JP3394576B2 - Prepolymerization catalyst, olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a prepolymerization catalyst capable of producing an olefin polymer having excellent heat resistance and rigidity, an olefin polymerization catalyst containing the prepolymerization catalyst, and an α-olefin polymerization method.

[0002]

BACKGROUND OF THE INVENTION So-called Kaminsky catalysts are well known as transition metal compounds of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton.
This catalyst has a feature that a polymer having a very high polymerization activity and a narrow molecular weight distribution can be obtained.

Among the transition metal compounds used for the Kaminsky catalyst, transition metal compounds for producing isotactic polyolefin include ethylene bis (indenyl) zirconium dichloride and ethylene bis (4,5,6,7-
Tetrahydroindenyl) zirconium dichloride (JP-A-61-130314) is known. However, polyolefins produced using such catalysts generally have problems such as low stereoregularity and low melting points due to the formation of heterogeneous bonds.

It has been known that a high molecular weight compound can be produced by using a hafnium compound instead of a zirconium compound as a transition metal compound (Journal).
of Molecular Catalysis, 56 (1989) p.237-247), but this method has a problem that the polymerization activity is low. Further, dimethylsilylbis-substituted cyclopentadienyl zirconium dichloride and the like are disclosed in JP-A-1-301704,
Polymer Preprints, Japan vol.39, No.6 p.1614-1616 (1
990) and the like, but there is a problem that high polymerization activity, high melting point and high molecular weight cannot be satisfied at the same time.

Further, Japanese Patent Laid-Open No. 4-268307 discloses that
An olefin polymerization catalyst comprising a metallocene compound represented by the following formula and an aluminoxane is described.

[0006]

[Chemical 1]

Further, EP 0 530 648 A1 describes an olefin polymerization catalyst comprising a metallocene compound represented by the following formula and an aluminoxane.

[0008]

[Chemical 2]

(In the formula, A represents a lower alkyl group.) However, even the polyolefins obtained by these catalysts are not always satisfactory in melting point and molecular weight.

In the above formula, the catalyst in which A is a phenyl group is 40YEARS ZIEGLER CATALYSISIN HONOR OF KARL ZI
It is published by Hoechst in the EGLER ANNDO WORKSHOP (Sept. 1-3, 1993). However, the polyolefin obtained by this catalyst still has a problem that its melting point is low.

Under these circumstances, the advent of a catalyst capable of increasing the melting point of the obtained polyolefin and producing a polyolefin having excellent heat resistance and rigidity is desired.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional techniques, and an object of the present invention is to provide a catalyst capable of producing an olefin polymer having excellent heat resistance and rigidity. Specifically, a prepolymerization catalyst obtained by prepolymerizing an olefin having a specific structure in a specific catalyst component, an olefin polymerization catalyst containing the prepolymerization catalyst, and a method for polymerizing an α-olefin using the prepolymerization catalyst are described. It is intended to be provided.

[0013]

SUMMARY OF THE INVENTION A prepolymerization catalyst [I] according to the present invention comprises (A) a transition metal compound of Group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton, and (B) (B- 1) Organoaluminum oxy compounds, and (B
-2) At least one compound selected from the group consisting of compounds that react with the above transition metal compound (A) to form an ion pair, and (C) an organoaluminum compound, if necessary, in the ring. It is characterized in that a cycloolefin having a heavy bond is prepolymerized.

The olefin polymerization catalyst according to the present invention is selected from the group consisting of the above-mentioned prepolymerization catalyst [I] and, if necessary, [II] above (B-1) and (B-2). And / or [III] organoaluminum compound.

The olefin polymerization method according to the present invention comprises a prepolymerization catalyst [I] as described above and, if necessary, [II].
The α-olefin is polymerized or copolymerized in the presence of at least one compound selected from the group consisting of (B-1) and (B-2) above, and / or [III] an organoaluminum compound, to obtain It is characterized in that the prepolymer contained in the obtained olefin polymer is contained in an amount of 10 to 10,000 ppm.

The present invention provides an olefin polymer having a high melting point and excellent heat resistance and rigidity.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The following is a prepolymerization catalyst according to the present invention,
The olefin polymerization catalyst and the olefin polymerization method will be specifically described.

In the present specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may refer to not only homopolymer but also copolymer. It may be used to include a polymer.

The prepolymerization catalyst [I] according to the present invention comprises (A) a transition metal compound, (B) (B-1) an organoaluminum oxy compound, and (B)
-2) At least one compound selected from the group consisting of compounds that react with the above transition metal compound (A) to form an ion pair, and (C) an organoaluminum compound, if necessary, in the ring. It is prepared by prepolymerizing a cycloolefin having a heavy bond.

First, these catalyst components (A), (B),
(C) will be described. (A) Transition metal compound

The transition metal compound of Group IVB of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton is specifically a transition metal compound represented by the following formula [I]. ML _x ... [I] In the formula, M is a transition metal selected from the group consisting of Zr, Ti, Hf, V, Nb, Ta and Cr, and x is the valence of the transition metal.

L is a ligand that coordinates to a transition metal,
At least one L is a ligand having a cyclopentadienyl skeleton, and at least two L is preferably a ligand having a cyclopentadienyl skeleton.

Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group, indenyl group, 4,5,6,7-tetrahydroindenyl group, 4,5,6,6a.
-Tetrahydropentalenyl group, 7,8-dihydro-3H, 6H-as
Examples thereof include an indacenyl group and a fluorenyl group. These groups may be substituted with an alkyl group, an aryl group, an aralkyl group, a trialkylsilyl group, a halogen atom, an alkoxy group, an aryloxy group, a chain or cyclic alkylene group and the like. Further, these groups having a cyclopentadienyl skeleton may be condensed with a benzene ring, a naphthalene ring, an acenaphthene ring, an indene ring or the like.

Among the ligands having a cyclopentadienyl skeleton coordinated to these transition metals, a group having an indenyl skeleton is preferable, and a group having an indenyl skeleton having a substituent is particularly preferable.

When the transition metal compound represented by the above general formula [I] contains two or more groups having a cyclopentadienyl skeleton, the two groups having a cyclopentadienyl skeleton among them are ethylene. , Alkylene groups such as propylene, substituted alkylene groups such as 1,2-di (α-naphthyl) ethylene, cycloalkylene groups such as 1,4-cyclohexylene and 1,3-cyclopentylene, 2,5-diisopropyl-
A substituted cycloalkylene group such as 1,4-cyclohexylene,
Substituted alkylidene group such as isopropylidene, diphenylmethylene, phenylene group, silylene group, dimethylsilylene group, diphenylsilylene group, substituted silylene group such as methylphenylsilylene group, germyl group, -P (R ^a ).
-, - P (O) ( R b) -, - SO 2 N- (R c) -, -
Sn (R ^d ₂ )-, -Fe- [provided that R ^a , R ^c and R ^d ₂
Is an alkyl group, and R ^b is an aryl group. ] And the like are preferred.

Of these, it is particularly preferable that the groups are bonded via a substituted silylene group such as a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group.

L other than the ligand having a cyclopentadienyl skeleton is an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, propyl group, pentyl group, neopentyl group; cyclopentyl group, cyclohexyl group. Groups such as cycloalkyl groups; aryl groups such as phenyl groups, tolyl groups, mesityl groups; benzyl groups, hydrocarbon groups having 1 to 10 carbon atoms such as aralkyl groups such as neofil groups, methoxy groups, ethoxy groups, propoxy groups, C1-C10 alkoxy group such as butoxy group, C6-C10 aryloxy group such as phenoxy group, mesitylsulfonato group, phenylsulfonato group, benzylsulfonato group, methylsulfonato group, p-toluene -OSO ₂ such as sulfonate and trifluoromethanesulfonate group
^{_{R 8, -CH 2 SiR 8 3}} ( where, R ⁸ is 1 to 10 carbon atoms
Is a hydrocarbon group), a halogen atom such as fluorine, chlorine, bromine and iodine, or a hydrogen atom, which may be the same or different.

The transition metal compound (A) containing such a ligand having a cyclopentadienyl skeleton is more specifically represented by the following formula [II] when the valence of the transition metal is 4. To be done.

R ² _k R ³ _l R ⁴ _m R ⁵ _n M ... [II] In the formula, M is the above transition metal, and R ² is a group having a cyclopentadienyl skeleton similar to the above formula [I]. (Ligand)
And R ³ , R ⁴ and R ⁵ are the same as those of the above formula [I] having a cyclopentadienyl skeleton or a ligand having a cyclopentadienyl skeleton as described above, which is the same as L. It is a base. k is an integer of 1 or more, and k + 1
+ M + n = 4.

In the present invention, in the above formula [II], R ² ,
At least two of R ³ , R ⁴ and R ⁵ , eg R ²
A transition metal compound in which R ³ is an indenyl group having a substituent is preferably used. The groups having these two cyclopentadienyl skeletons are preferably bound to each other via a group similar to the above formula [I].

Below, a transition metal in which M is zirconium
Specific compounds are exemplified as the compounds. Ethylene vinyl
Su (2-phenyl-1-indenyl) zirconium dichloride
Substance, ethylene bis (2-isopropyl-1-indenyl) di
Ruconium dichloride, ethylene bis (2-methyl-1-yne
Denyl) zirconium dihydride, ethylene bis (2-meth
Cyl-1-indenyl) zirconium difluoride, ethylene
Bis (2-methyl-1-indenyl) zirconium dibromide
, Ethylene bis (2-methyl-1-indenyl) zirconi
Um diiodide, ethylene bis (2-methyl-1-indeni
Z) Zirconium dimethoxide, ethylene bis (2-meth
Ru-1-indenyl) zirconium di-n-butoxide, ethyl
Lenbis (2-methyl-1-indenyl) zirconium dif
Enoxide, ethylenebis (2-methyl-1-indenyl)
Zirconium di-t-butoxide, ethylene bis (2-methyl
Ru-1-indenyl) zirconium dimethyl, ethylene bi
Sus (2-methyl-1-indenyl) zirconium Dineopen
Chill, ethylene bis (2-methyl-1-indenyl) zirco
Indium ditrimethylsilylmethyl, ethylene bis (2-me
Cyl-1-indenyl) zirconium ditosylate, ethi
Lenbis (2-methyl-1-indenyl) zirconium dime
Sylate, ethylenebis (2-methyl-1-indenyl) di
Ruconium di (mesityl sulfonate), ethylene vinyl
Sus (2-methyl-1-indenyl) zirconium di (phenylene
Sulfonate), ethylenebis (2-methyl-1-indene)
Nyl) zirconium di (benzyl sulfonate), d
Tylene bis (2-methyl-1-indenyl) zirconium di
(Trifluoromethanesulfonate), ethylene bis
(2-Methyl-1-indenyl) zirconium monochloride
Monohydride, ethylenebis (2-methyl-1-indeni
Le) Zirconium monochloride monofluoride, ethylene vinyl
Sus (2-methyl-1-indenyl) zirconium monochloro
Domonobromide, ethylene bis (2-methyl-1-indeni
Le) Zirconium monochloride monoiodide, ethylene vinyl
Sus (2-methyl-1-indenyl) zirconium monochloro
Domonomethoxide, ethylene bis (2-methyl-1-indene
Nil) zirconium monochloride mono-n-butoxide,
Ethylene bis (2-methyl-1-indenyl) zirconium
Monochloride monophenoxide, ethylene bis (2-meth
Ru-1-indenyl) zirconium monochloride mono-t-bu
Toxide, ethylenebis (2-methyl-1-indenyl) di
Ruconium monochloride monomethyl, ethylenebis (2-
Methyl-1-indenyl) zirconium monochloride mono
Neopentyl, ethylene bis (2-methyl-1-indeni
Le) Zirconium monochloride Monotrimethylsilylme
Chill, ethylene bis (2-methyl-1-indenyl) zirco
Nium monochloride monotosylate, ethylene bis (2-
Methyl-1-indenyl) zirconium monochloride mono
Mesylate, ethylene bis (2-methyl-1-indenyl)
Zirconium Monochloride Mono (mesityl sulphoner)
G), ethylenebis (2-methyl-1-indenyl) zirco
Nimonochlorid mono (phenyl sulfonate),
Ethylene bis (2-methyl-1-indenyl) zirconium
Monochlorid mono (benzyl sulfonate), ethyl
Bis (2-methyl-1-indenyl) zirconium monoc
Lolidmono (trifluoromethanesulfonate), d
Tylene bis (2-methyl-1-indenyl) zirconium
Nohydride monofluoride, ethylene bis (2-methyl-1-yl)
Ndenyl) zirconium monohydride monochloride, ethi
Lenbis (2-methyl-1-indenyl) zirconium mono
Hydride monobromide, ethylene bis (2-methyl-1-yne
Denyl) zirconium monohydride monoiodide, ethyl
Bis (2-methyl-1-indenyl) zirconium monohi
Dorido monomethoxide, ethylene bis (2-methyl-1-yl)
Ndenyl) zirconium monohydride mono-n-butoxy
De, ethylene bis (2-methyl-1-indenyl) zirconi
Ummonohydridomonophenoxide, ethylenebis (2-
Methyl-1-indenyl) zirconium monohydride mono-t
-Butoxide, ethylenebis (2-methyl-1-indenyl)
Zirconium monohydride monomethyl, ethylene bis
(2-Methyl-1-indenyl) zirconium monohydride
Mononeopentyl, ethylene bis (2-methyl-1-indene
Nyl) zirconium monohydride monotrimethylsilyl
Methyl, ethylene bis (2-methyl-1-indenyl) dil
Conium monohydride monotosylate, ethylene bis
(2-Methyl-1-indenyl) zirconium monohydride
Monomesylate, ethylene bis (2-methyl-1-indeni
Z) Zirconium monohydrido mono (mesityl sulfo)
Nato), ethylenebis (2-methyl-1-indenyl) di
Ruconium monohydrido mono (phenyl sulfonate
G), ethylenebis (2-methyl-1-indenyl) zirco
Nium monohydrido mono (benzyl sulfonate),
Ethylene bis (2-methyl-1-indenyl) zirconium
Monohydrido mono (trifluoromethanesulfonate
G), ethylenebis (2-methyl-1-indenyl) zirco
Dichloride, dimethylsilylene bis (2-methyl-1-
Indenyl) zirconium dichloride, dimethyl silylene
Bis (2-phenyl-1-indenyl) zirconium dichloride
Dimethylsilylene bis (2-isopropyl-1-indene
Nyl) zirconium dichloride, diphenylsilylene bis
(2-Methyl-1-indenyl) zirconium dichloride, di
Phenylsilylene bis (2-phenyl-1-indenyl) di
Ruconium dichloride, diphenylsilylene bis (2-iso
Propyl-1-indenyl) zirconium dichloride, methyl
Ruphenylsilylene bis (2-methyl-1-indenyl) di
Ruconium dichloride, silylene bis (2-methyl-1-yne
(Denyl) zirconium dichloride, dimethylgermylene bi
Sus (2-methyl-1-indenyl) zirconium dichloride,
Phenylphosphinylene bis (2-methyl-1-indeni
Ru) zirconium dichloride, ethylene bis (3-methyl-1)
-Indenyl) zirconium dichloride, dimethylsilyl
Bis (3-methyl-1-indenyl) zirconium dichloride
, Diphenylsilylene bis (3-methyl-1-indeni
Le) Zirconium dichloride, methylphenyl silylene bi
Sus (3-methyl-1-indenyl) zirconium dichloride,
Ethylene bis (2,4-dimethyl-1-indenyl) zirconi
Umium dichloride, ethylene bis (2-methyl, 4-isopropylamine
Ru-1-indenyl) zirconium dichloride, ethylene vinyl
Sus (2-isopropyl, 4-methyl-1-indenyl) zirconi
Umium dichloride, ethylene bis (2-phenyl, 4-methyl-1-
Indenyl) zirconium dichloride, dimethyl silylene
Bis (2,4-dimethyl-1-indenyl) zirconium di-salt
Compound, dimethylsilylene bis (2-methyl, 4-isopropylamine
Ru-1-indenyl) zirconium dichloride, dimethyl
Rylene bis (2-isopropyl, 4-methyl-1-indenyl)
Zirconium dichloride, dimethylsilylene bis (2-phen
Nyl, 4-methyl-1-indenyl) zirconium dichloride,
Diphenylsilylene bis (2,4-dimethyl-1-indeni
Ru) Zirconium dichloride, diphenylsilylene bis
(2-Methyl, 4-isopropyl-1-indenyl) zirconium
Dichloride, diphenylsilylene bis (2-isopropylamine)
Ru, 4-methyl-1-indenyl) zirconium dichloride, di
Phenylsilylenebis (2-phenyl, 4-methyl-1-indene
Nyl) zirconium dichloride, methylphenylsilylene
Bis (2,4-dimethyl-1-indenyl) zirconium di-salt
Compound, methylphenylsilylenebis (2-methyl, 4-iso
Propyl-1-indenyl) zirconium dichloride, methyl
Ruphenylsilylene bis (2-isopropyl, 4-methyl-1-
Indenyl) zirconium dichloride, methylphenyloxy
Rylene bis (2-phenyl, 4-methyl-1-indenyl) dil
Conium dichloride, ethylene bis (2,5-dimethyl-1-y
Ndenyl) zirconium dichloride, ethylene bis (2-me
Chill, 5-isopropyl-1-indenyl) zirconium di-salt
Compound, ethylenebis (2-isopropyl, 5-methyl-1-yne
Denyl) zirconium dichloride, ethylene bis (2-phen)
Nyl, 5-methyl-1-indenyl) zirconium dichloride,
Dimethyl silylene bis (2,5-dimethyl-1-indenyl)
Zirconium dichloride, dimethyl silylene bis (2-methyl
Le, 5-isopropyl-1-indenyl) zirconium dichloride
, Dimethylsilylene bis (2-isopropyl, 5-methyl-
1-indenyl) zirconium dichloride, dimethyl silyl
Bis (2-phenyl, 5-methyl-1-indenyl) zirconi
Umium dichloride, diphenylsilylene bis (2,5-dimethyl
-1-Indenyl) zirconium dichloride, diphenyl
Rylene bis (2-methyl, 5-isopropyl-1-indenyl)
Zirconium dichloride, diphenylsilylene bis (2-
Sopropyl, 5-methyl-1-indenyl) zirconium di-salt
Compound, diphenylsilylene bis (2-phenyl, 5-methyl-
1-indenyl) zirconium dichloride, methylphenyl
Silylene bis (2,5-dimethyl-1-indenyl) zirconi
Um dichloride, methylphenylsilylene bis (2-methyl
Le, 5-isopropyl-1-indenyl) zirconium dichloride
, Methylphenylsilylenebis (2-isopropyl, 5-
Methyl-1-indenyl) zirconium dichloride, methyl
Phenylsilylene bis (2-phenyl, 5-methyl-1-indene
Nyl) zirconium dichloride, ethylene bis (2,6-dimethyl)
Cyl-1-indenyl) zirconium dichloride, ethylene
Bis (2-methyl, 6-isopropyl-1-indenyl) zirco
Dichloride, ethylene bis (2-isopropyl, 6-meth
Cyl-1-indenyl) zirconium dichloride, ethylene
Bis (2-phenyl, 6-methyl-1-indenyl) zirconium
Dichloride, dimethylsilylene bis (2,6-dimethyl-1-
Indenyl) zirconium dichloride, dimethyl silylene
Bis (2-methyl, 6-isopropyl-1-indenyl) zirco
Dichloride, dimethylsilylene bis (2-isopropylamine)
Ru, 6-methyl-1-indenyl) zirconium dichloride, di
Methylsilylene bis (2-phenyl, 6-methyl-1-indeni
Ru) Zirconium dichloride, diphenylsilylene bis
(2,6-Dimethyl-1-indenyl) zirconium dichloride
, Diphenylsilylene bis (2-methyl, 6-isopropyl
Ru-1-indenyl) zirconium dichloride, diphenyl
Silylenebis (2-isopropyl, 6-methyl-1-indeni
Ru) Zirconium dichloride, diphenylsilylene bis
(2-phenyl, 6-methyl-1-indenyl) zirconium di
Chloride, methylphenylsilylene bis (2,6-dimethyl-1
-Indenyl) zirconium dichloride, methylphenyl
Silylenebis (2-methyl, 6-isopropyl-1-indeni
Le) Zirconium dichloride, methylphenyl silylene bi
Sus (2-isopropyl, 6-methyl-1-indenyl) zirconi
Um dichloride, methylphenylsilylene bis (2-phenylene
1,6-methyl-1-indenyl) zirconium dichloride, d
Tylene bis (2,7-dimethyl-1-indenyl) zirconium
Dichloride, ethylene bis (2-methyl, 7-isopropyl-
1-indenyl) zirconium dichloride, ethylene bis
(2-Isopropyl, 7-methyl-1-indenyl) zirconium
Dichloride, ethylene bis (2-phenyl, 7-methyl-1-y)
Ndenyl) zirconium dichloride, dimethyl silylene bi
Sus (2,7-dimethyl-1-indenyl) zirconium dichloride
Dimethylsilylenebis (2-methyl, 7-isopropyl-
1-indenyl) zirconium dichloride, dimethyl silyl
Bis (2-isopropyl, 7-methyl-1-indenyl) dil
Conium dichloride, dimethylsilylene bis (2-phenylene
Ru, 7-methyl-1-indenyl) zirconium dichloride, di
Phenylsilylenebis (2,7-dimethyl-1-indenyl)
Zirconium dichloride, diphenylsilylene bis (2-me
Chill, 7-isopropyl-1-indenyl) zirconium di-salt
Compound, diphenylsilylene bis (2-isopropyl, 7-meth
Cyl-1-indenyl) zirconium dichloride, dipheni
Lucillene bis (2-phenyl, 7-methyl-1-indenyl)
Zirconium dichloride, methylphenylsilylene bis
(2,7-Dimethyl-1-indenyl) zirconium dichloride
, Methylphenylsilylene bis (2-methyl, 7-isop
Ropyl-1-indenyl) zirconium dichloride, methyl
Phenylsilylene bis (2-isopropyl, 7-methyl-1-y
Ndenyl) zirconium dichloride, methylphenylsilyl
Lenbis (2-phenyl, 7-methyl-1-indenyl) zirco
Dichloride, ethylene bis (2,3-dimethyl-1-yne
Denyl) zirconium dichloride, dimethylsilylene bis
(2,3-Dimethyl-1-indenyl) zirconium dichloride
Diphenylsilylene bis (2,3-dimethyl-1-indene
Nyl) zirconium dichloride, methylphenylsilylene
Bis (2,3-dimethyl-1-indenyl) zirconium di-salt
Compound, ethylene bis (2,4,5-trimethyl-1-indeni
Ru) zirconium dichloride, ethylene bis (2-isopro
Pyr-4,5-dimethyl-1-indenyl) zirconium dichloride
Product, ethylene bis (2-phenyl-4,5-dimethyl-1-indene
Nyl) zirconium dichloride, dimethyl silylene bis
(2,4,5-Trimethyl-1-indenyl) zirconium di-salt
Compound, dimethylsilylene bis (2-isopropyl-4,5-di
Methyl-1-indenyl) zirconium dichloride, dimethy
Lucillene bis (2-phenyl-4,5-dimethyl-1-indeni
Ru) Zirconium dichloride, diphenylsilylene bis
(2,4,5-Trimethyl-1-indenyl) zirconium di-salt
Compound, diphenylsilylene bis (2-isopropyl-4,5-
Dimethyl-1-indenyl) zirconium dichloride, dif
Phenylsilylene bis (2-phenyl-4,5-dimethyl-1-yne
Denyl) zirconium dichloride, methylphenylsilyl
Bis (2,4,5-trimethyl-1-indenyl) zirconium
Dichloride, methylphenylsilylene bis (2-isoproline
Pyr-4,5-dimethyl-1-indenyl) zirconium dichloride
, Methylphenylsilylene bis (2-phenyl-4,5-di
Methyl-1-indenyl) zirconium dichloride, ethyl
Bis (2,4,7-trimethyl-1-indenyl) zirconium
Dichloride, dimethylsilylene bis (2,4,7-trimethyl
-1-Indenyl) zirconium dichloride, dimethylsilyl
Lenbis (2-isopropyl-4,7-dimethyl-1-indeni
Ru) zirconium dichloride, dimethylsilylene bis (2-
Phenyl-4,7-dimethyl-1-indenyl) zirconium di
Chloride, dimethylsilylene bis (2-methyl-4-isoproline
Pyr-7-methyl-1-indenyl) zirconium dichloride,
Dimethyl silylene bis (2-methyl-4,7-diisopropyl-
1-indenyl) zirconium dichloride, dimethyl silyl
Bis (2-phenyl-4-isopropyl-7-methyl-1-yne
Denyl) zirconium dichloride, diphenyl silylene bi
Su (2,4,7-trimethyl-1-indenyl) zirconium
Chloride, diphenylbis (2-isopropyl-4,7-dimethyl)
Ru-1-indenyl) zirconium dichloride, diphenyl
Silylene bis (2-phenyl-4,7-dimethyl-1-indeni
Ru) Zirconium dichloride, diphenylsilylene bis
(2-methyl-4-isopropyl-7-methyl-1-indenyl)
Zirconium dichloride, diphenylsilylene bis (2-me
Chill-4,7-diisopropyl-1-indenyl) zirconium
Dichloride, diphenylsilylene bis (2-phenyl-4-yl
Sopropyl-7-methyl-1-indenyl) zirconium di-salt
Compound, methylphenylsilylene bis (2,4,7-trimethyl
-1-Indenyl) zirconium dichloride, ethylene bis
(2,5,6-Trimethyl-1-indenyl) zirconium di-salt
Compound, dimethylsilylene bis (2,5,6-trimethyl-1-yl
Ndenyl) zirconium dichloride, diphenylsilylene
Bis (2,5,6-trimethyl-1-indenyl) zirconium
Dichloride, methylphenylsilylene bis (2,5,6-trimethyl
Cyl-1-indenyl) zirconium dichloride, ethylene
Bis (2,4,5,6,7-pentamethyl-1-indenyl) zirco
Dichloride, dimethylsilylene bis (2,4,5,6,7-pe
N-methyl-1-indenyl) zirconium dichloride, di
Phenylsilylene bis (2,4,5,6,7-pentamethyl-1-y
Ndenyl) zirconium dichloride, methylphenylsilyl
Lenbis (2,4,5,6,7-pentamethyl-1-indenyl) di
Ruconium dichloride, ethylene bis (2-methyl-5-t-bu
Cyl-1-indenyl) zirconium dichloride, dimethyl
Silylene bis (2-methyl-5-t-butyl-1-indenyl) di
Ruconium dichloride, diphenylsilylene bis (2-methyl
Ru-5-t-butyl-1-indenyl) zirconium dichloride,
Methylphenylsilylene bis (2-methyl-5-t-butyl-1-
Indenyl) zirconium dichloride, ethylene bis (2-
Methyl-6-t-butyl-1-indenyl) zirconium dichloride
Dimethylsilylene bis (2-methyl-6-t-butyl-1-y)
Ndenyl) zirconium dichloride, diphenylsilylene
Bis (2-methyl-6-t-butyl-1-indenyl) zirconium
Dichloride, methylphenylsilylene bis (2-methyl-6
-t-Butyl-1-indenyl) zirconium dichloride, ethi
Lenbis (2-methyl-7-t-butyl-1-indenyl) zirco
Dichloride, dimethylsilylene bis (2-methyl-7-t
-Butyl-1-indenyl) zirconium dichloride, diphe
Nylsilylene bis (2-methyl-7-t-butyl-1-indeni
Le) Zirconium dichloride, methylphenyl silylene bi
Sus (2-methyl-7-t-butyl-1-indenyl) zirconium
Dichloride, ethylene bis (2-methyl-5,6-di-t-butyl-1)
-Indenyl) zirconium dichloride, dimethylsilyl
Bis (2-methyl-5,6-di-t-butyl-1-indenyl) di
Ruconium dichloride, diphenylsilylene bis (2-methyl
-5,6-di-t-butyl-1-indenyl) zirconium di-salt
Compound, methylphenylsilylenebis (2-methyl-5,6-di-
t-Butyl-1-indenyl) zirconium dichloride, ethi
Lenbis (2-methyl-5-trimethylsilyl-1-indeni
Ru) zirconium dichloride, dimethylsilylene bis (2-
Methyl-5-trimethylsilyl-1-indenyl) zirconium
Dichloride, diphenylsilylene bis (2-methyl-5-to
Limethylsilyl-1-indenyl) zirconium dichloride
, Methylphenylsilylene bis (2-methyl-5-trimethyl
Tylsilyl-1-indenyl) zirconium dichloride, d
Tylene bis (2-methyl-6-trimethylsilyl-1-indeni
Ru) zirconium dichloride, dimethylsilylene bis (2-
Methyl-6-trimethylsilyl-1-indenyl) zirconium
Dichloride, diphenylsilylene bis (2-methyl-6-to
Limethylsilyl-1-indenyl) zirconium dichloride
Substance, methylphenylsilylenebis (2-methyl-6-trimethyl)
Tylsilyl-1-indenyl) zirconium dichloride, d
Tylene bis (2-methyl-5,6-bistrimethylsilyl-1-i
Ndenyl) zirconium dichloride, dimethyl silylene bi
Su (2-methyl-5,6-bistrimethylsilyl-1-indeni
Ru) Zirconium dichloride, diphenylsilylene bis
(2-methyl-5,6-bistrimethylsilyl-1-indenyl)
Zirconium dichloride, methylphenylsilylene bis
(2-methyl-5,6-bistrimethylsilyl-1-indenyl)
Zirconium dichloride, ethylene bis (2-methyl-5,6-
Bistriphenylsilyl-1-indenyl) zirconium
Dichloride, dimethylsilylene bis (2-methyl-5,6-bis
Triphenylsilyl-1-indenyl) zirconium di-salt
Compound, ethylene bis (2-methyl-4-methoxy-1-indeni
Ru) zirconium dichloride, dimethylsilylene bis (2-
Methyl-4-methoxy-1-indenyl) zirconium dichloride
Substance, diphenylsilylene bis (2-methyl-4-methoxy-1-
Indenyl) zirconium dichloride, methylphenyloxy
Rylene bis (2-methyl-4-methoxy-1-indenyl) zyl
Conium dichloride, ethylene bis (2-methyl-5-methoxy)
Si-1-indenyl) zirconium dichloride, dimethyl
Rylene bis (2-methyl-5-methoxy-1-indenyl) dil
Conium dichloride, diphenylsilylene bis (2-methyl
-5-Methoxy-1-indenyl) zirconium dichloride,
Tylphenylsilylene bis (2-methyl-5-methoxy-1-y
Ndenyl) zirconium dichloride, ethylene bis (2-me
Cyl-6-methoxy-1-indenyl) zirconium dichloride
Dimethylsilylene bis (2-methyl-6-methoxy-1-yl)
Ndenyl) zirconium dichloride, diphenylsilylene
Bis (2-methyl-6-methoxy-1-indenyl) zirconium
Dichloride, methylphenylsilylene bis (2-methyl-6
-Methoxy-1-indenyl) zirconium dichloride, ethi
Lenbis (2-methyl-7-methoxy-1-indenyl) zirco
Dichloride, dimethylsilylene bis (2-methyl-7-
Methoxy-1-indenyl) zirconium dichloride, dif
Phenyl silylene bis (2-methyl-7-methoxy-1-indeni
Le) Zirconium dichloride, methylphenyl silylene bi
Su (2-methyl-7-methoxy-1-indenyl) zirconium
Dichloride, ethylenebis (2-methyl-4,7-dimethoxy-1-)
Indenyl) zirconium dichloride, dimethyl silylene
Bis (2-methyl-4,7-dimethoxy-1-indenyl) zirco
Dichloride, diphenylsilylene bis (2-methyl-
4,7-Dimethoxy-1-indenyl) zirconium dichloride
, Methylphenylsilylene bis (2-methyl-4,7-dimethyl
Toxy-1-indenyl) zirconium dichloride, ethyl
Bis (2-methyl-5,6-dimethoxy-1-indenyl) dil
Conium dichloride, dimethylsilylene bis (2-methyl-
5,6-dimethoxy-1-indenyl) zirconium dichloride
, Diphenylsilylenebis (2-methyl-5,6-dimethoxy)
Ci-1-indenyl) zirconium dichloride, methylphen
Nylsilylene bis (2-methyl-5,6-dimethoxy-1-indene
Nyl) zirconium dichloride, ethylenebis (2-methyl)
-4,5,6,7-Tetramethoxy-1-indenyl) zirconium
Dichloride, dimethylsilylene bis (2-methyl-4,5,6,7-
Tetramethoxy-1-indenyl) zirconium dichloride
Diphenylsilylene bis (2-methyl-4,5,6,7-teto
Lamethoxy-1-indenyl) zirconium dichloride,
Tylphenylsilylenebis (2-methyl-4,5,6,7-tetra
Methoxy-1-indenyl) zirconium dichloride, ethi
Lenbis (2-trimethylsilyl-1-indenyl) zirco
Aluminum dihydride, ethylenebis (2-trimethylsilyl)
-1-Indenyl) zirconium difluoride, ethylene bis
(2-Trimethylsilyl-1-indenyl) zirconium di
Bromide, ethylene bis (2-trimethylsilyl-1-indene
Nyl) zirconium diiodide, ethylene bis (2-trimethyl)
Cylsilyl-1-indenyl) zirconium dimethoxy
De, ethylene bis (2-trimethylsilyl-1-indeni
Ru) Zirconium di-n-butoxide, ethylene bis (2-
Trimethylsilyl-1-indenyl) zirconium diphe
Noxide, ethylene bis (2-trimethylsilyl-1-yne
Denyl) zirconium di-t-butoxide, ethylene bis
(2-Trimethylsilyl-1-indenyl) zirconium di
Methyl, ethylene bis (2-trimethylsilyl-1-indene
Nyl) zirconium dineopentyl, ethylene bis (2-
Trimethylsilyl-1-indenyl) zirconium ditri
Methylsilylmethyl, ethylenebis (2-trimethylsilyl)
Ru-1-indenyl) zirconium ditosylate, ethyl
Bis (2-trimethylsilyl-1-indenyl) zirconi
Ummedimesylate, ethylenebis (2-trimethylsilyl)
-1-Indenyl) zirconium di (mesityl sulphona)
), Ethylenebis (2-trimethylsilyl-1-indene)
Nil) zirconium di (phenyl sulfonate), d
Tylene bis (2-trimethylsilyl-1-indenyl) zyl
Konium di (benzyl sulfonate), ethylene bis
(2-Trimethylsilyl-1-indenyl) zirconium bi
Su (trifluoromethanesulfonate), ethylene vinyl
Su (2-trimethylsilyl-1-indenyl) zirconium
Monochlorid monohydridoethylene bis (2-trimethylsilyl-1-indenyl) di
Ruconium monochloride monofluoride, ethylenebis (2-
Trimethylsilyl-1-indenyl) zirconium monoc
Lolid monobromide, ethylenebis (2-trimethylsilyl)
-1-Indenyl) zirconium monochloride monoiodination
Product, ethylene bis (2-trimethylsilyl-1-indeni
Le) Zirconium monochloride monomethoxide, ethyl
Bis (2-trimethylsilyl-1-indenyl) zirconi
Ummonochlorid mono-n-butoxide, ethylene bis (2
-Trimethylsilyl-1-indenyl) zirconium monoc
Lolid monophenoxide, ethylenebis (2-trimethyl
Silyl-1-indenyl) zirconium monochloride mono-
t-butoxide, ethylenebis (2-trimethylsilyl-1-
Indenyl) zirconium monochloride monomethyl, d
Tylene bis (2-trimethylsilyl-1-indenyl) zyl
Conium monochloride mononeopentyl, ethylene bis
(2-Trimethylsilyl-1-indenyl) zirconium
Nochloride monotrimethylsilylmethyl, ethylenebis
(2-Trimethylsilyl-1-indenyl) zirconium
Nochloride monotosylate, ethylene bis (2-trimethyl
Rusilyl-1-indenyl) zirconium monochromido
Nomesylate, ethylene bis (2-trimethylsilyl-1-
Indenyl) zirconium monochloride mono (mesityl)
Sulfonate), ethylenebis (2-trimethylsilyl)
-1-Indenyl) zirconium monochloride mono (fe
Nyl sulfonate), ethylene bis (2-trimethylsilane)
Ryl-1-indenyl) zirconium monochloride mono
(Benzyl sulfonate), ethylene bis (2-trimethyl)
Cylsilyl-1-indenyl) zirconium monochloride
Mono (trifluoromethanesulfonate), ethylene
Bis (2-trimethylsilyl-1-indenyl) zirconium
Mumonohydrido monofluoride, ethylene bis (2-trimethyl
Rusilyl-1-indenyl) zirconium monohydridomo
No chloride, ethylene bis (2-trimethylsilyl-1-yne
Denyl) zirconium monohydride monobromide, ethyl
Bis (2-trimethylsilyl-1-indenyl) zirconi
Ummonohydridomonoiodide, ethylene bis (2-trimethyl
Cylsilyl-1-indenyl) zirconium monohydride
Monomethoxide, ethylenebis (2-trimethylsilyl-1)
-Indenyl) zirconium monohydrido mono n-butoki
Sid, ethylene bis (2-trimethylsilyl-1-indeni
Le) Zirconium monohydride monophenoxide, ethi
Lenbis (2-trimethylsilyl-1-indenyl) zirco
N-monohydrido mono-t-butoxide, ethylene bis
(2-Trimethylsilyl-1-indenyl) zirconium
Nohydridomonomethyl, ethylenebis (2-trimethylsilane
Ryl-1-indenyl) zirconium monohydride monone
Opentyl, ethylenebis (2-trimethylsilyl-1-y)
Ndenyl) zirconium monohydride monotrimethyloxy
Rylmethyl, ethylenebis (2-trimethylsilyl-1-y)
Ndenyl) zirconium monohydride monotosylate,
Ethylene bis (2-trimethylsilyl-1-indenyl) di
Ruconium monohydride monomesylate, ethylene bis
(2-Trimethylsilyl-1-indenyl) zirconium
Nohydrido mono (mesityl sulfonate), ethylene
Bis (2-trimethylsilyl-1-indenyl) zirconium
Mumono hydrido mono (phenyl sulfonate), ethi
Lenbis (2-trimethylsilyl-1-indenyl) zirco
Nium monohydrido mono (benzyl sulfonate),
Ethylene bis (1-indenyl) zirconium monohydroxide
Domono (trifluoromethanesulfonate), ethyl
Bis (2-trimethylsilyl-1-indenyl) zirconi
Umium dichloride, dimethylsilylene bis (2-trimethylsilane
Ryl-1-indenyl) zirconium dichloride, dipheni
Lucillene bis (2-trimethylsilyl-1-indenyl)
Zirconium dichloride, methylphenylsilylene bis
(2-Trimethylsilyl-1-indenyl) zirconium di
Chloride, ethylene bis (4,5,6,7-tetrahydroindeni
Ru) zirconium dichloride, ethylene bis (2-methyl-
4,5,6,7-Tetrahydroindenyl) zirconium dichloride
Dimethylsilylene bis (4,5,6,7-tetrahydroin
Denyl) zirconium dichloride, dimethylsilylene bis
(2-Methyl-4,5,6,7-tetrahydroindenyl) zirco
Dichloride, dimethylsilylene bis (2-methyl-1-
Cyclopentadienyl) zirconium dichloride, dimethy
Lucillene bis (3-methyl-1-cyclopentadienyl)
Zirconium dichloride, dimethylsilylene bis (4-methyl
Ru-1-cyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (5-methyl-1-cyclopentadiene
Nyl) zirconium dichloride, dimethyl silylene bis
(2,4-dimethyl-1-cyclopentadienyl) zirconium
Dichloride, dimethylsilylene bis (2,5-dimethyl-1-
Cyclopentadienyl) zirconium dichloride, dimethy
Lucillene bis (2,4,5-trimethyl-1-cyclopentadi
(Enyl) zirconium dichloride,

[0032]

[Chemical 3]

[0033]

[Chemical 4]

[0034]

[Chemical 5]

[0035]

[Chemical 6]

In the zirconium compound as described above, a compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum or chromium can be used.

In the present invention, as the transition metal compound (A), a zirconocene compound having a central metal atom of zirconium and having a ligand containing at least two indenyl skeletons is preferably used.

These compounds may be used alone,
You may use it in combination of 2 or more type. It may be diluted with a hydrocarbon or a halogenated hydrocarbon before use. The transition metal compound (A) as described above can also be used by supporting it on a fine particle carrier as described later.

The above-mentioned transition metal compound (A), which is usually used in a racemic form as a catalyst component for olefin polymerization, contains R
Mold or S shape can also be used. (B) Catalyst component (B-1) or (B-2) In the present invention, when a prepolymerization catalyst is prepared, the transition metal compound (A) as described above and the following catalyst component (B) ( A compound that reacts with B-1) an organoaluminum oxy compound or (B-2) a transition metal compound (A) to form an ion pair, or a combination thereof is used.

(B-1) Organoaluminum Oxy Compound

The (B-1) organoaluminum oxy compound used in the present invention (hereinafter sometimes referred to as “component (B-1)”) may be a conventionally known aluminoxane. A benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 may be used.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted. (2) A method in which water, ice, or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organic metal component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane and then redissolved in the solvent.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butyl. Aluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum chloride, diethylaluminum Chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, etc. Alkylaluminum halides; diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are particularly preferable.
Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following general formula [II] can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z ... [II] (In the formula, x, y, and z are positive numbers, and z ≧ 2x). Such organoaluminum compounds may be used alone or in combination.

As the solvent used in the aluminoxane solution, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. , Cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides Among these, hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

The above-mentioned (B-1) organoaluminum oxy compounds may be used in combination of two or more kinds.

(B-2) Compound that forms an ion pair (B-2) The transition metal compound (A) used in the present invention
A compound that reacts with an ion pair to form an ion pair (hereinafter referred to as “component (B-
2) ”may be described. ), The special table 1-5
No. 01950, Japanese Patent Publication No. 1-502036, Japanese Patent Laid-Open No. 3-179005, Japanese Patent Laid-Open No. 3-179006.
Japanese Patent Laid-Open No. 3-207703 and Japanese Patent Laid-Open No. 3-2
Examples thereof include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A-07704, US-547718 and the like.

As the Lewis acid, Mg-containing Lewis acid, Al
Examples thereof include a Lewis acid containing B and a Lewis acid containing B, and among these, the Lewis acid containing B is preferable. Specific examples of the Lewis acid containing a boron atom include compounds represented by the following general formula.

BR ⁴ R ⁵ R ^{6 In the} formula, R ⁴ , R ⁵ and R ⁶ are each independently a phenyl group which may have a substituent such as a fluorine atom, a methyl group and a trifluoromethyl group. , Or a fluorine atom.

Specific examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron and tris (4-fluoro). Methylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron and the like can be mentioned. Of these, tris (pentafluorophenyl) boron is particularly preferable.

The ionic compound used in the present invention is a salt composed of a cationic compound and an anionic compound. The anion has a function of cationizing the transition metal compound (A) by reacting with the transition metal compound (A) and stabilizing the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and those which are relatively bulky and stabilize the transition metal cation species are preferable. Examples of the cation include a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, it includes a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, and a ferrocenium cation.

Of these, an ionic compound containing a boron compound as an anion is preferable, and specifically,
Examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron,
Trimethylammonium tetra (p-tolyl) boron, Trimethylammonium tetra (o-tolyl) boron, Tributylammonium tetra (pentafluorophenyl)
Boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron,
Examples thereof include tri (n-butyl) ammonium tetra (o-tolyl) boron and tri (n-butyl) ammonium tetra (4-fluorophenyl) boron. Examples of N, N-dialkylanilinium salts include N, N -Dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron and the like, dialkylammonium salts Are, for example, di (n-propyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron, etc., triarylphosphonium salts such as triphenylphosphonium tetra (phenyl) boron, Tri (methylphenyl) phosphonium tetra (phenyl) pho Element, such as tri (dimethylphenyl) phosphonium tetra (phenyl) boron and the like.

In the present invention, as an ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluoro) Mention may also be made of (phenyl) borate.

The following compounds can also be exemplified.
(In the ionic compounds listed below, the counter ion is, but not limited to, tri (n-butyl) ammonium.) Anion salts such as bis [tri (n-butyl) ammonium] nonaborate and bis [tri] (N-Butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl)]
Ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium-1-carbadecaborate, tri (n-butyl) ammonium-1-carbaundecaborate , Tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, etc .; Examples thereof include borane compounds and carborane compounds. These compounds are used as Lewis acids and ionic compounds.

Borane and carborane complex compounds and salts of carborane anions, such as decaborane (14),
7,8-Dicarbaundecaborane (13), 2,7-Dicarbaundecaborane (13), Undecahydride-7,8-Dimethyl-7,8-dicarbaundodecaborane, Dodecahydride-11-Methyl- 2,7-Dicarbaundecaborane, tri (n
-Butyl) ammonium 6-carbadecaborate (1
4), tri (n-butyl) ammonium 6-carbadecaborate (12), tri (n-butyl) ammonium 7-carbaundecaborate (13), tri (n-butyl) ammonium 7,8-dicarbaundeca Borate (12), bird (n-
Butyl) ammonium 2,9-dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl 7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride 8-ethyl -7,9-Dicarbaundecaborate, tri (n-butyl)
Ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammoniumun Deca hydride-9-
Trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6
-Dibromo-7-carbaundecaborate, etc .; carborane and salts of carborane, such as 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodeca Hydride-1-Phenyl-1,3-dicarbanonaborane, Dodeca Hydride-1-
Further, the following compounds can be exemplified, such as methyl-1,3-dicarbanonaborane and undecahydride-1,3-dimethyl-1,3-dicarbanonaborane. (Note that the counter ion in the ionic compounds listed below is, but not limited to, tri (n-butyl) ammonium.) A salt of a metal carborane and a metal borane anion such as tri (n-butyl) ammonium bis (nona). Hydride-
1,3-Dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) ferrate (ferrate) (III), tri (n-) Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8- Dicarbaundecaborate) cubrate (cuprate) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (metal salt) (III), tri (n-) Butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8- Dicarbaundecaborate) Chromate (Chromate) (II
I), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarbaundecaborate)
Cobaltate (III), tri (n-butyl) ammonium bis (dodecahydride dicarbadodecaborate) Cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) nickelate (III), Tris [Tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) Manganate (IV), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) Cobaltate (II
I), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) nickelate (IV) and the like.

The compound (B-2) which reacts with the above transition metal compound (A) to form an ion pair may be used in combination of two or more kinds. (C) Organoaluminum Compound In the present invention, when the prepolymerization catalyst is prepared, along with the catalyst components (A) and (B) as described above, (C) an organoaluminum compound (hereinafter referred to as “component (C)” Is used.) As such (C) organoaluminum compound, an organoaluminum compound represented by the following general formula [III] can be exemplified.

R ⁷ _n AlX _3-n ... [III] In the formula, R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen atom or a hydrogen atom, and n is 1 to 3.

The hydrocarbon group having 1 to 12 carbon atoms is, for example, an alkyl group, a cycloalkyl group or an aryl group. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an isobutyl group. , Pentyl group,
Hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Such an organoaluminum compound (C)
Specifically, the following compounds may be mentioned. Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum; alkenyl aluminum such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride. , Diisobutylaluminum chloride, dimethylaluminum bromide and other dialkylaluminum halides; methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide and other alkylaluminum sesquihalides; methyl Alkylaluminum dihalides such as aluminum aluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

As the organoaluminum compound (C), a compound represented by the following general formula [IV] can also be used. R ⁷ _n AlL _3-n ... [IV] In the formula, R ⁷ represents a hydrocarbon group similar to the above, and L represents-
OR ⁸ group, -OSiR ⁹ ₃ group, -OAlR ¹⁰ ₂ group, -NR ¹¹ ₂
A group, —SiR ¹² ₃ group or —N (R ¹³ ) AlR ¹⁴ ₂ group,
n is 1 to 2, R ⁸ , R ⁹ , R ¹⁰ and R ¹⁴ represent a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ¹¹ represents a hydrogen atom, methyl Group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and R ¹² and R ¹³
Represents a methyl group, an ethyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds. (1) A compound represented by R ⁷ _n Al (OR ⁸ ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (2) R ⁷ _n Al (OSiR ⁹ ₃ ) ₃ a compound represented by _-n , such as Et ₂ Al (OSi Me ₃ ), (iso-Bu) ₂ Al (OSiM
e ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc .; (3) A compound represented by R ⁷ _n Al (OAlR ¹⁰ ₂ ) _3-n , for example, Et ₂ AlOAiLet ₂ , (iso-Bu) ₂ AlOAl (iso-
Bu) _{2, ^{etc.; (4) R 7 n Al}} (NR 11 2) a compound represented by _3-n, e.g., _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2 AlNHEt
, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiMe ₃ ) ₂
(5) A compound represented by R ⁷ _n Al (SiR ¹² ₃ ) _3-n , such as (iso-Bu) ₂ AlSi Me ₃ ; (6) R ⁷ _n Al (N (R ¹³ ) AlR ¹⁴ ₂ ) _3-n , for example Et ₂ AlN (Me) AlEt ₂ , (iso-Bu) ₂ Al
N (Et) Al (iso-Bu) _{2 and the} like.

[0064] Among the above general formula [III] and an organoaluminum compound represented by the [IV], formula R ⁷ ₃ Al,
The compounds represented by R ⁷ _n Al (OR ⁸ ) _3-n and R ⁷ _n Al (OAlR ¹⁰ ₂ ) _3-n are preferable, and the compound in which R is an isoalkyl group and n = 2 is particularly preferable.

Other Components In the present invention, when the prepolymerized catalyst is prepared, the fine particle carrier (D) may be used together with the above catalyst components (A), (B) and (C).

The particulate carrier (D) used in the present invention is an inorganic or organic compound having a particle size of 10 to 10.
It is a solid in the form of granules or fine particles of 300 μm, preferably 20 to 200 μm.

Among these, porous oxide is used as the inorganic carrier.
Preferably, specifically, SiO₂, Al₂O₃, MgO, Z
rO₂, TiO₂, B₂O₃, CaO, ZnO, BaO, T
hO ₂Or a mixture thereof, such as SiO₂-
MgO, SiO₂-Al₂O₃, SiO₂-TiO₂, SiO₂
-V₂O_Five, SiO₂-Cr₂O₃, SiO₂-TiO₂-MgO
And the like. Among these SiO₂Oh
And Al₂O₃At least one selected from the group consisting of
Those having a component as a main component are preferable.

The above inorganic oxide contains a small amount of Na ₂ C.
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O, Li ₂ O and other carbonates, sulfates, nitrates and oxides may be contained.

The properties of such a fine particle carrier vary depending on the type and production method, but the fine particle carrier preferably used in the present invention has a specific surface area of 50 to 1000 m ² /
g, preferably 100 to 700 m ² / g, and the pore volume is desirably 0.3 to 2.5 cm ² / g. The fine particle carrier is used by firing at a temperature of 100 to 1000 ° C., preferably 150 to 700 ° C., if necessary.

Further, examples of the fine particle carrier which can be used in the present invention include granular or fine particle solids of an organic compound having a particle size of 10 to 300 μm. These organic compounds include ethylene, propylene, 1-butene, 4-methyl-1-pentene and the like having 2 to 2 carbon atoms.
Produced mainly from 14 α-olefins (co)
Examples thereof include polymers, and polymers or copolymers containing vinylcyclohexane or styrene as a main component.

Such a fine particle carrier may contain surface hydroxyl groups or water. In that case, it is desirable that the amount of surface hydroxyl groups is 1.0% by weight or more, preferably 1.5 to 4.0% by weight, particularly preferably 2.0 to 3.5% by weight, and water is 1.0% by weight. 0% by weight or more, preferably 1.2 to
The amount is preferably 20% by weight, more preferably 1.4 to 15% by weight. The water contained in the fine particle carrier means water adsorbed on the surface of the fine particle carrier.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) of the particulate carrier are determined as follows. [Amount of adsorbed water] 4 at normal temperature and nitrogen flow at a temperature of 200 ° C
The weight loss when dried for an hour is defined as the amount of adsorbed water. [Amount of surface hydroxyl groups] X (g) is the weight of the carrier obtained by drying at a temperature of 200 ° C under normal pressure and nitrogen flow for 4 hours.
Furthermore, the weight of the calcined product obtained by calcining the carrier at 1000 ° C. for 20 hours in which the surface hydroxyl groups have disappeared is Y (g),
Calculate by the following formula.

Surface hydroxyl group amount (wt%) = {(X−Y) / X} × 100 When such a specific amount of adsorbed water and a fine particle carrier having a surface hydroxyl group are used, high polymerization activity and excellent particle properties are obtained. It is possible to obtain an olefin polymerization catalyst capable of producing an olefin polymer.

Further, in the present invention, water may be used as the catalyst component (E) when preparing the prepolymerized catalyst. Water as the (E) catalyst component used in the present invention is
Water or components dissolved in a polymerization solvent as described below
Examples include adsorbed water and water of crystallization contained in the compound or salt used in the production of (B-1).

Preliminary Polymerization Catalyst The preliminarily polymerized catalyst [I] according to the present invention comprises the above-mentioned catalyst components (A) and (B) and, if necessary (C), and optionally (D) and (E). ) Is preliminarily polymerized with a cycloolefin having a double bond in the ring as described below.

When the prepolymerization catalyst [I] is prepared, the catalyst components as described above may be contacted in the polymerization vessel, or the previously contacted catalyst components may be added to the polymerization vessel. For example, they can be contacted as follows. (1) Catalyst component (A), component (B-1) (or component (B-
2)) and optionally (E) water as a catalyst component,
Contact is made in an inert hydrocarbon solvent or in a prepolymerized monomer solvent.

At this time, the order of contacting each component is arbitrary, but the component (B-1) (or the component (B-2)) and the (E) water are brought into contact with each other, and then the component (A) is brought into contact therewith. It is preferable. (2) Catalyst component (A), component (B-1) (or component (B-
2)), component (C) and optionally (E) water as catalyst component are contacted in an inert hydrocarbon solvent or in a prepolymerized monomer solvent.

In this case, the order of contacting each component is arbitrary, but when the component (B-1) is used, the component (B-1) and the component (C) are used.
It is preferable to contact with and then contact the component (A).

When using the component (B-2), the component (C)
It is preferable that the component (A) and the component (A) are brought into contact with each other, and then the component (B-2) is brought into contact therewith. (3) Catalyst component (A), component (B-1) (or component (B-
2)), particulate carrier (D), and optionally water (E)
And are contacted in any order in an inert hydrocarbon solvent or prepolymerized monomer medium. By using the particulate carrier (D) in this way, a solid catalyst component is formed. More specifically, the particulate carrier (D) is contacted with the component (B-1) (or the component (B-2)), then the component (A) is contacted, and further water (E) is added if desired. Contact or ingredients (B
-1) (or component (B-2)) and component (A) are contacted with the fine particle carrier (D), and then water (E) is optionally contacted, or fine particle carrier Carrier (D)
It is preferable that the component (B-1) (or the component (B-2)) and the water are brought into contact with each other, and then the component (A) is brought into contact therewith.

It is desirable that the above contact be performed with stirring. A component (C) can be further added to the above contact, and for example, a solid catalyst component obtained by supporting a transition metal compound (A) and a catalyst component (B) on a particulate carrier (D). And the organoaluminum compound (C) may be brought into contact with each other.

Examples of the inert hydrocarbon solvent used in the contact include propane, butane, pentane,
Aliphatic hydrocarbons such as hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Examples thereof include halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, or a mixture thereof.

The method of contacting each catalyst component is not limited to the above example.

When the above components are brought into contact with each other, the components
The concentration of (A) is usually about 10^-8-10 ^-1Mol / liter
(Solvent), preferably 10^-7~ 5 x 10^-2Mol / lit
Range (solvent).

The atomic ratio of the aluminum in component (B-1) to the transition metal in component (A) (Al / transition metal) is
It is usually 10 to 10,000, preferably 20 to 5,000, and when the component (B-2) is used, the molar ratio of the component (A) and the component (B-2) (component (A) / component (B-2)). ) Is usually 0.01-
10, preferably in the range of 0.1 to 5, and the component (A)
The concentration of about 10 ^-8 to 10 ^-1 mol / liter (solvent),
Preferably 10 ^{−7 to} 5 × 10 ⁻² mol / liter (solvent)
Is the range.

When the component (C) is used, it is usually used in an amount of not more than 500 mol, preferably 5 to 200 mol, per gram atom of the transition metal atom in the component (A). Further, the aluminum atom (Al _C ) in the component ( _C ) and the aluminum atom (A in the component (B-1)
l _B-1) and the atomic ratio of _{(Al C / Al B-1} ) is usually 0.02
-20, preferably 0.2-10.

When water (E) is used as the catalyst component, the aluminum atom (Al _B-1 ) in the component (B-1) is used.
And the molar ratio of water (H ₂ O) (Al _B-1 / H ₂ O) is usually 0.5 to 50, preferably 1 to 40.

When the fine particle carrier (D) is used, the component (A) is usually 10 per 1 g of the fine particle carrier.
^{-6 to} 5 × 10 ^-3 mol, preferably 3 × 10 ^-6 to 10 ^-3 mol, and the concentration of the component (A) is about 5 × 10 ^-6.
~ 2 × 10 ^-2 mol / liter (solvent), preferably 10
It is in the range of ^-5 to 10 ^-2 mol / liter (solvent).

The contact temperature for contacting the above components is
Usually, it is -50 to 150 ° C, preferably -20 to 120 ° C, and the contact time is 1 to 1000 minutes, preferably 5 to 6 minutes.
00 minutes. Further, the contact temperature may be changed at the time of contact.

Specific examples of the cycloolefin having a double bond in the ring used for the prepolymerization include 3 to 10 carbon atoms.
20 cycloolefins, more specifically, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and the like, and cycloolefins having 1 to 6 hydrocarbon residues having 1 to 10 carbon atoms bonded thereto as substituents. , For example methylcyclopropene,
Methylcyclobutene, ethylcyclobutene, dimethylcyclobutene, methyl-ethylcyclobutene, methylcyclopentene, ethylcyclopentene, methylcyclohexene, ethylcyclohexene, butylcycloheptene and the like can be mentioned. You may use these in combination of 2 or more types.

Each of the above catalyst components (A) and (B) and, if necessary, (C) and, if necessary, (D),
When the cycloolefin having a double bond in the ring is prepolymerized with (E), the component (A) is usually 10 ⁻⁸ to
10 ^-1 mol / liter (polymerization volume), preferably 10 ^-7
Used in an amount of -10 ^-2 mol / liter (polymerization volume).

The components (B-1), (B-2), (C), (D),
(E) is used in an amount as shown for the above-mentioned contact with the component (A). For the prepolymerization, the same inert hydrocarbon solvent as that used for contacting the catalyst components can be used.

The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 50 ° C, and the prepolymerization time is 0.5 to 10 ° C.
It is desirable that the time is 0 hour, preferably about 1 to 50 hours.

The amount of prepolymerization is not particularly limited, but is from 1 to 100,000 per 1 g of transition metal atom in the catalyst component (A).
g preferably 5 to 10000 g, more preferably 10 to
It is desirable that the amount is 1000 g, particularly preferably 10 to 500 g.

The prepolymerization amount is 10 to 10000 ppm, preferably 50 to 1000 ppm, and particularly preferably 100 to 500 pp relative to the amount of the α-olefin described below.
is the proportion of m.

When the α-olefin is polymerized using the prepolymerization catalyst according to the present invention as described above, an olefin polymer having a high melting point and a high molecular weight can be obtained. Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention comprises the above-mentioned prepolymerization catalyst [I] and, if necessary, [II] catalyst component (B) (B-1) organoaluminum oxy compound. And (B-2) at least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form an ion pair, and / or [III] catalyst component (C)
And the organoaluminum compound shown as.

In preparing the olefin polymerization catalyst, the catalyst component (B-1) is used in an amount of 0 to 10000 mol, preferably 10 to 1 mol of the transition metal atom in the prepolymerization catalyst.
In an amount of 5000 mol, (B-2) is 0 to 10 mol, preferably 0.1 to 5 mol, and the catalyst component (C) is based on 1 mol of the transition metal atom in the prepolymerization catalyst. It is optionally used in an amount of 0 to 500 mol, preferably 5 to 20 mol.

Olefin Polymerization Method Next, the olefin polymerization method according to the present invention will be described. In the present invention, α-olefin is polymerized in the presence of an olefin polymerization catalyst containing the above-mentioned prepolymerization catalyst [I].

FIG. 1 shows the olefin polymerization method according to the present invention.
Shown in. The polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method.

In the liquid phase polymerization method, the same inert hydrocarbon solvent as used for preparing the catalyst can be used, and α-
The olefin itself can also be used as a solvent. α-
In carrying out the main polymerization of the olefin, the prepolymerization catalyst has a concentration of transition metal atoms derived from the component (A),
It is desirable to use it in an amount of usually 10 ^-12 to 10 ^-4 g atom / liter (polymerization volume), preferably 10 ^-10 to 10 ^-6 g atom / liter.

At this time, when the organoaluminum oxy compound (component (B-1)) supported on the carrier is used, an unsupported organoaluminum oxy compound may be added.

The α-olefin polymerized in the present invention is an α-olefin having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene. , 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.

These may be used in combination of two or more kinds. Further, styrene, vinylcyclohexane, diene and the like may be copolymerized with these α-olefins.

In the liquid phase polymerization method, the same inert hydrocarbon solvent as used for contacting the catalyst components can be used,
The α-olefin itself can also be used as a solvent.
When carrying out the slurry polymerization method, the polymerization temperature of the α-olefin is usually −50 to 100 ° C., preferably 0 to 90.
It is preferably in the range of 0 ° C, and when carrying out the liquid phase polymerization method, it is usually 0 to 250 ° C, preferably 20 to 200 ° C.
It is desirable that the range is. Further, when carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 100 ° C. The polymerization pressure is usually from atmospheric pressure to 100 kg / cm ² , preferably from atmospheric pressure to 50 kg / cm ² , and the polymerization reaction may be carried out by any of batch, semi-continuous and continuous methods. You can It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. In the present invention,
In the main polymerization of the α-olefin, the above-mentioned prepolymer contained in the obtained olefin polymer is 10 to 10,000.
ppm preferably 50 to 1000 ppm, particularly preferably 10
It is carried out so as to be contained in an amount of 0 to 500 ppm.

[0105]

By using the specific prepolymerization catalyst according to the present invention, it is possible to produce an olefin polymer having a high melting point and excellent heat resistance and rigidity.

[0106]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

In the present invention, the intrinsic viscosity [η] and the melting point (Tm) are measured as follows. [Intrinsic viscosity [η]] measured in decalin at 135 ° C, dl
/ G.

[Melting point (Tm)] About 5 mg of a sample was packed in an aluminum pan and heated to 200 ° C. at 10 ° C./min to 200 ° C.
After 5 minutes of holding, the temperature was lowered to room temperature at 20 ° C./min, and then it was determined from the endothermic curve when the temperature was raised at 10 ° C./min. The measurement was performed using a Perkin Elmer DSC-7 type measuring machine.

[0109]

In Example 1 equipped with a stirrer glass flask of prepolymerization 400 ml, purified decane 200ml and cyclopentene 50ml was added, further 2 mmol of ethylene bis-indenyl zirconium dichloride 0.02 mmol of methyl aluminoxane with aluminum atom in terms Toluene solution containing 10 ml
Was added and the mixture was stirred at 30 ° C. for 4 hours.

Then, the solid part (preliminary polymerization catalyst (i)) was separated from the above reaction solution and suspended in decane. The amount of preliminary polymerization was 248 g / g-Zr.

Main Polymerization In a 2-liter autoclave, 750 ml of hexane was added.
Then, 0.175 mmol of methylaluminoxane in terms of aluminum atom and 0.0005 mmol of zirconium in the prepolymerization catalyst (i) (decane suspension) obtained as described above were added to obtain 7 kg. / Cm ² G, 50 ° C
Then, propylene was polymerized for 0.5 hours.

The obtained polymer (polypropylene) is
24.6 g, therefore the polymerization activity is 5.4 × 10 ⁵ g
/ G-Zr, polycyclopentene (prepolymer)
Was 460 ppm.

This polypropylene has a melting point of 15
It was 0.4 ° C and the intrinsic viscosity [η] was 0.50 dl / g.

[0114]

Comparative Example 1 Main Polymerization In Example 1, the prepolymerization was not conducted, and 0.0005 mmol of ethylenebisindenylzirconium dichloride was added in place of the prepolymerized catalyst (i) in which cyclopentene was prepolymerized to conduct the main polymerization. Propylene was polymerized in the same manner as in Example 1 except for the above.

The polypropylene obtained was 39.8 g, and therefore the polymerization activity was 8.8 × 10 ⁵ g / g-Zr. This polypropylene also has a melting point of 137.1.
C., and the intrinsic viscosity [η] was 0.49 dl / g.

[0116]

Example 2 Preliminary Polymerization 200 ml of purified decane and 50 ml of cyclopentene were added to a 400 ml glass flask equipped with a stirrer, and methylaluminoxane was added to 2 mmol in terms of aluminum atom, and dimethylsilylbis (methylcyclopentadienyl) zirconium. 10 ml of a toluene solution containing 0.02 mmol of dichloride was added, and the mixture was stirred at 30 ° C. for 4 hours.

Then, the solid portion (preliminary polymerization catalyst (ii)) was separated from the above reaction solution and suspended in decane. The amount of prepolymerization was 75 g / g-Zr.

Main Polymerization In a 2-liter autoclave, 750 ml of hexane was added.
0.175 mmol of methylaluminoxane in terms of aluminum atoms, and 0.0005 mmol of zirconium in terms of the prepolymerization catalyst (ii) (decane suspension) obtained as described above to give 7 kg. / Cm ² G, 50 ° C
Then, propylene was polymerized for 0.5 hours.

The obtained polymer (polypropylene) is
9.8 g, and therefore the polymerization activity is 2.1 × 10 ⁵ g /
It was g-Zr, and the content of polycyclopentene (prepolymer) was 360 ppm.

This polypropylene has a melting point of 15
It was 5.3 ° C. and the intrinsic viscosity [η] was 0.18 dl / g.

[0121]

Comparative Example 2 Main Polymerization Propylene was polymerized in the same manner as in Example 2 except that prepolymerization was not performed.

The polypropylene obtained was 12.5 g, and the polymerization activity was therefore 2.7 × 10 ⁵ g / g-Zr. Also, this polypropylene has a melting point of 142.3.
C., and the intrinsic viscosity [η] was 0.17 dl / g.

[Brief description of drawings]

FIG. 1 is a flowchart of an olefin polymerization method according to the present invention.

Claims (6)

(57) [Claims] 1. A transition metal compound of Group IVB of the periodic table containing (A) a ligand having a cyclopentadienyl skeleton, (B) (B-1) an organoaluminum oxy compound, and (B)
-2) At least one compound selected from the group consisting of compounds that react with the above transition metal compound (A) to form an ion pair, and (C) an organoaluminum compound, if necessary A prepolymerization catalyst prepared by prepolymerizing a cycloolefin having a heavy bond. 2. A transition metal compound of Group IVB of the periodic table containing [I] (A) a ligand having a cyclopentadienyl skeleton, (B) (B-1) an organoaluminum oxy compound, and ( B
-2) At least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form an ion pair, and (C) an organoaluminum compound, if necessary, and A prepolymerization catalyst prepared by prepolymerizing a cycloolefin having a heavy bond, and optionally [II] at least one compound selected from the group consisting of (B-1) and (B-2) above, and / Alternatively, a catalyst for olefin polymerization comprising [III] an organoaluminum compound. 3. A transition metal compound of group IVB of the periodic table containing [I] (A) a ligand having a cyclopentadienyl skeleton, (B) (B-1) an organoaluminum oxy compound, and ( B
-2) At least one compound selected from the group consisting of compounds that react with the transition metal compound (A) to form an ion pair, and (C) an organoaluminum compound, if necessary, and A prepolymerization catalyst prepared by prepolymerizing a cycloolefin having a heavy bond, and optionally [II] at least one compound selected from the group consisting of (B-1) and (B-2) above, and / Alternatively, the prepolymer contained in the olefin polymer obtained by polymerizing or copolymerizing α-olefin in the presence of [III] organoaluminum compound is 10 to 100.
A method for polymerizing an α-olefin, characterized in that it is contained in an amount of 00 ppm. 4. The α-olefin is an α-olefin having 3 to 6 carbon atoms.
The α according to claim 3, which is an olefin.
-Method for polymerizing olefins. 5. The α-olefin is propylene or 1-
The method for polymerizing an α-olefin according to claim 3, which is butene. 6. The method for polymerizing an α-olefin according to claim 3, wherein the olefin polymer obtained has an intrinsic viscosity [η] of 0.01 to 20 dl / g.