JP2988226B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst comprising a metallocene compound, an organoaluminum compound and an ionized ionic compound, and a method for producing a polyolefin using the olefin polymerization catalyst.

[0002]

2. Description of the Related Art As a catalyst for olefin polymerization, JP-A-3-197513 discloses that ethylene is polymerized using a metallocene compound and an organoaluminum compound as catalysts. 290
No. 408 discloses a method for obtaining a polymer using a zirconocene compound, an organic aluminum compound and an organic magnesium compound as catalysts. However, these catalysts were not satisfactory in terms of activity and the like.

Furthermore, it has been disclosed that an olefin polymer containing propylene can be produced with high activity by using a metallocene compound and methylaluminoxane as catalysts.
No. 9309, and the like. However, in this catalyst, methylaluminoxane is relatively expensive, and it is necessary to use a large amount of this methylaluminoxane during polymerization. There was a problem.

Recently, a catalyst exhibiting high activity in the polymerization of olefins including propylene by adding an organoaluminum compound to an ionic metallocene catalyst has been disclosed in JP-A-3-20.
No. 7704. Further, it is disclosed that an ionic metallocene catalyst which is a main catalyst in this catalyst is generally produced by a reaction of a metallocene compound with an ionized ionic compound. However, the ionized ionic compound, which is the raw material of the ionic metallocene catalyst,
It is synthesized by ammonium chloride or triphenylcarbenium chloride of a metal salt of boric acid or aluminate, and many complicated synthesis steps are required to synthesize an ionized ionic compound.

On the other hand, Japanese Patent Application Laid-Open No. Hei 5-202125 describes the use of a metal salt of boric acid or a metal salt of aluminate as an ionized ionic compound. The metal salt of boric acid or the metal salt of aluminate is a raw material of the existing ionized ionic compound, and enables to avoid a complicated synthesis method of the ionized ionic compound. However, these catalysts are not satisfactory in terms of activity and the like, and also have many problems such as purity, reproducibility in synthesis, deactivation during storage and transfer to a polymerization vessel.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide an olefin polymerization catalyst comprising a metallocene compound, an organoaluminum compound and an ionized ionic compound, and a polyolefin using the same. It is intended to provide a manufacturing method.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an ionized ionic compound of an olefin polymerization catalyst comprising a metallocene compound, an organoaluminum compound and an ionized ionic compound. Furthermore, they have found that a polyolefin having high activity and excellent physical properties and processability can be efficiently produced by using a specific metal salt of boric acid or a metal salt of aluminate, thereby completing the present invention.

That is, the present invention comprises (A) a metallocene compound, (B) an organoaluminum compound and (C) a metal salt of boric acid or a metal salt of aluminate, wherein the metallocene compound (A) is represented by the following general formula (A): 1)

[0009]

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Wherein Cp ¹ and Cp ² are each independently a cyclopentadienyl group or a substituted cyclopentadienyl group, and R ¹ is an alkylene group having 1 to 20 carbon atoms, an arylalkylene group, or a dialkylsilylene. A dialkylgermanylene group, an alkylphosphinediyl group or an alkylimino group, R ¹ acts to crosslink Cp ¹ and Cp ² , m is 0 or 1, M is a titanium atom, zirconium Atom or hafnium atom,
X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group or an aryloxy group. ) Wherein the organoaluminum compound (B) is represented by the following general formula (2)

[0011]

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Wherein R ² is a hydrogen atom, an alkyl group, an alkoxy group or an aryl group, each R ² may be the same or different, and at least one R ² is an alkyl group. Wherein the metal salt of boric acid or the metal salt of aluminate (C) is represented by the following general formula (3)

[0013]

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Wherein C is a cation of an alkali metal or an alkaline earth metal, L is a Lewis base, A is an anion containing a boron element or an aluminum element, and n is 0 <n ≦ 6. , B and d are integers selected so as to balance the charges.) And a method for producing a polyolefin, which comprises polymerizing an olefin in the presence of the olefin polymerization catalyst. .

Hereinafter, the present invention will be described in detail.

The metallocene compound (A) used in the present invention is represented by the general formula (1). Specific examples of these compounds include bis (cyclopentadienyl) zirconium dimethyl and bis (methylcyclopentadienyl). ) Zirconium dimethyl, bis (butylcyclopentadienyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dimethyl, isopropylidene (cyclopentadienyl-1-fluorenyl) zirconium dimethyl, diphenylmethylene (cyclopentadienyl-1-fluorenyl) Zirconium dimethyl, dimethyl
Silylene-bis (2,4,5-trimethyl cyclopentadienyl) zirconium dimethyl, dimethyl silylene bis (2,4-dimethyl-cyclopentadienyl) zirconium dimethyl, dimethyl silylene bis (3-methylcyclopentadienyl) zirconium dimethyl, Bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-1- Fluorenyl) zirconium dichloride,
Diphenylmethylene (cyclopentadienyl-1-fluorenyl) zirconium dichloride, dimethyl Shirire
Emissions bis (2,4,5-trimethyl cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (2,4-dimethyl-cyclopentadienyl) zirconium dichloride, dimethyl silylene bis (3-methylcyclopentadienyl) zirconium dichloride, Bis (cyclopentadienyl) zirconium diphenyl, bis (methylcyclopentadienyl) zirconium diphenyl, bis (butylcyclopentadienyl) zirconium diphenyl, ethylenebis (indenyl) zirconium diphenyl, isopropylidene (cyclopentadienyl-1- fluorenyl) zirconium diphenyl, diphenyl methylene (cyclopentadienyl-1-fluorenyl) zirconium diphenyl, dimethyl silylene bis (2,4,5 Chill cyclopentadienyl) zirconium diphenyl, dimethyl silylene bis (2,4
Dimethyl cyclopentadienyl) zirconium diphenyl, dimethyl silylene bis (3-methylcyclopentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (methylcyclopentadienyl) zirconium dibenzyl, bis (butyl Cyclopentadienyl) zirconium dibenzyl,
Ethylenebis (indenyl) zirconium dibenzyl,
Isopropylidene (cyclopentadienyl-1-fluorenyl) zirconium dibenzyl, diphenylmethylene (cyclopentadienyl-1-fluorenyl) zirconium dibenzyl, dimethyl silylene bis (2,4,5
Trimethyl cyclopentadienyl) zirconium dibenzyl, dimethyl silylene bis (2,4-dimethyl-cyclopentadienyl) zirconium dibenzyl, dimethyl sheet
Perylene bis (3-methylcyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium methoxy monochloride, bis (methylcyclopentadienyl) zirconium methoxy monochloride, bis (butylcyclopentadienyl) zirconium methoxy monochloride, ethylenebis (indenyl) zirconium methoxy monochloride, isopropylidene (cyclopentadienyl-1-fluorenyl) zirconium methoxy monochloride, diphenylmethylene (cyclopentadienyl-1-fluorenyl) zirconium methoxy monochloride, dimethyl silylene bis (2,4,5-trimethyl cyclopentadienyl) zirconium methoxy monochloride, dimethyl silylene bis (2,4-dimethyl-cyclopentadienyl Le) zirconium methoxy monochloride, dimethyl silylene bis (3-methylcyclopentadienyl) zirconium methoxy monochloride, bis (cyclopentadienyl) methyl zirconium monochloride, bis (methylcyclopentadienyl) methyl zirconium monochloride, bis (Butylcyclopentadienyl) methyl zirconium monochloride, ethylenebis (indenyl) methyl zirconium monochloride, isopropylidene (cyclopentadienyl-1-fluorenyl) methyl zirconium monochloride, diphenylmethylene (cyclopentadienyl-1-fluorenyl) ) methyl zirconium monochloride, dimethyl silylene bis (2,4,5-trimethyl cyclopentadienyl) methyl zirconium monochloride, dimethyl Perylene bis (2,4-dimethyl-cyclopentadienyl) methyl zirconium monochloride, dimethyl silylene bis (3-methyl-cyclopentadienyl) methyl zirconium monochloride, etc., and the zirconium metal of the above zirconium compound to titanium metal or hafnium metal The substituted metallocene compound and the like can be exemplified.

The organoaluminum compound (B) is
The specific compound represented by the general formula (2) includes trimethylaluminum, triethylaluminum, triisopropylaluminum, tri (n-propyl) aluminum, triisobutylaluminum, tri (n-butyl) aluminum, and triamyl. Aluminum, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum ethoxide, di (n-propyl) aluminum ethoxide, diisobutylaluminum ethoxide, di (n
-Butyl) aluminum ethoxide, dimethylaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, di (n
-Propyl) aluminum hydride, diisobutyl aluminum hydride, di (n-butyl) aluminum hydride and the like.

The metal salt of boric acid or metal salt of aluminate (C) used in the present invention is represented by the following general formula (3). Specific examples of these compounds include lithium tetrakis (pentafluorophenyl) borate. , Lithium tetrakis (phenyl) borate, lithium tetrakis (p-
Tolyl) borate, lithium tetrakis (m-tolyl)
Borate, lithium tetrakis (2,4-dimethylphenyl) borate, lithium tetrakis (3,5-dimethylphenyl) borate, lithium tetrafluoroborate, sodium tetrakis (pentafluorophenyl)
Borate, sodium tetrakis (phenyl) borate, sodium tetrakis (p-tolyl) borate, sodium tetrakis (m-tolyl) borate, sodium tetrakis (2,4-dimethylphenyl) borate,
Sodium tetrakis (3,5-dimethylphenyl) borate, sodium tetrafluoroborate, potassium tetrakis (pentafluorophenyl) borate, potassium tetrakis (phenyl) borate, potassium tetrakis (p-tolyl) borate, potassium tetrakis (m
-Tolyl) borate, potassium tetrakis (2,4-dimethylphenyl) borate, potassium tetrakis (3
5-dimethylphenyl) borate, potassium tetrafluoroborate, magnesium tetrakis (pentafluorophenyl) borate, magnesium tetrakis (phenyl) borate, magnesium tetrakis (p-tolyl) borate, magnesium tetrakis (m-tolyl)
Borate, magnesium tetrakis (2,4-dimethylphenyl) borate, magnesium tetrakis (3,5
-Dimethylphenyl) borate, magnesium tetrafluoroborate, calcium tetrakis (pentafluorophenyl) borate, calcium tetrakis (phenyl) borate, calcium tetrakis (p-tolyl) borate, calcium tetrakis (m-tolyl) borate, calcium tetrakis (2, 4-dimethylphenyl) borate, calcium tetrakis (3,5-dimethylphenyl) borate, calcium tetrafluoroborate, lithium tetrakis (pentafluorophenyl)
Aluminate, lithium tetrakis (phenyl) aluminate, lithium tetrakis (p-tolyl) aluminate, lithium tetrakis (m-tolyl) aluminate,
Lithium tetrakis (2,4-dimethylphenyl) aluminate, lithium tetrakis (3,5-dimethylphenyl) aluminate, lithium tetrafluoroaluminate, sodium tetrakis (pentafluorophenyl) aluminate, sodium tetrakis (phenyl)
Aluminate, sodium tetrakis (p-tolyl) aluminate, sodium tetrakis (m-tolyl) aluminate, sodium tetrakis (2,4-dimethylphenyl) aluminate, sodium tetrakis (3.5)
-Dimethylphenyl) aluminate, sodium tetrafluoroaluminate, potassium tetrakis (pentafluorophenyl) aluminate, potassium tetrakis (phenyl) aluminate, potassium tetrakis (p-
Tolyl) aluminate, potassium tetrakis (m-tolyl) aluminate, potassium tetrakis (2,4-dimethylphenyl) aluminate, potassium tetrakis (3,5-dimethylphenyl) aluminate, potassium tetrafluoroaluminate, magnesium tetrakis ( (Pentafluorophenyl) aluminate, magnesium tetrakis (phenyl) aluminate, magnesium tetrakis (p-tolyl) aluminate, magnesium tetrakis (m-tolyl) aluminate, magnesium tetrakis (2,4-dimethylphenyl) aluminate, magnesium tetrakis (3,5-dimethylphenyl) aluminate, magnesium tetrafluoroaluminate, calcium tetrakis (pentafluorophenyl) aluminate, cal Umutetorakisu (phenyl)
Aluminate, calcium tetrakis (p-tolyl) aluminate, calcium tetrakis (m-tolyl) aluminate, calcium tetrakis (2,4-dimethylphenyl) aluminate, calcium tetrakis (3.5)
Ether complexes such as-(dimethylphenyl) aluminate and calcium tetrafluoroaluminate; and tetrahydrofuran complexes.

The olefin polymerization catalyst of the present invention is obtained, for example, by mixing a metallocene compound (A) and an organoaluminum compound (B) with an olefin, and mixing the mixture with a metal salt of boric acid or a metal salt of aluminate (C). It can be obtained by contact.

The molar ratio of the metallocene compound (A) and the metal salt of boric acid or the metal salt of aluminate (C) is not particularly limited, but is preferably a metallocene compound (A):
Mol of metal salt of boric acid or metal salt of aluminate (C)
The ratio is preferably in the range from 1: 0.01 to 1: 1000, particularly preferably in the range from 1: 0.2 to 1: 200. The preferred concentration of the organoaluminum compound (B) used here is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mo.
1 / l.

The olefin used in the polymerization reaction of the present invention is ethylene, propylene, 1-butene, 4-methyl-
Α-olefins such as 1-pentene and 1-hexene; conjugated and non-conjugated dienes such as butadiene and 1,4-hexadiene; and cyclic olefins such as styrene and cyclobutene. Polymerization of a mixture of two or more of these components is also possible. it can.

The polymerization of the olefin in the present invention can be carried out in a liquid phase or a gas phase. If the polymerization is performed in the liquid phase, any solvent may be used as long as it is a commonly used organic solvent, and specifically, benzene, toluene,
Xylene, pentane, hexane, methylene chloride and the like can be mentioned, or the olefin itself can be used as a solvent.

The catalyst according to the invention can also be used on inert supports. This is a metallocene compound, a reaction product of a metallocene compound and a metal salt of boric acid or aluminic acid, a reaction product of a metallocene compound and an organoaluminum compound, a metal salt of boric acid or a metal salt of aluminate itself, Or the organoaluminum compound itself, for example,
It can be obtained by deposition on an inert carrier such as silica, alumina, magnesium chloride, styrene-divinylbenzene copolymer or polyethylene.

The solid component thus obtained is particularly advantageously used for polymerization in the gas phase. The polymerization temperature is not particularly limited, but is preferably in the range of -100 to 230C.

[0025]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The polymerization operation, reaction, and solvent purification were all performed under an inert gas atmosphere. The solvents used for the reaction were all purified, dried and / or deoxygenated by a known method. The compounds used for the reaction were those synthesized and identified by a known method.

Example 1 To a 2-liter autoclave, 500 ml of toluene was added, followed by 0.5 mmol of triisobutylaluminum.
Stirred for 10 minutes. To this solution, 0.5 μmol of ethylene bis (indenyl) zirconium dichloride synthesized by a known method was added as a 10 ml toluene solution, and added.
This mixed solution was stirred for 20 minutes. Propylene 5
00 ml was inserted and stirred for 10 minutes. To this [Li
2.5 μmol of (Et ₂ O)] [B (C ₆ F ₅ ) ₄ ] (diethyl ether complex of lithium tetrakis (pentafluorophenyl) borate) was pressed into an autoclave with 10 ml of toluene, and the mixture was heated at 40 ° C. for 1 hour. Polymerization was performed.

As a result, 188 g of isotactic polypropylene was obtained. This is 376kg / mmolZ
It corresponds to the polymerization activity of r · h.

Example 2 500 ml of toluene was added to a 2 l autoclave, and then 0.5 mmol of triisobutylaluminum was added.
Stirred for 10 minutes. Ethylene bis (indenyl) zirconium dichloride 1 synthesized by a known method was added to this solution.
μmol was added as a 10 ml toluene solution, and the mixed solution was stirred for 20 minutes. 500m of propylene
and stirred for 10 minutes. Add [Li (Et ₂
O) ₂ ] [B (C ₆ F ₅ ) ₄ ] (diethyl ether complex of lithium tetrakis (pentafluorophenyl) borate) was pressed into an autoclave with 10 ml of toluene and polymerized at 40 ° C. for 1 hour. .

As a result, 111 g of isotactic polypropylene was obtained. This is 111 kg / mmolZ
It corresponds to the polymerization activity of r · h.

Comparative Example 1 To a 2-liter autoclave, 500 ml of toluene was added, and then 0.5 mmol of triisobutylaluminum was added.
Stirred for 10 minutes. Ethylene bis (indenyl) zirconium dichloride 1 synthesized by a known method was added to this solution.
0 μmol was added as a 10 ml toluene solution, and the mixed solution was stirred for 20 minutes. To this propylene 500
ml, and stirred for 10 minutes. [Li] [B
(C ₆ F ₅ ) ₄ ] (lithium tetrakis (pentafluorophenyl) borate) (50 μmol) was injected into an autoclave using 10 ml of toluene, and polymerization was carried out at 40 ° C. for 1 hour.

As a result, 10 g of isotactic polypropylene was obtained. This is 1 kg / mmol Zr · h
Corresponds to the polymerization activity of

Comparative Example 2 The method of Example 1 except that 2.5 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate was used instead of [Li (Et ₂ O)] [B (C ₆ F ₅ ) ₄ ]. Was repeated. As a result, 45 g of isotactic polypropylene was obtained. This is 90 kg / mmol
This corresponds to the polymerization activity of Zr · h.

Example 3 To a 2 l autoclave was added 500 ml of toluene, and then 0.5 mmol of triisobutylaluminum.
Stirred for 10 minutes. To this solution was added ethylenebis (indenyl) zirconium dimethyl 0.5 synthesized by a known method.
μmol was added as a 10 ml toluene solution, and the mixed solution was stirred for 20 minutes. 500m of propylene
and stirred for 10 minutes. Add [Li (Et ₂
O)] [B (C ₆ F ₅ ) ₄ ] 2.5 μmol was pressed into an autoclave with 10 ml of toluene,
Polymerization was carried out for hours. As a result, 170 g of isotactic polypropylene was obtained. This is 340kg / mm
It corresponds to the polymerization activity of olZr · h.

Comparative Example 3 The method of Example 3 except that 2.5 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate was used instead of [Li (Et ₂ O)] [B (C ₆ F ₅ ) ₄ ]. Was repeated. As a result, 40 g of isotactic polypropylene was obtained. This is 80 kg / mmol
This corresponds to the polymerization activity of Zr · h.

Example 4 To a 2-liter autoclave, 500 ml of toluene was added, and then 0.5 mmol of triisobutylaluminum was added.
Stirred for 10 minutes. 10 μl of 5 μmol of isopropylidene (cyclopentadienyl-1-fluorenyl) zirconium dichloride synthesized by a known method was added to this solution.
, And the mixture was stirred for 20 minutes. 500 ml of propylene was inserted into the mixture, and the mixture was stirred for 10 minutes. In addition to this, [Li (Et ₂ O)] [B (C
₆ F ₅ ) ₄ ] was pressed into an autoclave with 10 ml of toluene and polymerized at 40 ° C. for 1 hour. As a result, 110 g of syndiotactic polypropylene was obtained. This corresponds to a polymerization activity of 22 kg / mmol Zr · h.

Comparative Example 4 The method of Example 4 was repeated except that ₂₅ μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate was used instead of [Li (Et ₂ O)] [B (C ₆ F ₅ ) ₄ ]. Was. As a result, 30 g of syndiotactic polypropylene was obtained. This is 6kg / mmolZ
It corresponds to the polymerization activity of r · h.

Example 5 To a 2-liter autoclave, 500 ml of toluene was added, and then 0.5 mmol of triisobutylaluminum was added.
Stirred for 10 minutes. To this solution, 5 μmol of isopropylidene (cyclopentadienyl-1-fluorenyl) zirconium dimethyl synthesized by a known method was added as a 10 ml toluene solution, and the mixed solution was stirred for 20 minutes. 500 ml of propylene was inserted into the mixture, and the mixture was stirred for 10 minutes. [Li (Et ₂ O)] [B (C ₆ F ₅ ) ₄ ]
25 μmol was injected into the autoclave using 10 ml of toluene, and polymerization was carried out at 40 ° C. for 1 hour. As a result, 95 g of syndiotactic polypropylene was obtained. This corresponds to a polymerization activity of 19 kg / mmol Zr · h.

Comparative Example 5 Dimethylanilinium tetrakis (pentafluorophenyl) borate 2 was used instead of the diethyl ether complex of lithium tetrakis (pentafluorophenyl) borate.
The method of Example 5 was repeated except that 5 μmol was used. As a result, 25 g of syndiotactic polypropylene was obtained. This corresponds to a polymerization activity of 5 kg / mmol Zr · h.

Example 6 To a 2-liter autoclave, 500 ml of toluene was added, and then 0.25 mmol of triisobutylaluminum was added, followed by stirring for 10 minutes. To this solution, 0.05 μmol of ethylene bis (indenyl) zirconium dichloride synthesized by a known method was added as a 10 ml toluene solution, and the mixed solution was stirred for 20 minutes. To this [Li
(Et ₂ O)] [B (C ₆ F ₅ ) ₄ ] 0.25 μmol
It was inserted as a 0 ml toluene solution. The autoclave is pressurized with ethylene to 4 kg / cm ² ,
Stirred at 40 ° C. for 1 hour.

As a result, 36 g of polyethylene was obtained.
This corresponds to a polymerization activity of 720 kg / mmol Zr · h.

Example 7 To a 2-liter autoclave, 500 ml of toluene was added, and then 0.25 mmol of triisobutylaluminum was added, followed by stirring for 10 minutes. To this solution, 0.25 μmol of ethylene bis (indenyl) zirconium dichloride synthesized by a known method was added as a 10 ml toluene solution, and the mixed solution was stirred for 20 minutes. To this [Li
(Et ₂ O) ₂ ] [B (C ₆ F ₅ ) ₄ ], 1.25 μmol, was inserted into a 10 ml toluene solution. The autoclave was pressurized with ethylene to 4 kg / cm ² and stirred at 40 ° C. for 1 hour.

As a result, 72 g of polyethylene was obtained.
This corresponds to a polymerization activity of 288 kg / mmol Zr · h.

Comparative Example 6 To a 2-liter autoclave, 500 ml of toluene was added, and then 0.25 mmol of triisobutylaluminum was added, followed by stirring for 10 minutes. 1 μmol of ethylenebis (indenyl) zirconium dichloride synthesized by a known method was added to this solution in a 10 ml toluene solution, and the mixed solution was stirred for 20 minutes. [Li] [B
(C ₆ F ₅ ) ₄ ] was inserted into a 10 ml toluene solution of 5 μmol. The autoclave was pressurized with ethylene to 4 kg / cm ² and stirred at 40 ° C. for 1 hour.

As a result, 52 g of polyethylene was obtained.
This corresponds to a polymerization activity of 52 kg / mmol Zr · h.

Example 8 To a 2-liter autoclave, 500 ml of toluene was added, and then 0.25 mmol of triisobutylaluminum was added, followed by stirring for 10 minutes. To this solution, 0.1 μmol of ethylene bis (indenyl) zirconium dichloride synthesized by a known method was added as a 10 ml toluene solution, and the mixed solution was stirred for 20 minutes. To this [Li
0.5 μmol of (Et ₂ O) ₂ ] [Al (C ₆ F ₅ ) ₄ ] (diethyl ether complex of lithium tetrakis (pentafluorophenyl) aluminate) was inserted into a 10 ml toluene solution and inserted. 4 kg / c of the autoclave
The mixture was pressurized with ethylene so as to obtain m ² and stirred at 40 ° C. for 1 hour.

As a result, 15 g of polyethylene was obtained.
This corresponds to a polymerization activity of 150 kg / mmol Zr · h.

Comparative Example 7 To a 2-liter autoclave, 500 ml of toluene was added, and then 0.25 mmol of triisobutylaluminum was added, followed by stirring for 10 minutes. To this solution, 0.5 μmol of ethylene bis (indenyl) zirconium dichloride synthesized by a known method was added as a 10 ml toluene solution, and the mixed solution was stirred for 20 minutes. This is [Li]
0.25 μmol of [Al (C ₆ F ₅ ) ₄ ] (lithium tetrakis (pentafluorophenyl) aluminate)
It was inserted as a 0 ml toluene solution. The autoclave is pressurized with ethylene to 4 kg / cm ² ,
Stirred at 40 ° C. for 1 hour.

As a result, 13 g of polyethylene was obtained.
This corresponds to a polymerization activity of 26 kg / mmol Zr · h.

Example 9 To a 2-liter autoclave, 500 ml of toluene was added, and then 0.25 mmol of triisobutylaluminum was added, followed by stirring for 10 minutes. To this solution, 0.25 μmol of ethylene bis (indenyl) zirconium dichloride synthesized by a known method was added as a 10 ml toluene solution, and the mixed solution was stirred for 20 minutes. To this [Li
(Et ₂ O) ₂ ] [Al (C ₆ F ₅ ) ₄ ] 1.25 μmol
Into a 10 ml toluene solution and inserted. The autoclave was pressurized with ethylene to 8 kg / cm ² and stirred at 40 ° C. for 1 hour. As a result, 110 g of polyethylene was obtained. This is 440 kg / mmol Zr
-It corresponds to the polymerization activity of h.

Comparative Example 8 [Li (Et ₂ O) ₂ ] [Al (C ₆ F ₅ ) ₄ ] 1.25 μm
mol instead of dimethylanilinium tetrakis (pentafluorophenyl) aluminate 1.25 μmol
And the method of Example 9 was repeated. As a result, 60
g of polyethylene were obtained. This is 240kg / mmo
It corresponds to the polymerization activity of 1Zr · h.

[0052]

As described above, according to the catalyst of the present invention and the method for polymerizing olefins using the same, it is possible to omit a complicated process for synthesizing a catalyst component, and to obtain a polyolefin having excellent physical properties and processability. It can be manufactured efficiently.

Claims (2)

(57) [Claims] A metallocene compound (A) comprising (A) a metallocene compound, (B) an organoaluminum compound and (C) a metal salt of boric acid or a metal salt of aluminate, wherein the metallocene compound (A) is represented by the following general formula (1): Formula 1 Wherein Cp ¹ and Cp ² are each independently a cyclopentadienyl group or a substituted cyclopentadienyl group, and R ¹ is an alkylene group having 1 to 20 carbon atoms, an arylalkylene group, a dialkylsilylene group, a dialkyl A germanylene group, an alkylphosphinediyl group or an alkylimino group, R ¹ acts to crosslink Cp ¹ and Cp ² , m is 0 or 1, M is a titanium atom, a zirconium atom or a hafnium X ¹ and X ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group or an aryloxy group.)
Wherein the organoaluminum compound (B) is represented by the following general formula (2): Wherein R ² is a hydrogen atom, an alkyl group, an alkoxy group or an aryl group, each R ² may be the same or different, and at least one R ² is an alkyl group. The metal salt of an acid or the metal salt of aluminate (C) is represented by the following general formula (3): (Wherein C is an alkali metal or alkaline earth metal cation, L is a Lewis base, A is an anion containing a boron element or an aluminum element, and n is 0 <
n ≦ 6, and b and d are integers selected to balance the charges. An olefin polymerization catalyst represented by the formula: 2. A method for producing a polyolefin, comprising polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.