° C. The temperature was raised to 9 Kgf / cm ² G and ethylene was introduced to start the polymerization, and the total pressure was changed to 9 Kgf / cm ^2.
Polymerization was carried out for 2 hours while maintaining cm ² G.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 26 g of a white polymer. The polymer obtained has an MFR of 15 g / 10 min, Mw / M
n was 6.1 and the catalyst efficiency was 11000 g / gHf.

Example 11 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 2.6 g of trichloromonopropoxyzirconium and 9.3 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, then, the system was kept at 0 ° C., 9.1 g of AlEt ₃ was added dropwise, and after completion of the addition, the system was brought to room temperature. After stirring for 24 hours, a transition metal component was prepared. The concentration of this solution is Zr.
It is 059 mmol / ml.

Then, a stainless steel autoclave with a volume of 3 L equipped with a stirrer was purged with nitrogen, and 1 liter of purified toluene was added thereto to obtain a concentration (1 mmol / m 2).
1) 8.8 ml of a solution of diethylaluminum chloride (toluene solution) (the amount ratio with trichloromonopropoxyzirconium is Al / Zr = 50 in terms of metal ratio).
0) is added, and 0.30 ml of the above transition metal component (Z
r of 1.6 mg) and diphenylmagnesium (concentration of 1 mmol / ml heptane solution) of 5.3 ml (the ratio of trichloromonopropoxyzirconium to Mg / Zr = 300 in terms of metal ratio) were added to the system. Polymerization was started by raising the temperature to 60 ° C. and then injecting ethylene to 9 Kgf / cm ² G so that polymerization was continued for 2 hours while maintaining the total pressure at 9 Kgf / cm ² G.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 30 g of a white polymer. The polymer obtained has an MFR of 14 g / 10 min, Mw / M.
n was 4.8 and the catalyst efficiency was 19000 g / gZr.

Example 12 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 2.3 g of zirconium tetrachloride and 5.2 g of cyclopentadiene were added, and after stirring at room temperature for 30 minutes, the system was kept at 0 ° C. and 9.1 g of AlEt ₃ was added dropwise. After stirring for 24 hours, a transition metal component was prepared. The concentration of this solution is 0.065 mmo as Zr.
1 / ml.

A stainless steel autoclave with a volume of 3 L equipped with a stirrer was purged with nitrogen, and 1 liter of purified toluene was added to the autoclave to add 18.6 ml of a solution (toluene solution) of diethylaluminum chloride having a concentration (1 mmol / ml). The amount ratio with respect to zirconium tetrachloride is the amount of metal, Al / Zr = 1000, and 0.30 ml of the above transition metal component (Zr 1.7 m).
g), ethylbutyl magnesium (concentration 1 mmol / m
1 heptane solution) (5.6 ml) (the ratio of the amount of zirconium tetrachloride to that of zirconium tetrachloride is Mg / Zr = 300) was added, the system was heated to 60 ° C., and ethylene was added at 9 Kgf / c.
m ² G was added to start polymerization and the total pressure was adjusted to 9
Polymerization was carried out for 2 hours while maintaining Kgf / cm ² G.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 54 g of a white polymer. The obtained polymer has an MFR of 76 g / 10 min, Mw / M
n was 4.7 and the catalyst efficiency was 32000 g / gZr.

Example 13 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 0.45 g of benzylzirconium and 0.93 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, then the system was kept at 0 ° C. and 5.7 g of triethylaluminum was added dropwise.
After the dropping was completed, the system was brought to room temperature and stirred for 24 hours to prepare a transition metal component. The concentration of this solution is 0.00 as Zr.
64 mmol / ml.

A stainless steel autoclave with a volume of 3 L equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added thereto, and 0.3 ml of a solution (toluene solution) of diethylaluminum fluoride having a concentration (1 mmol / ml) was added. (The amount ratio with benzyl zirconium is Al / Zr = 20 in terms of metal amount ratio), and 2.4 ml of the above transition metal component (1.4 mg as Zr) and dibutyl magnesium (concentration 1 mmol / ml heptane solution) ) Of 4.6 ml (the amount ratio with benzylzirconium is the metal amount ratio Mg / Zr = 300) was added, and the system was adjusted to 6
The temperature was raised to 0 ° C., and then ethylene was introduced so as to be 9 Kgf / cm ² G to start polymerization, and the total pressure was 9 Kgf / c.
Polymerization was carried out for 2 hours while maintaining m ² G.

After the completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 5.6 g of a white polymer. The obtained polymer has an MFR of 4.2 g / 10 min, Mw
/ Mn is 3.9, catalyst efficiency is 4000 g / gZr
Met.

Example 14 A 3 L capacity stainless steel autoclave equipped with a stirrer was purged with nitrogen, and 1 liter of purified toluene was added thereto, and 25 ml of a solution (toluene solution) of diethylaluminum chloride having a concentration (1 mmol / ml) was added.
(The amount ratio with Zr (On-Pr) ₄ is A in terms of the amount of metal.
1 / Zr = 1500) was added, and 0.3 ml of the transition metal component in Example 1 (1.5 mg as Zr), E
8 of tBuMg (concentration 1 mmol / ml heptane solution)
ml (the ratio of Zr (On-Pr) ₄ to the amount of metal is Mg / Zr = 500), the temperature of the system was raised to 60 ° C., and then a mixed gas of ethylene and butene-1 (butene- 1 /
Ethylene and butene-1 were added by injecting ethylene with a molar ratio of 0.25) to 9 Kgf / cm ² G to start the polymerization.
While continuously supplying the mixed gas (butene-1 / ethylene molar ratio of 0.05), the total pressure was maintained at 9 Kgf / cm ² G to carry out polymerization for 2 hours.

After completion of the polymerization, the excess gas was discharged and the contents were taken out by cooling to obtain 73 g of a white polymer. The density of the obtained polymer was 0.9233 g / cm ³ , the melting point was 116.5 ° C., the MFR was 2.3 g / 10 min, and the Mw /
Mn was 4.3 and the catalyst efficiency was 49000 g / gZr.

Example 15 150 ml of purified toluene in a 300 ml flask under nitrogen
And then add tetrapropoxy zirconium 0.33
g and 0.93 g of indene were added, the mixture was stirred at room temperature for 30 minutes, and then 0
The system was kept at ℃, and diethylaluminum chloride 6
g was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 4 hours to prepare a transition metal component. The concentration of this solution is 0.0064 mmol / ml as Zr.

A stainless steel autoclave having a volume of 3 L and equipped with a stirrer was replaced with nitrogen, and 1 liter of purified toluene was added to the autoclave, and 1.2 ml of a solution (toluene solution) of diethylaluminum chloride having a concentration (1 mmol / ml) was added ( The amount ratio with tetrapropoxyzirconium is Al / Zr = 50 in terms of the amount of metal, and 3.6 ml of the above transition metal component (2.1 m as Zr).
g), 2.3 ml of dibutylmagnesium (concentration 1 mmol / ml heptane solution) (the amount ratio with tetrapropoxy zirconium is Mg / Zr = 100 in terms of metal amount ratio).
Was added to bring the system to 40 ° C., and then 7 kg of propylene was added.
Polymerization was started by injecting so as to be f / cm ² G, and polymerization was carried out for 1 hour while maintaining the total pressure at 7 Kgf / cm ² G.

After the completion of the polymerization, the excess gas was discharged and cooled to obtain 5.6 g of atactic polypropylene. The catalyst efficiency of the obtained polymer was 18,000 g / gZr.

Comparative Example 1 150 ml of purified toluene in a 300 ml flask under nitrogen.
Then, 3.3 g of Zr (On-Pr) ₄ was added, 9.1 g of AlEt ₃ was added dropwise while keeping the system at 0 ° C., and after completion of the addition, the system was brought to room temperature and stirred for 24 hours, A transition metal component was prepared. The concentration of this solution is Zr.
061 mmol / ml.

Next, a 3 L capacity stainless steel autoclave equipped with a stirrer was purged with nitrogen, and 1 liter of purified toluene was added to the autoclave to give a concentration (1 mmol / m 2).
25 ml of a solution of 1) of diethylaluminum chloride (toluene solution) (the ratio of Zr (On-Pr) ₄ to the metal is Al / Zr = 1500), and 0.3 ml of the above transition metal component. (1.6m as Zr
g), 8 ml of EtBuMg (concentration 1 mmol / ml heptane solution) (the ratio of Zr (On-Pr) ₄ to Mg is Mg / Zr = 500), and the system was added at 60 ° C.
Then the temperature was raised to 9 Kgf / cm ² G and ethylene was introduced to start the polymerization, and the total pressure was changed to 9 Kgf / cm ²
While maintaining at G, polymerization was carried out for 2 hours.

After completion of the polymerization, excess gas was discharged, the autoclave was opened by cooling and no polymer was obtained.

[Brief description of drawings]

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

Claims (1)

[Claims] 1. A general formula: (Wherein R ¹ is a hydrocarbon residue having 1 to 24 carbon atoms, X is a halogen atom, Me is Zr, Ti, or Hf, and n is 0 ≦ n ≦ 4). , (2) General formula: (Wherein R ² is a hydrocarbon residue having 1 to 24 carbon atoms, X is a halogen atom, and p is a number satisfying 0 <p ≦ 3), (3) conjugated double An organic cyclic compound having two or more bonds and (4) the general formula: (Wherein R ³ and R ⁴ have 1 to 24 carbon atoms)
Is a hydrocarbon group. A method for producing an olefin polymer, characterized by polymerizing or copolymerizing olefins in the presence of a catalyst comprising: