JP3046882B2 - Olefin polymerization catalyst component and method for producing olefin polymer using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst component which can be used in homopolymerization or copolymerization of olefins to produce an olefin polymer having a relatively wide molecular weight distribution. The present invention also relates to a method for producing an olefin polymer using the catalyst component.

[0002]

BACKGROUND OF THE INVENTION Olefin polymers, especially ethylene homopolymers or ethylene α
The use of a catalyst composition comprising a zirconium compound (typically a metallocene) and an alumoxane in producing an olefin copolymer is disclosed in Japanese Patent Application Laid-Open No. 58-19309.
It is publicly known as shown in Japanese Patent Publication No. However, this technique can produce a homopolymer or a copolymer of ethylene in high yield, but has the drawback that the molecular weight of the produced polymer is low and the molecular weight distribution of the homopolymer is narrow.

[0003] In terms of only increasing the molecular weight of the produced polymer, it is possible to increase the molecular weight to some extent by selecting the type of transition metal of metallocene, which is one of the components of the catalyst composition. For example, JP-A-63-25140
No. 5 proposes to use a dicyclopentadienyl hafnium compound. However, this hafnium compound is not only difficult to synthesize in general, but also has a disadvantage that the polymerization activity is inferior to the dicyclopentadienyl zirconium compound. In addition to this, even when a dicyclopentadienyl hafnium compound is used, there is a disadvantage that the molecular weight distribution of the produced polymer is widened, and in the case of the copolymer, the composition distribution cannot be narrowed at the same time as the molecular weight distribution is expanded. there were.

In the art, there is a demand for the development of an olefin polymer having a high molecular weight and a wide molecular weight distribution, and in the case of a copolymer, a narrower composition distribution. The fact is that an olefin polymer that can meet the needs of the industry cannot be produced by using a catalyst composition containing as a catalyst component. In this specification, an olefin polymer means both a homopolymer and a copolymer of olefins.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies with the aim of producing a polyolefin that can sufficiently meet the demands of the industry, and as a result, have found that the catalyst components used in the conventional catalyst system are different from those used in the conventional catalyst system. And a novel catalyst component which is completely different from the above, and found that an olefin polymer having desired properties can be produced in high yield by employing a catalyst system using this catalyst component. Accordingly, the catalyst component for olefin polymerization according to the present invention comprises: (1) a compound represented by the general formula Me ¹ (OR ¹ ) _p R ² _q X ¹⁴ _-pq (wherein R ¹ and R ² are individually A hydrocarbon residue having 1 to 24 carbon atoms, X ¹ is a halogen atom, Me ¹ is Ti, Zr or H
and p is 0 ≦ p ≦ 4, q is 0 ≦ q ≦ 4, and p + q is 0 ≦ p + q ≦ 4) and (2) a carbon atom, a hydrogen atom, an oxygen atom, and a silicon atom.
It consists construction element selected from the group that, Chi lifting conjugated double bonds two or more carbon atoms constituting the ring 5 or 7
The organic cyclic compound of at least one have the a 24 ring brought into contact with each other and characterized in that it is obtained by also producing an olefin polymer according to the present invention, the above components (1)
And a catalyst component obtained by contacting component (2) with each other,
Olefins are polymerized or copolymerized in the presence of a catalyst composition comprising a modified organoaluminum compound containing an Al-O-Al bond obtained by reacting an organoaluminum compound with water.

[0006] The catalyst composition used in the process of the present invention has a high activity per transition metal and has the ability to produce a high molecular weight olefin polymer. The obtained olefin polymer has a relatively wide molecular weight distribution, and when this is a copolymer, particularly when it is an ethylene / α-olefin copolymer, the composition distribution is narrow, and the copolymer is When formed into a film or sheet, there is no inconvenience such that the films or sheets adhere to each other.

Catalyst component The catalyst component of the present invention can be obtained by bringing the above-mentioned components (1) and (2) into contact with each other. component
(1) the general formula Me ¹ (OR ¹⁾ represented by _{^{p R 2 q X 1 4-}} pq. In the formula, R ¹ and R ^{2 each} independently represent a hydrocarbon residue having 1 to 24, preferably 1 to 12, more preferably 1 to 8 carbon atoms. This includes methyl, ethyl, propyl,
Butyl group, pentyl group, hexyl group, alkyl group such as octyl group, vinyl group, alkenyl group such as allyl group,
Aryl groups such as phenyl, tolyl, and xylyl groups;
And aralkyl groups such as a benzyl group, a phenethyl group, a styryl group, and a neophyl group. When component (1) has two or more R ¹ or R ² , those hydrocarbon residues may be the same or different. X
¹ is a halogen atom such as fluorine, iodine, chlorine or bromine. Me ¹ represents Zr, Ti or Hf, and is preferably Zr. p is 0 ≦ p ≦ 4, q is 0 ≦ p ≦ 4, p + q
Is 0 ≦ p + q ≦ 4.

Specific examples of the compounds that can be used as the component (1) include tetramethyl zirconium, tetraethyl zirconium, tetrapropyl zirconium,
n-butyl zirconium, tetrapentyl zirconium,
Tetraphenyl zirconium, tetratolyl zirconium, tetrabenzyl zirconium, tetraallyl zirconium, tetraneofil zirconium, trimethyl monochlorodisilconium, triethyl monochlorodisilconium, tripropyl monochlorodisilconium, tri-n-butyl monochlorodisilconium, tribenzyl monochlorodisilconium, dimethyldichlorozirconium, Diethyl dichloro zirconium, di-n-butyl dichloro zirconium, dibenzyl dichloro zirconium, monomethyl trichloro zirconium, monoethyl trichloro zirconium, mono n-butyl trichloro zirconium, monobenzyl trichloro zirconium, tetrachloro zirconium, trimethyl monobromo zirconium, triethyl monobromo zirconium C , Tripropylamine monobromo zirconium, tri -n- butyl monobromophenol zirconium tribenzyl monobromo zirconium, dimethyl dibromo zirconium,

Diethyl dibromo zirconium, di-n-butyl dibromo zirconium, dibenzyl dibromo zirconium, monomethyl tribromo zirconium, monoethyl tribromo zirconium, mono n-butyl tribromo zirconium, monobenzyl tribromo zirconium, tetrabromo zirconium, trimethyl mono Iodo zirconium, triethyl monoiodo zirconium, tripropyl monoiodo zirconium, tri-n-butyl monoiodo zirconium, tribenzyl monoiodo zirconium,
Dimethyl diiodo zirconium, diethyl diiodo zirconium, di-n-butyl diiodo zirconium, dibenzyl diiodo zirconium, monomethyl triiodo zirconium, monoethyl triiodo zirconium, mono n-butyl triiodo zirconium, monobenzyl triiodo zirconium, tetra Iodo zirconium, tetramethoxy zirconium, trimethoxy monochloro zirconium, dimethoxy dichloro zirconium, monomethoxy trichloro zirconium, tetraethoxy zirconium,
Triethoxy monochlorozirconium, diethoxydichloro zirconium, monoethoxy trichloro zirconium, tetraisopropoxy zirconium, triisopropoxy monochlorozirconium, diisopropoxy dichloro zirconium, monoisopropoxy trichloro zirconium, tetra n-butoxy zirconium, tri n-
Butoxy monochloro rhodiconium, di-n-butoxy dichloro zirconium, mono n-butoxy trichloro zirconium, tetrapentoxy zirconium, tripentoxy monochloro rhodiconium, dipentoxy dichloro zirconium, monopentoxy trichloro zirconium, tetraphenoxy zirconium, triphenoxy monochloro rhodiconium, Diphenoxydichlorozirconium,
Monophenoxytrichlorozirconium, tetratolyloxyzirconium, tolyloxymonochlorodizirconium, ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium,

[0010] Tetrabenzyloxyzirconium, triberesyloxymonochlorodisilconium, dibenzyloxydichlorozirconium, monobenzyloxytrichlorozirconium, tribenzylmonomethoxyzirconium, tribenzylmonoethoxyzirconium, tribenzylmonopropoxyzirconium, tribenzylmonobutoxyzirconium , Tribenzyl monophenoxy zirconium, dibenzyl dimethoxy zirconium, dibenzyl diethoxy zirconium, dibenzyl dipropoxy zirconium, dibenzyl dibutoxy zirconium,
Dibenzyl diphenoxy zirconium, monobenzyl trimethoxy zirconium, monobenzyl triethoxy zirconium, monobenzyl tripropoxy zirconium, monobenzyl tributoxy zirconium, monobenzyl triphenoxy zirconium, trineofil monomethoxy zirconium, trineofil monoethoxy zirconium, Trineophile monopropoxy zirconium, trineofil monobutoxy zirconium, tineofil monophenoxy zirconium, dineophile dimethoxy zirconium, dineophile diethoxy zirconium, dineophile dipropoxy zirconium, dineophile dibutoxy zirconium, dineo Fildiphenoxy zirconium, mononeofil trimethoxy zirconium, mononeo I le triethoxy zirconium,
Mononeophyl tripropoxy zirconium, mononeophyl tributoxy zirconium, mononeophyl triphenoxy zirconium,

[0011] Tetramethyltitanium, tetraethyltitanium, tetrapropyltitanium, tetran-butyltitanium, tetrapentyltitanium, tetraphenyltitanium, tetratolyltitanium, tetrabenzyltitanium, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium Titanium, tetraphenoxytitanium, tetratolyloxytitanium, tetrapentyloxytitanium, tetrabenzyloxytitanium, tetraallyl titanium, tetraneofil titanium, trimethyl monochlorotitanium, triethyl monochlorotitanium, tripropyl monochlorotitanium, tri-n-butyl monochlorotitanium, Tribenzyl monochlorotitanium, dimethyl Dichlorotitanium, diethyldichlorotitanium, di-n-butyldichlorotitanium, dibenzyldichlorotitanium, monomethyltrichlorotitanium, monoethyltrichlorotitanium, monon-butyltrichlorotitanium, monobenzyltrichlorotitanium, trimethylmonobromotitanium, triethylmonobromotitanium, Tripropylmonobromotitanium, tri-n-butylmonobromotitanium, tribenzylmonobromotitanium, dimethyldibromotitanium, diethyldibromotitanium, di-n-butyldibromotitanium,

Dibenzyldibromotitanium, monomethyltribromotitanium, monoethyltribromotitanium, mono-n-butyltribromotitanium, monobenzyltribromotitanium, tetrabromotitanium, trimethylmonoiodotitanium, triethylmonoiodotitanium, tripropylmono Iodo titanium, bird
-n-butyl monoiodo titanium, tribenzyl monoiodo titanium, dimethyl diiodo titanium, diethyl diiodo titanium, di n-butyl diiodo titanium, dibenzyl diiodo titanium, monomethyl triiodo titanium, monoethyl triiodo titanium, mono n-butyltriiodotitanium, monobenzyltriiodotitanium, tetraiodotitanium, tetramethoxytitanium, trimethoxymonochlorotitanium,
Dimethoxydichlorotitanium, monomethoxytrichlorotitanium, tetraethoxytitanium, triethoxymonochlorotitanium, diethoxydichlorotitanium, monoethoxytrichlorotitanium, tetraisopropoxytitanium, triisopropoxymonochlorotitanium, diisopropoxydichlorotitanium, monoisopropoxytrichlorotitanium , Tetra-n-butoxytitanium, tri-n-butoxymonochlorotitanium, di-n-butoxydichlorotitanium, mono-n-butoxytrichlorotitanium, tetrapentoxytitanium, tripentoxymonochlorotitanium,

Dipentoxydichlorotitanium, monopentoxytrichlorotitanium, tetraphenoxytitanium, triphenoxymonochlorotitanium, diphenoxydichlorotitanium, monophenoxytrichlorotitanium, tetratolyloxytitanium, tolyloxymonochlorotitanium, ditolyloxydichlorotitanium , Monotolyloxytrichlorotitanium, tetrabenzyloxytitanium, tribenzyloxymonochlorotitanium, dibenzyloxydichlorotitanium, monobenzyloxytrichlorotitanium, tribenzylmonomethoxytitanium, tribenzylmonoethoxytitanium, tribenzylmonopropoxytitanium, Tribenzylmonobutoxytitanium,
Tribenzylmonophenoxytitanium, dibenzyldimethoxytitanium, dibenzyldiethoxytitanium, dibenzylpropoxytitanium, dibenzyldibutoxytitanium, dibenzyldiphenoxytitanium, monobenzyltrimethoxytitanium, monobenzyltriethoxytitanium, monobenzyltrititanium Propoxytitanium, monobenzyltributoxytitanium,
Monobenzyltriphenoxytitanium, trineofil monomethoxytitanium, trineofil monoethoxytitanium, trineofil monopropoxytitanium, trineofil monobutoxytitanium, trineofil monophenoxytitanium, dineophile dimethoxytitanium, dineophile Diethoxy titanium,
Dineophile dipropoxytitanium, Dineophile dibutoxytitanium, Dineophile diphenoxytitanium, Mononeophyltrimethoxytitanium, Mononeophyltriethoxytitanium, Mononeophyltripropoxytitanium, Mononeophyltributoxytitanium, Mono Neofil triphenoxy titanium,

Tetramethylhafnium, tetraethylhafnium, tetrapropylhafnium, tetran-butylhafnium, tetrapentylhafnium, tetraphenylhafnium, tetratolylhafnium, tetrabenzylhafnium, tetramethoxyhafnium, tetraethoxyhafnium, tetrapropoxyhafnium, tetrabutoxy Hafnium, tetraphenoxyhafnium, tetratolyloxyhafnium, tetrapentyloxyhafnium, tetrabenzyloxyhafnium, tetraallylhafnium, tetraneophylhafnium, trimethylmonochlorohafnium, triethylmonochlorohafnium, tripropylmonochlorohafnium, tri-n-butylmonochlorohafnium, Tribenzyl monochlorohafnium, dimethyl Dichlorohafnium, diethyldichlorohafnium, di-n-butyldichlorohafnium, dibenzyldichlorohafnium, monomethyltrichlorohafnium, monoethyltrichlorohafnium, monon-butyltrichlorohafnium, monobenzyltrichlorohafnium, trimethylmonobromohafnium, triethylmonobromohafnium, Tripropylmonobromohafnium, tri-n-butylmonobromohafnium, tribenzylmonobromohafnium, dimethyldibromohafnium, diethyldibromohafnium, di-n-butyldibromohafnium,

Dibenzyldibromohafnium, monomethyltribromohafnium, monoethyltribromohafnium, mono-n-butyltribromohafnium, monobenzyltribromohafnium, tetrabromohafnium, trimethylmonoiodohafnium, triethylmonoiodohafnium, tripropylmono Iodohafnium, bird
-n-butylmonoiodohafnium, tribenzylmonoiodohafnium, dimethyldiiodohafnium, diethyldiiodohafnium, din-butyldiiodohafnium, dibenzyldiiodohafnium, monomethyltriiodohafnium, monoethyltriiodohafnium, mono n-butyltriiodohafnium, monobenzyltriiodohafnium, tetraiodohafnium, tetramethoxyhafnium, trimethoxymonochlorohafnium,
Dimethoxydichlorohafnium, monomethoxytrichlorohafnium, tetraethoxyhafnium, triethoxymonochlorohafnium, diethoxydichlorohafnium, monoethoxytrichlorohafnium, tetraisopropoxyhafnium, 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, ditolyloxydichlorohafnium , Monotolyloxytrichlorohafnium, tetrabenzyloxyhafnium, tribenzyloxymonochlorohafnium, dibenzyloxydichlorohafnium, monobenzyloxytrichlorohafnium, tribenzylmonomethoxyhafnium, tribenzylmonoethoxyhafnium, tribenzylmonopropoxyhafnium, tribenzyl Monobutoxy hafnium,
Tribenzyl monophenoxy hafnium, dibenzyl dimethoxy hafnium, dibenzyl diethoxy hafnium, dibenzyl propoxy hafnium, dibenzyl dibutoxy hafnium, dibenzyl diphenoxy hafnium, monobenzyl trimethoxy hafnium, monobenzyl triethoxy hafnium, monobenzyl tripropoxy Hafnium, monobenzyltributoxy hafnium,
Monobenzyltriphenoxyhafnium, trineofil monomethoxyhafnium, trineofil monoethoxyhafnium, trineofil monopropoxyhafnium, trineofil monobutoxyhafnium, trineofil monophenoxyhafnium, dineophile dimethoxyhafnium, dineophile Diethoxyhafnium,
Dineophile dipropoxyhafnium, Dineophile dibutoxyhafnium, Dineophile diphenoxyhafnium, Mononeophile trimethoxyhafnium, Mononeophile triethoxyhafnium, Mononeophile tripropoxyhafnium, Mononeophile tributoxyhafnium, Mono Neofiltriphenoxyhafnium and the like can be mentioned, and among them, tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetraethoxy zirconium, tetraisopromoxy zirconium, and tetra n-butoxy zirconium are preferable. These compounds may be used in combination of two or more.

As the component (2), an organic cyclic compound having two or more conjugated double bonds is used. Ingredient (2) contains
A cyclic hydrocarbon compound having 2 or more conjugated double bonds, preferably 2 to 4, more preferably 2 to 3, and having a total carbon number of 4 to 24, preferably 4 to 12; A cyclic hydrocarbon compound in which the compound is partially substituted with 1 to 6 hydrocarbon residues (typically, an alkyl group or an aralkyl group having 1 to 12 carbon atoms); two or more conjugated double bonds, An organosilicon compound having a cyclic hydrocarbon group having preferably 2 to 4, more preferably 2 to 3, and having a total carbon number of 4 to 24, preferably 4 to 12; Include organosilicon compounds substituted with 1 to 6 hydrocarbon residues. Incidentally, the organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. (Cp) _L SiR _4-L where Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, or a cyclic hydrocarbon group exemplified by a substituted indenyl group, and R is a methyl group, ethyl Group, propyl group, isopropyl group, butyl group, t-
Alkyl groups such as butyl, hexyl, and octyl;
Alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups; aryl groups such as phenyl groups; aryloxy groups such as phenoxy groups; aralkyl groups such as benzyl groups; Represents 24 to 24, preferably 1 to 12 hydrocarbon residues or hydrogen, and L is 1 ≦
L ≦ 4, preferably 1 ≦ L ≦ 3.

Accordingly, specific examples of the compound usable as the component (2) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethyl Cyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4-methyl-1-indene, 4 , 7-dimethylindene,
7 carbon atoms such as 4,5,6,7-tetrahydroindene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, methylcyclooctatetraene, azulene, methylazulene, ethylazulene, fluorene, methylfluorene ~ 24 cyclopolyenes or substituted cyclopolyenes,

Monocyclopentadienyl silane, dicyclopentadienyl silane, tricyclopentadienyl silane, tetracyclopentadienyl silane, monocyclopentadienyl monomethyl silane, monocyclopentadienyl monoethyl silane, monocyclo Pentadienyldimethylsilane, monocyclopentadienyldiethylsilane, monocyclopentadienyltrimethylsilane, monocyclopentadienyltriethylsilane, monocyclopentadienylmonomethoxysilane, monocyclopentadienylmonoethoxysilane, monocyclo Pentadienylmonophenoxysilane, dicyclopentadienylmonomethylsilane, dicyclopentadienylmonoethylsilane, dicyclopentadienyldimethylsilane, dicyclopentadienyldie Silane, dicyclopentadienylmethylethylsilane, dicyclopentadienyldipropylsilane, dicyclopentadienylethylpropylsilane, dicyclopentadienyldiphenylsilane, dicyclopentadienylphenylmethylsilane, dicyclopentadisilane Enylmonomethoxysilane, dicyclopentadienylmonoethoxysilane, tricyclopentadienylmonomethylsilane,

Tricyclopentadienylmonoethylsilane, tricyclopentadienylmonomethoxysilane, tricyclopentadienylmonoethoxysilane, 3-methylcyclopentadienylsilane, bis3-methylcyclopentadienylsilane, 3 -Methylcyclopentadienylmethylsilane, 1,2-dimethylcyclopentadienylsilane, 1,3-dimethylcyclopentadienylsilane, 1,2,4-trimethylcyclopentadienylsilane, 1,2,3 4-tetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsilane,
Monoindenyl silane, diindenyl silane, triindenyl silane, tetraindenyl silane, monoindenyl monomethylsilane, monoindenyl monoethylsilane, monoindenyldimethylsilane, monoindenyldiethylsilane, monoindenyltrimethylsilane , Monoindenyltriethylsilane, monoindenylmonomethoxysilane, monoindenylmonoethoxysilane, monoindenylmonophenoxysilane, diindenylmonomethylsilane, diindenylmonoethylsilane, diindenyldimethylsilane, diindenyl Diethylsilane, diindenylmethylethylsilane, diindenyldipropylsilane, diindenylethylpropylsilane, diindenyldiephenylsilane, diindenylphenylmethylsilane, diindene Monomethoxysilane, diindenylmonoethoxysilane, triindenylmonomethylsilane, triindenylmonoethylsilane, triindenylmonomethoxysilane, triindenylmonoethoxysilane, 3-methylindenylsilane, bis-3-methylindene Nylsilane, 3-methylindenylmethylsilane,
1,2-dimethylindenylsilane, 1,3-dimethylindenylsilane, 1,2,4-trimethylindenylsilane, 1,2,3,4-tetramethylindenylsilane, pentamethylindenylsilane, etc. is there.

In addition, any one of the above-mentioned compounds may be an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 8).
Compounds linked via 3) can also be used as component (2) of the present invention. For example, bisindenylethane, bis (4,5,6,7-tetrahydro-1-indenyl) ethane, 1,3
-Propandinyl bisindene, 1,3-propanedinyl bis (4,5,6,7-tetrahydro) indene, propylene bis (1-indene), isopropyl (1-indenyl) cyclopentadiene, diphenylmethylene (9-fluorenyl) ) Cyclopentadiene, isopropylcyclopentadienyl-1-fluorene and the like are all the components (2) of the present invention.
Is a compound that can be used as

The catalyst component used in the present invention comprises the above-mentioned two components, namely, component (1) and component (2), and component (1) 1
Component (2) is used in an amount of 0.01 to 100 moles, preferably
It is prepared by contacting each other at a ratio of 0.1 to 10 mol. The contacting method is optional, but usually, the components (1) and (2) are mixed in an inert atmosphere such as nitrogen or argon.
The method of contacting in the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene and xylene is preferred. The temperature condition in this case is usually in the range of -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C, and the contact time is in the range of 30 minutes to 50 hours, preferably 1 hour to 24 hours. When the two components are brought into contact in an inert hydrocarbon solvent, the catalyst component of the present invention can be obtained in a solution state, but can be directly used for polymerization. Alternatively, the catalyst component can be used for polymerization after being once removed from the solution as a solid by an appropriate means.

The catalyst component of the present invention obtained by bringing component (1) into contact with component (2) as described above is usually used in combination with a promoter component to homopolymerize or copolymerize olefins. used. As the promoter component, any promoter component known in the art can be used as long as the object of the present invention and the performance of the catalyst component are not impaired. Such modified organoaluminum compounds are used. A modified organoaluminum compound , a reaction product of an organoaluminum compound and water,
It contains 1 to 100, preferably 1 to 50 Al-O-Al bonds in the molecule. The reaction between the organoaluminum and water is usually performed in an inert hydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, and xylene, alicyclic hydrocarbons, and aromatic hydrocarbons can be used. It is preferred to use group hydrocarbons.

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

The reaction ratio of water to the organoaluminum compound (water / Al molar ratio) is 0.25 / 1 to 1.2 / 1, especially 0.5 / 1.
The reaction temperature is usually -70 to 10
0 ° C, preferably in the range of -20 to 20 ° C. The reaction time is selected in the range of usually 5 to 24 hours, preferably 10 to 5 hours. As the water required for the reaction, water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like can also be used.

According to the present invention, an olefin is homopolymerized or copolymerized in the presence of a catalyst composition comprising the above-mentioned catalyst component and a promoter component exemplified by a modified organoaluminum compound. . In this case, the catalyst component and the modified organoaluminum compound can be supplied separately or in advance in the polymerization reaction system. In any case, the use ratio of the catalyst component and the modified organoaluminum compound is such that the atomic ratio of aluminum in the modified organoaluminum compound to the transition metal in the catalyst component is 1 to 10
It is selected to be in the range of 0,000, preferably 5 to 1,000.

The olefins referred to in the present invention include α-olefins, cyclic olefins, dienes, trienes and styrene analogs. The α-olefins include those having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specifically include ethylene, propylene, butene-1,
Hexene-1, 4-methylpentene-1 and the like are exemplified. The α-olefins can be homopolymerized by using the catalyst component of the present invention, and can also be copolymerized with two or more α-olefins. Either polymerization or block copolymerization may be used. For copolymerization of α-olefins, ethylene and C 3 to C 12, preferably C 3 to C 12, such as ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, and ethylene and 4-methylpentene-1 are used.
To copolymerize propylene and butene-1, propylene and 4-methylpentene-1,
Examples include the case where propylene is copolymerized with an α-olefin having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, such as propylene and 4-methylbutene-1, propylene and hexene-1, and propylene and otylene-1. When ethylene or propylene is copolymerized with another α-olefin, the amount of the other α-olefin can be arbitrarily selected within a range of 90 mol% or less of all monomers. In the case of the copolymer, it is 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, and in the propylene copolymer, it is 1 to 90 mol%, preferably 5 mol% or less.
To 90 mol%, more preferably 10 to 70 mol%.

As the cyclic olefin, 3 to 24 carbon atoms;
Preferably from 3 to 18 can be used in the present invention, for example, cyclopentene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, cyclodecene, cyclododecene,
Tetracyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5, 5,6-trimethyl-2-norbornene, ethylidene norbornene and the like are included. Usually, the cyclic olefin is copolymerized with the above-mentioned α-olefin, in which case the amount of the cyclic olefin is 50% of the copolymer.
Mol% or less, usually in the range of 1 to 50 mol%, preferably 2 to 50 mol%. Dienes and trienes that can be used in the present invention can be represented by the following general formula. It is a chain polyene. CH ₂ CH (CH) _n (CHCH ₂ ) _m where m is 1 or 2, n is 0 to 20, preferably 2 to 20
Indicates the number of Specifically, butadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene,
1,13-tetradecadiene, 2,6-dimethyl-1,5
Heptadiene, 2-methyl-2,7-octadiene,
2,7-dimethyl-2,6-octadiene, 1,5,9
-Decatriene and the like. When a chain diene or triene is used in the present invention, it is customary to copolymerize with the above-mentioned α-olefin, but the content of the chain diene and / or triene in the copolymer is generally , 0.1 to 50 mol%, preferably 0.2 to 10 mol%. Styrene analogs that can be used in the present invention are styrene and styrene derivatives.
t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene,
N, N-diethyl-p-aminoethylstyrene and the like can be exemplified. The catalyst component of the present invention can also be suitably used in the case where a homopolymer or copolymer of olefins is further polymerized with a polar monomer to modify the homopolymer or copolymer. Examples of the polar monomer include unsaturated carboxylic acid esters exemplified by methyl acrylate, methyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, monomethyl maleate, diethyl fumarate, dimethyl itaconate, and the like. Can be mentioned. The polar monomer content of the modified copolymer is usually in the range from 0.1 to 10 mol%, preferably from 0.2 to 2 mol%.

The polymerization reaction can be carried out by slurry polymerization, solution polymerization or gas phase polymerization in the presence of the above-mentioned specific polymerization catalyst. In particular, slurry polymerization or gas phase polymerization is preferable, and hexane,
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, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, olefins Is polymerized. The polymerization conditions at this time are a temperature of 20 to 200 ° C, preferably 50 to 100 ° C, a pressure of normal pressure to 70 kg / cm ² G, preferably a normal pressure to 20 kg / cm ² G, and a polymerization time of 5 minutes. It is usually employed for up 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 more effectively adjusted by adding hydrogen to the polymerization reaction system. It can be carried out.

[0031]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. Prior to this, preparation of modified organoaluminum compounds and catalyst components used in Examples and Comparative Examples will be described. Modified organoaluminum compound (methylalumoxane)
13 g of the prepared copper sulfate pentahydrate was placed in a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, and suspended in 50 ml of toluene. Then a solution of tolmethylaluminum with a concentration of 1 mmol / ml 150 m
was added dropwise to the above suspension over 2 hours under a temperature condition of 0 ° C., and after the completion of the dropwise addition, the temperature was raised to 25 ° C. and reacted at that temperature for 24 hours. Thereafter, the reaction product was filtered, and toluene in the liquid containing the reaction product was removed to obtain 4 g of white crystalline methylalumoxane (MAO). The physical properties of the polymers obtained in Examples and Comparative Examples were evaluated by the following methods. Melt index (MI) Measured based on ASTM D 1238-57T. The density was measured according to ASTM D 1505-68. Melting Point Measurement by Differential Thermal Scanning Calorimeter (DSC) Using a DSC-20 melting point measuring apparatus manufactured by Seiko Denshi Co., Ltd., hold 5 mg of sample at 180 ° C. for 3 minutes, then to 10 ° C./min to 0 ° C. The mixture was cooled, kept at 0 ° C. for 10 minutes, and then heated at a rate of 10 ° C./min to measure the melting point. Measurement of molecular weight distribution (Mw / Mn) The measurement was performed at a temperature of 135 ° C. using gel permeation chromatography (model 150-C type) manufactured by Waters, using orthodichlorobenzene as a solvent.

[0032] The toluene 100mL of purified preparation 300cc three-necked flask of Example 1 catalyst component A01, and the mixture was stirred further added tetrapropoxyzirconium 4.2g cyclopentadiene 3.6 g, a solution like catalyst component A
Got 01 . All operations were performed in a nitrogen atmosphere. A 3 L stainless steel autoclave equipped with a polymerization stirrer was purged with nitrogen, 300 mL of purified toluene was added thereto, and 3.6 mL of 1,5-hexadiene was further added, followed by 2 mL of a 1 mmol / mL methylalumoxane solution. Then, 0.2 mg of catalyst component A01 was added as zirconium atom. Then the pressure is 9 kg / cm ²
Glue ethylene into the autoclave so that G
The polymerization was started at a temperature of 30 ° C., and thereafter, the polymerization was carried out for 6 hours while continuously supplying ethylene to the autoclave and maintaining the internal pressure at 9 kg / cm ² G. After completion of the polymerization, surplus gas in the reactor is discharged, the reactor is cooled, and ethylene / 1,5-
8 g of a hexadiene copolymer was obtained. The density of this copolymer is
0.9276 g / cm ³ , melting point 138.3 ° C, ethylene content 97,9
Mol%. The catalyst efficiency was 40,000 g copolymer /
gZr.

Example 2 Preparation of Catalyst Component A02 75 mL of purified toluene was added to a 300 cc three-necked flask.
Further, 6.7 g of bisindenylethane and 2.1 g of tetrapropoxyzirconium were added, and the mixture was stirred at room temperature to obtain a uniform solution-form catalyst component A02 . All operations were performed in a nitrogen atmosphere. A 3 L stainless steel autoclave equipped with a polymerization stirrer was purged with nitrogen, and 300 mL of purified toluene was added thereto.
, And 10.0 mL of a 1 mmol / mL methylalumoxane solution, and the catalyst component A02 as zirconium atoms.
After adding 1.0 mg, the mixture was heated to 50 ° C. while stirring. Then, propylene and butene were adjusted to a pressure of 5 kg / cm ² G.
The mixed gas (1) (85 mol% of propylene, 115 mol% of butene) was charged into an autoclave to start polymerization, and thereafter the above mixed gas was continuously supplied to the autoclave. Polymerization was carried out for 2 hours while maintaining the internal pressure at 5 kg / cm ² G. After completion of the polymerization, the excess gas in the reactor is discharged, methanol is added to the reactor to precipitate a product, and the product is washed with methanol and dried to obtain 25 g of a copolymer. Obtained. The obtained copolymer had a butene-1 content of 9.6 mol% ( ¹³ C-MNR), Mw / Mn of 4.2 (GPC), an intrinsic viscosity of 0.6 dl / g (135 ° C. tetralin) and a catalyst efficiency of Was 25,000 g copolymer / gZr.

Example 3 A 3 L stainless steel autoclave equipped with a polymerization stirrer was purged with nitrogen, and 300 mL of purified toluene was added thereto.
And 11.0 mL of a 1 mmol / mL methylalumoxane solution, and the catalyst component A02 as zirconium atom.
After adding 1.0 mg, ethylene was charged into the autoclave so that the pressure became 9 kg / cm ² G, polymerization was started at 30 ° C., and then ethylene was continuously supplied to the autoclave. Polymerization was carried out while maintaining the internal pressure at 9 kg / cm ² G. Thereafter, 54 mL of methyl methacrylate was added to the autoclave, and ethylene was further supplied to carry out polymerization at 30 ° C. for 3 hours while maintaining the internal pressure at 9 kg / cm ² G. After completion of the polymerization, excess gas in the reactor was discharged, and the reactor was cooled to obtain 4 g of a polymer. After dissolving this polymer in toluene, acetone was added to this solution to precipitate the polymer. After drying the obtained polymer, it was molded into a sheet having a thickness of 25 μm (pressed at 190 ° C. × 5 minutes), and the infrared absorption spectrum was measured.
At -1, absorption by a carbonyl group was observed. The dried polymer had an Mw / Mn of 4.8 and an intrinsic viscosity of 1.7 dl / g (135
° C tetralin) and the catalyst efficiency is 4,000g copolymer /
gZr.

Example 4 A 3 L stainless steel autoclave equipped with a polymerization stirrer was purged with nitrogen, and 300 mL of purified toluene was added thereto.
Was added thereto, and 5 mL of a 1 mmol / mL methylalumoxane solution and 1.0 mg of a catalyst component A02 as zirconium atoms were added thereto.
Polymerization was performed at 30 ° C. for 24 hours. Thereafter, ethylene was poured into the autoclave so that the internal pressure became 3.5 kg / cm ² G, and the polymerization was restarted. Thereafter, the autoclave was continuously supplied with ethylene to reduce the internal pressure to 3.5 kg / cm ² G. The polymerization was carried out for 1 hour while maintaining the pressure at kg / cm ² G. After the polymerization was completed, excess gas in the reactor was discharged, and then methanol was added to precipitate a produced copolymer. The obtained copolymer was washed with methanol and dried to obtain 6 g. Was obtained. The ethylene content of this polymer is 97.2 mol% ( ^13C -MNR), Mw / Mn
Was 4.2 (GPC), the intrinsic viscosity was 1.1 dl / g (tetralin at 135 ° C.), and the catalytic efficiency was 2,000 g copolymer / gZr.

Example 5 Preparation of Catalyst Component A03 100 mL of purified toluene was placed in a 300 mL three-necked flask, and 4.2 g of tetrapropoxyzirconium and 5.1 g of cyclopentadiene were added thereto and stirred at room temperature to obtain a homogeneous solution. In another 300 mL three-necked flask, 50 mL of a toluene solution of methylalumoxane (concentration 2 mmol / mL) and 1.7 mL of the above solution were added, and 150 mL of purified n-
Hexane was gradually added to precipitate a solid, and the supernatant was removed, followed by drying under reduced pressure to obtain a solid catalyst component A03 . Stainless steel autoclave 3L marked with prepolymerization stirrer was purged with nitrogen, after the addition of the solid catalyst component A03 of n- hexane and 2g of 100mL thereto, stakeout ethylene, room temperature, 0.5 kg / cm ² G Prepolymerization was performed at an ethylene pressure of 30 minutes. A 3 L stainless steel autoclave equipped with a polymerization stirrer was purged with nitrogen, 200 g of dried salt was added thereto, and triisobutylaluminum and water were further added to Al:
0.5 mL of an isobutylalumoxane solution (concentration: 1 mmol / mL) obtained by reacting at a ratio of H ₂ O = 1: 0.5 and 0.14 g of the prepolymerized product prepared above were added, and heated to 60 ° C.
Next, ethylene was charged into the autoclave so that the pressure became 9 kg / cm ² G, and polymerization was started. Thereafter, ethylene was continuously supplied to the autoclave to reduce the internal pressure to 9 kg / cm 2. ^Two
While maintaining at G, polymerization was carried out for 1 hour. After completion of the polymerization, excess gas in the reactor was discharged, and the reactor was cooled to obtain 32 g of a white polymer. Ethylene / butene-1 thus obtained
The melt index (MI) of the copolymer is 3.9g / 10mi
n, Mw / Mn was 4.5.

Example 6 Preparation of Catalyst Component A04 In a 300 mL three-necked flask, 75 mL of purified toluene was placed, and
3.6 g of monocyclopentadienyltrimethylsilane
And 2.1 g of tetrapropoxyzirconium, and the mixture was stirred to obtain a uniform solution-form catalyst component A04 . A 3 L stainless steel autoclave equipped with a polymerization stirrer was purged with nitrogen, and 250 g of dried salt, 0.2 mL of the above catalyst component A04 (toluene solution) and a concentration of 1 mmol were added.
8.0 mL of a / mL solution of methylalumoxane was added. Thereafter, a mixed gas of ethylene and butene-1 (butene-1 /
(The molar ratio of ethylene = 0.25) when the internal pressure of the autoclave is 9
kg / cm ² so that the G o - Tokure - Bed in the polymerization initiated by Harikon, then continuously mixed gas above Oh - Tokure - the supply to the internal pressure in Bed to 9 kg / cm ² G 1 while maintaining
Polymerization was carried out for hours. After completion of the polymerization, excess gas in the reactor was discharged, and the reactor was cooled to obtain 23 g of a copolymer. The ethylene / butene-1 copolymer thus obtained had a melt index (MI) of 1.9 g / 10 min, a density of 0.9236 g / cm ³ and a melting point of 114.9 ° C. The catalyst efficiency was 16,000 copolymer / gZr.

Example 7 Preparation of Catalyst Component A05 100 mL of purified toluene was placed in a 300 mL three-necked flask, and 2.5 g of indene was added thereto, followed by cooling to -60 ° C. to obtain a solution (a). 50 mL of toluene was placed in another 100 mL flask, and tetrabenzyl zirconium (Zr (Bz))
₄ ) A solution (b) was prepared by adding 4.2 g and 1.8 g of indene. Next, solution (b) was added to solution (a) over 20 minutes. After completion of the addition, stirring was continued at -60 ° C for 1 hour, and the temperature was gradually raised to 20 ° C over 2 hours while stirring. Further, this mixed solution was reacted by stirring at 45 ° C. for 3 hours to obtain a catalyst component A05 in the form of a solution. The Zr concentration in this solution was 5.4 mg / ml. All experiments were performed in a nitrogen atmosphere.
Tetrabenzyl zirconium was synthesized by the following method. In a one-liter three-necked flask equipped with an electromagnetic induction stirrer,
At 0 ° C. under a nitrogen atmosphere, 500 mL of a diethyl ether solution containing 70 g of benzylmagnesium chloride was added, and then 30 g of zirconium tetrachloride was added over 30 minutes under a nitrogen atmosphere. The mixture was stirred for 2 hours, during which time the temperature was raised to room temperature. Next, 300 mL of decalin was added, and the mixture was stirred at room temperature for 1 hour. The generated magnesium chloride was isolated, and the resulting decalin solution was heated to 50 ° C., and ether was removed while blowing nitrogen gas. From the obtained decalin solution, tetrabenzyl zirconium 32
g was obtained. A 3 L stainless steel autoclave equipped with a polymerization stirrer was purged with nitrogen, and 200 g of dried salt was added thereto.
28 ml of the catalyst component A and 16 ml of a methylalumoxane solution (concentration: 1 mmol / mL) were added, and the mixture was heated to 60 ° C. with stirring. Next, ethylene and butene-1 were adjusted so that the internal pressure became 9 kg / cm ² G.
A mixture gas (butene-1 / ethylene molar ratio = 0.25) was charged into an autoclave to start polymerization, and thereafter, a mixture gas of ethylene and butene-1 (butene-1 / ethylene molar ratio = 0.25). 0.05) continuously, while the internal pressure is 9kg / cm
The polymerization was carried out for 1 hour while maintaining the temperature at ² G and the temperature at 60 ° C. After completion of the polymerization, an excess mixed gas was discharged and cooled, and the content was taken out to obtain a white copolymer.

Examples 8 to 19 Preparation of catalyst components A06 to A16 Catalyst components A06 to A16 were prepared in the same manner as for catalyst component A05 , using the two components shown in Table 1 in the proportions indicated. Polymerization Ethylene and butene-1 were copolymerized in the same manner as in Example 7 except that the catalyst component A05 used in Polymerization Example 7 was replaced with any of the catalyst components A06 to A16 shown in Table 1. However,
In Example 18, instead of using a mixed gas of ethylene and butene-1, homopolymerization of ethylene was performed using only ethylene, and similarly, in Example 19, homopolymerization of propylene was performed using only propylene. . Table 2 shows the amount of the catalyst component used and the properties of the produced polymer.

[0040]

[Table 1]

[0041]

[Table 2]

Comparative Examples 1 to 9 Preparation of Catalyst Component B01 100 mL of purified toluene was placed in a 300 mL three-necked flask, and 4.2 g of tetrabenzylzirconium was added thereto and stirred at room temperature to obtain a catalyst component B01 . Preparation of Catalyst Components B02 to B09 Catalyst components B02 to B09 were prepared in the same manner as the catalyst component B01 , except that the transition metal compounds shown in Table 2 were used instead of tetrabenzylzirconium. Polymerization Ethylene and butene-1 were copolymerized in the same manner as in Example 7 except that the catalyst component A05 used in Polymerization Example 7 was replaced with any of the catalyst components B01 to B09 shown in Table 1. Table 2 shows the amount of the catalyst component used and the properties of the produced polymer.

Example 20 Preparation of Catalyst Component A17 75 mL of purified toluene was placed in a 300 mL three-necked flask, and 3.0 g of indene and 2.1 g of tetrapropoxyzirconium were added thereto, followed by stirring at room temperature for 30 minutes to obtain a homogeneous solution. Was prepared as catalyst component A17 . The Zr concentration of this homogeneous solution was 7.8 mg / mL. A 3 liter stainless steel autoclave equipped with a polymerization stirrer was charged with 250 g of dried sodium chloride by purging with nitrogen, and 0.2 mL of the catalyst component A17 and 8.6 mL of a 1 mmol / mL alumoxane solution were added thereto, followed by stirring. While heating to 60 ° C. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio = 0.25) was charged into the autoclave so that the internal pressure became 9 kg / cm ² G, and polymerization was started. A mixed gas of butene-1 (butene-1 / ethylene molar ratio = 0.05) was continuously supplied to carry out polymerization for 1 hour while maintaining the internal pressure at 9 kg / cm ² G. After completion of the polymerization, excess gas was discharged to cool the autoclave, thereby obtaining 10.1 g of a copolymer.

Examples 21 to 29 Preparation of catalyst components A18 to A26 Catalyst components A18 to A26 were prepared in the same manner as for catalyst component A17 , using the two components shown in Table 3 in the proportions indicated. Ethylene and butene-1 were copolymerized in the same manner as in Example 20, except that the catalyst component A17 used in Polymerization Example 20 was replaced with any of the catalyst components A18 to A26 shown in Table 3. However, in Example 29, instead of using a mixed gas of ethylene and butene-1, homopolymerization of ethylene was performed using only ethylene. Table 4 shows the amount of the catalyst component used and the properties of the produced polymer.
Shown in

Comparative Examples 10 to 11 Preparation of Catalyst Components B10 and B11 A toluene solution of tetrapropoxyzirconium was used as catalyst component B10, and a toluene solution of dicyclopentadienyldichlorozirconium was used as catalyst component B11 . The catalyst component A17 used in the polymerization example 20, the catalyst component B10 or B1
But substituting the 1, obtained by copolymerizing ethylene and butene-1 in the same manner as in Example 20. Table 4 shows the amount of the catalyst component used and the properties of the produced polymer.

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

The catalyst component proposed by the present invention has a high polymerization activity per transition metal. This catalyst component is converted to a suitable promoter.
When the polymerization catalyst composition combined with the ter component is used for homopolymerization or copolymerization of α-olefins, a homopolymer having a high molecular weight and a wide molecular weight distribution or a copolymer having a narrow composition distribution is obtained. be able to. Ethylene or propylene obtained using the catalyst component of the present invention, and other α
-Copolymerization with an olefin can be formed into a highly transparent film or sheet, but the film or sheet does not adhere to each other during the forming process. In the case where ethylene and a diene are copolymerized using the catalyst composition containing the catalyst component of the present invention, it is possible to obtain a copolymer having a high melting point despite having a low density. It is possible. Further, the catalyst composition containing the catalyst component of the present invention can be used for copolymerization of an olefin and a polar monomer to produce a block copolymer having a wide molecular weight distribution.

[Brief description of the drawings]

FIG. 1 is a flow chart showing a preparation process of a catalyst composition used in the present invention.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takashi Seki 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Japan Japan Petroleum Co., Ltd. (72) Inventor Kazuo Matsuura 8 Chidori-cho, Naka-ku, Yokohama, Kanagawa Japan (56) References JP-A-1-301704 (JP, A) JP-A-2-84404 (JP, A) JP-A-2-242804 (JP, A) JP-A-55- 38870 (JP, A) JP-A-63-68621 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1) The general formula Me ¹ (OR ¹ ) _p R ² _q
A compound represented by X ¹⁴ _-pq (wherein R ¹ and R ² are each independently a hydrocarbon residue having 1 to 24 carbon atoms, X ¹ is a halogen atom, M
e ¹ represents Ti, Zr or Hf, p is 0 ≦ p ≦ 4, q
Is 0 ≦ q ≦ 4, and p + q is 0 ≦ p + q ≦ 4) and (2) a carbon atom, a hydrogen atom, an oxygen atom, and a silicon atom.
It consists construction element selected from the group that, Chi lifting conjugated double bonds two or more carbon atoms constituting the ring 5 or 7
An olefin polymerization catalyst composition obtained by bringing an organic cyclic compound having at least one ring of No. 24 into contact with each other. 2. The general formula Me ¹ (OR ¹ ) _p R ² _q X ¹
A compound represented by _4-pq (wherein R ¹ and R ² are each independently a hydrocarbon residue having 1 to 24 carbon atoms, X ¹ is a halogen atom, Me ¹
Represents Ti, Zr or Hf, p is 0 ≦ p ≦ 4, q is 0
≦ q ≦ 4, p + q is 0 ≦ p + q ≦ 4) and (2) a carbon atom, a hydrogen atom, an oxygen atom, and a silicon atom.
It consists construction element selected from the group that, Chi lifting conjugated double bonds two or more carbon atoms constituting the ring 5 or 7
A catalyst component obtained by mutually contacting an organic cyclic compound having at least one ring of No. 24, a modified organic aluminum compound containing an Al-O-Al bond obtained by reacting an organic aluminum compound with water, A method for producing an olefin polymer, comprising polymerizing or copolymerizing an olefin in the presence of a catalyst composition comprising: