JPH06336502A - Olefin polymerization catalyst and method for polymerizing olefin - Google Patents

Abstract

PURPOSE:To efficiently produce a particulate polyolefin having excellent material properties. CONSTITUTION:This catalyst comprises (a) a solid catalyst component comprising a metallocene compound represented by the formula Cp2MX2 (wherein Cp's each independently is a (substituted)cyclopentadianyl and may be bonded to each other; M is titanium, zirconium, or hafnium; and X's each independently is a halogen, an alkoxy, amino, or an amido group), an ionizing ionic compound represented by the formula [C<+>@{9147/28 [A<->] (wherein [C<+>] is a cation and [A<->] is an anion), and a finely powdered carrier and (b) and organometallic compound represented by the formula M'Rn (wherein M' is a metal capable of forming an M'-R bond reactive with the M-X bond of the metallocene compound; R's each independently is a hydrocarbon group, a halogen, hydrogen, an amido group, an alkoxy, or an aryl, provided that at least one R is a hydrocarbon group; and (n) is an integer of 1-4).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst comprising a solid catalyst component and an organometallic compound, and an olefin polymerization method using the same.

[0002]

As an olefin polymerization catalyst, JP-A-3-197513 discloses that ethylene is polymerized by using a metallocene compound and an organoaluminum compound as a catalyst, and JP-A-3-290408. The publication discloses that a polyethylene or ethylene copolymer can be obtained by using a zirconocene compound, an organoaluminum compound and an organomagnesium compound. Further, Kaminsky et al. Disclose that a catalyst composed of metallocene and methylaluminoxane exhibits high activity when producing an olefin polymer containing propylene, as disclosed in JP-A-58-19309. Further, polymerization of olefins by suspension polymerization or gas phase polymerization is carried out by using a catalyst in which one or both of metallocene and methylaluminoxane catalyst components are supported on an inorganic oxide carrier such as silica, and JP-A-63-51407.
It is disclosed in Japanese Patent Publication No. However, in these catalyst systems, it is necessary to use a relatively large amount of methylaluminoxane, which is relatively expensive, in order to produce a polymer having industrially useful physical properties, which causes a cost problem and a large amount of aluminum in the polymer. There was a problem that remained.

Recently, by adding an organoaluminum compound to an ionic metallocene catalyst, a catalyst showing high activity in the polymerization of olefins including propylene has been disclosed in Japanese Patent Laid-Open No. Hei 3 (1999) -311.
-124706 and Japanese Patent Laid-Open No. 3-207704. The ionic metallocene catalyst, which is the main catalyst in the above specification, is converted into a metal derivative of a metallocene compound by using a methylating reagent such as methyllithium or methylmagnesium chloride from a chloride of the metallocene compound, and further ionized with this methyl derivative. It is disclosed that it is produced by reaction with an ionic compound. However, the methyl derivative of the metallocene compound and the ionic metallocene catalyst disclosed herein are often unstable and cannot be synthesized without going through technically sophisticated and complicated multi-step processes. Therefore, there are many problems such as the purity of the catalyst, reproducibility of preparation, storage, and deactivation during transfer to the polymerization vessel.

Further, polymerization of an olefin by suspension polymerization or gas phase polymerization using a catalyst in which the above-mentioned ionic metallocene compound is supported on an inorganic oxide carrier such as silica is disclosed in JP-A-3.
No. 234709. However, this catalyst system is not sufficiently active, and unstable compounds such as methyl derivatives of metallocene compounds and ionic metallocene catalysts cannot be synthesized without going through technologically advanced and complicated multi-step processes. There was a problem.

Further, there has been an attempt to polymerize propylene using a catalyst obtained by contacting a reaction product obtained by treating a halogenated metallocene compound with an organometallic compound and a compound which reacts with the reaction product and becomes a stable anion. It is disclosed in PCT International Publication No. 92/01723. But,
Since this catalyst system is characterized by using a reaction product of a halogenated metallocene and an organoaluminum, although the stability is improved as compared with the above-mentioned ionic metallocene catalyst and the like, the halogenated metallocene and the organic metal are used. As disclosed in the above publication, the stability of the reaction product with aluminum significantly changes depending on the selection of organoaluminum, so that the stability of the catalyst system is still insufficient.

[0006]

The present invention has been made to solve the above-mentioned problems, and comprises a solid catalyst component composed of a stable metallocene compound, an ionized ionic compound and a particulate carrier and an organometallic compound. An object of the present invention is to provide a catalyst system suitable for polymerizing an olefin as a component.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and found that a solid catalyst component composed of a stable metallocene compound, an ionizable ionic compound and a fine particle carrier and an organic metal. It was found that a particulate polyolefin having excellent physical properties can be efficiently produced by using a catalyst system containing a compound as a constituent component, and the present invention has been completed.

That is, the present invention relates to an olefin polymerization catalyst comprising (a) a solid catalyst component and (b) an organometallic compound as constituent components, wherein the (a) solid catalyst component is represented by the general formula (1) Cp ₂ MX ₂ (1) (In the formula, Cp is independently a cyclopentadienyl group or a substituted cyclopentadienyl group, Cp may be bonded to each other. M is titanium, zirconium or hafnium, and X is each are independently halogen, alkoxy group, amino group, metallocene compounds represented by an amide group), the following general formula ^{(2) [C +] [} a -] (2) ( where, in [C ^+] is cation And [A ⁻ ] is an anion), and (b) the organometallic compound has the general formula (3) M′R _n (3) (wherein M is ´ is the above metalloc A metal capable of forming an M'-R bond having reactivity with M-X bond of the compound,
R is each independently a hydrocarbon group, halogen, hydrogen, an amido group, an alkoxy group or an aryl group, and at least one R is a hydrocarbon group, and n is an integer of 1 to 4) And a method for producing a polyolefin, which comprises polymerizing an olefin in the presence of the catalyst.

The present invention will be described in detail below.

The metallocene compound contained in the solid catalyst component used in the present invention is represented by the general formula (1). Of these, M is titanium, zirconium or hafnium. In addition, X is independently a halogen, an alkoxy group, an amino group, or an amide group.

As a specific example, when X is chlorine,
Bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) zirconium Dichloride, bis (methylcyclopentadienyl) hafnium titanium dichloride, bis (butylcyclopentadienyl) titanium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl)
Hafnium dichloride, ethylene bis (indenyl)
Titanium dichloride, ethylene bis (indenyl)
Zirconium dichloride, ethylenebis (indenyl) hafnium dichloride, isopropylidene (cyclopentadienyl-1-fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl-)
1-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-1-fluorenyl) hafnium dichloride, dimethylsilylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylbis (2,4-dimethyl) Cyclopentadienyl) titanium dichloride, dimethylsilylbis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylbis (4-t-butyl, 2-methylcyclopentadienyl) titanium dichloride, dimethylsilylbis (2,2 4,5-Trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (3-methylcyclopentadiene) ) Zirconium dichloride, dimethylsilyl bis (4-t-butyl, 2-
Methylcyclopentadienyl) zirconium dichloride, dimethylsilylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, dimethylsilylbis (2,4-dimethylcyclopentadienyl)
Hafnium dichloride, dimethylsilylbis (3-methylcyclopentadienyl) hafnium dichloride,
Dimethylsilylbis (4-t-butyl, 2-methylcyclopentadienyl) hafnium dichloride, diethylsilylbis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, diethylsilylbis (2,2
4-dimethylcyclopentadienyl) titanium dichloride, diethylsilylbis (3-methylcyclopentadienyl) titanium dichloride, diethylsilylbis (4-
t-Butyl, 2-methylcyclopentadienyl) titanium dichloride, diethylsilylbis (2,4,5-trimethylcyclopentadienyl) zirconium dichloride, diethylsilylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride , Diethylsilylbis (3-methylcyclopentadienyl) zirconium dichloride, diethylsilylbis (4-t-butyl, 2-methylcyclopentadienyl) zirconium dichloride, diethylsilylbis (2,4,5-trimethylcyclopenta) Dienyl) hafnium dichloride,
Diethylsilylbis (3-methylcyclopentadienyl) hafnium dichloride, diethylsilylbis (4
-T-butyl, 2-methylcyclopentadienyl) hafnium dichloride and the like are preferably used, and when X is other than chlorine, compounds similar to those in the case where X is chlorine can be mentioned, but are not limited thereto. is not.

The ionized ionic compound contained in the solid catalyst component of the present invention is represented by the general formula (2).
⁺ ] Is a cation, specifically, trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, N, N containing an active proton.
-Diethylanilinium, N, N, 2,4,5-pentamethylanilinium, triphenylphosphonium, tri (o-tolyl) phosphonium, tri (p-tolyl) phosphonium, tri (mesityl) phosphonium, etc. Examples of such Bronsted acid or carbonium, oxonium or sulfonium cations that do not contain active protons include compounds such as triphenylcarbenium and tropylium ion, but are not limited thereto.

On the other hand, [A ⁻ ] is an anion, and [Al ⁻ ]
R ₄ ⁻ ], [BR ₄ ⁻ ], [PR ₆ ⁻ ] or [ClO ₄ ⁻ ] exemplified compounds, specifically tetraphenyl borate, tetra (pentafluorophenyl) borate, tetra (o-fluorophenyl) ) Borate, tetra (p-fluorophenyl) borate, tetra (m-fluorophenyl) borate, tetra (3,5-difluorophenyl) borate, tetra (2,5-difluorophenyl)
Borate, tetra (2,6-difluorophenyl) borate, tetra (o-tolyl) borate, tetra (p-tolyl) borate, tetra (3,5-dimethylphenyl)
Examples thereof include borate, tetra (2,5-dimethylphenyl) borate, octadecaborate, dodecaborate, 1-carbaundecaborate, 1-carbadodecaborate, but are not limited thereto.

Specific examples of the ionized ionic compound include dimethylanilinium tetrakispentafluorophenyl borate, triphenylcarbenium tetrakispentafluorophenyl borate, and tropylium tetrakispentafluorophenyl borate, but the present invention is not limited thereto. Not something.

An inorganic solid compound or an organic solid compound is used as the fine particle carrier contained in the solid catalyst component used in the present invention. As the inorganic solid compound, a porous fine particle compound having an average particle size of 1 to 300 μm, preferably 10 to 100 μm is preferable. Specifically, oxides of typical elements such as silica, alumina and magnesia, oxides of transition metal elements such as titania and zirconia,
A halide such as magnesium chloride and a composite compound such as silica-alumina and silica-magnesia are used.

These inorganic solid compounds usually contain salts of alkali metals or alkaline earth metals such as Na ₂ O, K ₂ CO ₃ and BaSO ₄ as impurities. The above-mentioned porous, fine-particle inorganic solid compound may be used in a state containing these impurities, but it is preferable to use an inorganic solid compound which has been previously subjected to an operation of removing these impurities. Such a porous, fine-particle inorganic solid compound has different properties depending on its type and production method,
In the present invention, the specific surface area is preferably 10 to 1000 m
² / g, particularly preferably 50 to 800 m ² / g and a pore volume of 0.1 to 3 cc / g are used. These inorganic solid compounds are used by heat treatment at 100 to 1000 ° C., preferably 300 to 900 ° C. under reduced pressure or under gas flow, if necessary.

As the organic solid compound used for the fine particle carrier, particles having an average particle size of 1 to 300 μm are preferable. Specifically, a polymer or copolymer containing α-olefins such as ethylene and propylene as a main component and a polymer or copolymer containing styrene as a main component are used.

In order to serve as the carrier used in the present invention, the above-mentioned inorganic solid compound and organic solid compound may be used as they are, but it is preferable to contact them with a metal compound in advance. The metal compound used here is not particularly limited as long as it is a compound having reactivity with molecular water or a hydroxyl group. For example, an organic metal compound is used, and of these, an organic aluminum compound is particularly preferably used. The method of contacting the porous or particulate inorganic or organic compound with the metal compound in advance is not particularly limited, but the porous or particulate inorganic or organic compound is insoluble, and the metal compound is soluble in an organic solvent. Examples thereof include a method of contacting in a suspended state, a method of contacting in an organic solvent in which both are soluble, and a method of contacting with a ball mill or the like in a substantially solvent-free state.

The organometallic compound used in the present invention is represented by the general formula (3). Among them, M'is a metal capable of forming an M'-R bond having reactivity with the M-X bond of the metallocene compound contained in the solid catalyst component, and specifically, an alkali metal, an alkaline earth metal, or a transition metal. , Aluminum, silicon, germanium and the like. R may be the same or different and is hydrogen, halogen, amide, alkoxy group, aryl group or hydrocarbon group, and at least one of them is a hydrocarbon group.

Specific examples of the organometallic compound when M'is aluminum include trimethylaluminum, triethylaluminum, tri (n-propyl) aluminum, tri (isopropyl) aluminum, tri (n-aluminum).
Butyl) aluminum, tri (isobutyl) aluminum, tri (t-butyl) aluminum, triamyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisobutyl aluminum chloride, di (t-butyl) aluminum chloride,
Examples thereof include, but are not limited to, diamyl aluminum chloride, methyl aluminum chloride, ethyl aluminum dichloride, isobutyl aluminum dichloride, t-butyl aluminum dichloride and amyl aluminum dichloride.

The molar ratio of the metallocene compound and the ionized ionic compound contained in the solid catalyst component (a) of the catalyst of the present invention is not particularly limited, but the molar ratio of metallocene compound: ionized ionic compound is preferably 1: 0. .01-
The range is 1: 1000, particularly preferably 1: 0.2
It is performed in the range of to 1: 100. The amount of the organometallic compound (B) used is not particularly limited, but the molar ratio of the metallocene compound: the organometallic compound is preferably 1: 0.1 to 1.
It is performed in the range of 1: 10000.

The method for preparing a solid catalyst component in the present invention is a method of loading one kind of component selected from a metallocene compound or an ionized ionic compound and then carrying the rest of the components in order, or carrying two kinds of components simultaneously. The method of making it possible can be selected. As the supporting method, for example, an impregnation supporting reaction in a suitable solvent is used.
As these solvents, organic solvents such as toluene and hexane and halogen-containing solvents such as methylene chloride are used.

The olefins used in the polymerization reaction of the present invention are 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. It is also possible to polymerize a mixture of two or more of these. it can.

The olefin polymerization in the present invention can be carried out in the liquid phase or the gas phase. The solvent for carrying out the polymerization in the liquid phase may be any organic solvent that is generally used, and specifically, benzene, toluene, xylene, pentane, hexane, methylene chloride, etc. or the olefin itself may be used as the solvent. You can also

The polymerization temperature is not particularly limited, but it is from -100 to
It is preferably carried out in the range of 230 ° C.

[0026]

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

The melting index (MI) described in the examples is A
The measurement was carried out by a method according to STM D1238 Condition E.

Example 1 The polymerization operation, reaction and solvent purification were all carried out under an inert gas atmosphere. In addition, all the solvents and the like used in the reaction were previously purified, dried and / or deoxygenated by known methods. The compounds used in the reaction were those synthesized and identified by known methods.

[Preparation of Carrier] In a 300 ml glass container, silica (surface area 126 m ² / g, pore diameter 282 Å, pore volume 1.13 cc / g, 300 ° C.,
5.0 g, toluene solution of triethylaluminum (20 wt%) 10.4 ml, and toluene 50 m
1 was added and contact was carried out at room temperature for 1 hour. Furthermore, after heating at 80 ° C. and continuing contact for 1 hour, decantation was performed. The obtained solid was washed with toluene. At this time, washing was performed until no unreacted triethylaluminum was found in the washing liquid. 1.9wt% Al in the carrier
% Was included.

[Preparation of solid catalyst component] In a 300 ml glass container, ethylenebisindenylzirconium dichloride 73 mg, [NH (Me) ₂ Ph] [B (C ₆ F
₅ ) ₄ ] 1.1 g, 1.0 g of the carrier prepared in [Preparation of carrier] and 40 ml of toluene were added, and the mixture was reacted at room temperature for 60 minutes, and further reacted at 70 ° C. for 60 minutes. After decanting, it was washed with 80 ml of toluene. The obtained solid was dried under reduced pressure to obtain a solid catalyst component.
Zr is 0.7 wt% and B is 0.4 wt% in the solid catalyst.
%, And Al was contained by 1.8 wt%.

[Polymerization] To a 2-liter autoclave, 500 ml of hexane and 0.75 mmol of triisobutylaluminum were added and stirred for 10 minutes. The solid catalyst component 105 obtained in the above [Preparation of solid catalyst component] was added to this solution.
mg and triisobutylaluminum 0.75 mmol as a 20 ml hexane solution were charged into an autoclave, and the inside of the autoclave was 4 kg / cm ² with ethylene.
While maintaining at G, polymerization was carried out at 80 ° C. for 30 minutes. As a result, 60 g of polyethylene was obtained. The MI of the obtained polyethylene was 0.003 g / 10 minutes. Also,
There was almost no polyethylene adhering to the inside of the autoclave.

Comparative Example 1 [Polymerization] The reaction was carried out in the same manner as in Example 1 except that triisobutylaluminum was not used. As a result, polyethylene was not obtained.

Example 2 [Polymerization] In a 2 l autoclave, 500 ml of hexane was added.
In place of the above, 500 ml of toluene was added to add 21 parts of the solid catalyst component obtained in [Preparation of solid catalyst component] of Example 1.
The same operation as in Example 1 was performed except that mg was used.
As a result, 54 g of polyethylene was obtained. The MI of the obtained polyethylene was 8.19 g / 10 minutes. In addition, almost no polyethylene adhered to the inside of the autoclave.

Example 3 [Polymerization] 500 ml of hexane was added to a 2 l autoclave.
21 ml of the solid catalyst component obtained in [Preparation of solid catalyst component] of Example 1 by adding 500 ml of toluene instead of
The same operation as in Example 1 was performed, except that g was used after being stored in a nitrogen atmosphere for 30 days. As a result, 54g
Of polyethylene was obtained. MI of the obtained polyethylene
Was 0.003 g / 10 minutes. In addition, almost no polyethylene adhered to the inside of the autoclave.

Example 4 [Preparation of carrier] 5.0 g of silica (surface area 126 m ² / g, pore diameter 282 angstrom, pore volume 1.13 cc / g, calcined at 300 ° C. for 5 hours) in a 300 ml glass container. And 10 ml of a toluene solution of trimethylaluminum (20 wt%) and 50 ml of toluene were added,
Contact was carried out at room temperature for 1 hour. In addition, heat to 80 ℃ 1
After continuing contact for a time, decantation was performed. The obtained solid was washed with toluene. At this time, washing was performed until no unreacted trimethylaluminum was found in the washing liquid. The carrier contained 1.9 wt% of Al.

[Preparation of solid catalyst component] In a 300 ml glass container, ethylenebisindenylzirconium dichloride 20 mg, [NH (Me) ₂ Ph] [B (C ₆ F
₅ ) ₄ ] 176 mg, 1.0 g of the carrier prepared in [Preparation of carrier] and 40 ml of toluene were added, and the mixture was reacted at room temperature for 60 minutes, and further reacted at 70 ° C. for 60 minutes. After decanting, it was washed with 80 ml of toluene. The obtained solid was dried under reduced pressure to obtain a solid catalyst component.
Zr is 0.2 wt% and B is 0.16 wt% in the solid catalyst.
%, And Al was contained by 1.8 wt%.

[Polymerization] To a 2-liter autoclave, 500 ml of hexane and 0.2 mmol of triisobutylaluminum were added and stirred for 10 minutes. To this solution, 43 mg of the solid catalyst component obtained in [Preparation of solid catalyst component] and 0.2 mmol of triisobutylaluminum were added to 20 m.
1 hexane solution was charged into an autoclave, and polymerization was carried out at 80 ° C. for 30 minutes while maintaining the inside of the autoclave at 4 kg / cm ² G with ethylene. As a result, 6
5 g of polyethylene was obtained. M of the obtained polyethylene
I was 0.001 g / 10 minutes. In addition, almost no polyethylene adhered to the inside of the autoclave.

Example 5 [Polymerization] Propylene 1400 was added to a 2-liter autoclave.
ml and triethylaluminum 0.15 mmol were added and stirred for 10 minutes. To this solution, 46 mg of the solid catalyst obtained in [Preparation of solid catalyst component] of Example 4 and 0.15 mmol of triethylaluminum were made into 10 ml of a toluene solution under pressure into an autoclave, and polymerization was carried out at 60 ° C. for 60 minutes. As a result, 180 g of polypropylene was obtained. The bulk density of the obtained polypropylene is 0.34 g /
It was cm ³ . Further, there was almost no adhesion of polypropylene in the autoclave.

Example 6 [Preparation of carrier] 5.0 g of silica (surface area 126 m ² / g, pore size 282 Å, pore volume 1.13 cc / g, 700 ° C., 5 hours calcination) in a 300 ml glass container. Then, 10 ml of a toluene solution of dimethylaluminum chloride (20 wt%) and 50 ml of toluene were added, and they were contacted at room temperature for 1 hour. Furthermore, after heating at 80 ° C. and continuing contact for 1 hour, decantation was performed. The obtained solid was washed with toluene. At this time, washing was performed until no unreacted dimethylaluminum chloride was found in the washing liquid. Al is 0.
9 wt% was contained.

[Preparation of solid catalyst component] In a 300 ml glass container, ethylenebisindenyl zirconium dichloride 73 mg, [NH (Me) ₂ Ph] [B (C
₆ F ₅ ) ₄ ] 246 mg, 1.0 g of the carrier prepared in the above [Preparation of carrier] and 40 ml of toluene were added, and the mixture was stirred at room temperature for 60
After the minute reaction, the reaction was further performed at 70 ° C. for 60 minutes. After decanting, it was washed with 80 ml of toluene. The obtained solid was dried under reduced pressure to obtain a solid catalyst component. The solid catalyst component contained 0.7 wt% Zr, 0.03 wt% B, and 0.8 wt% Al.

[Polymerization] To a 2 l autoclave, 500 ml of toluene and 0.75 mmol of triisobutylaluminum were added and stirred for 10 minutes. 91 m of the solid catalyst component obtained in the above [Preparation of solid catalyst component]
g and 0.75 mmol of triisobutylaluminum as a 20 ml toluene solution were charged into an autoclave, and the inside of the autoclave was 4 kg / cm ² with ethylene.
While maintaining at G, polymerization was carried out at 80 ° C. for 30 minutes. As a result, 46 g of polyethylene was obtained. The MI of the obtained polyethylene was 10.41 g / 10 minutes. Also,
There was almost no polyethylene adhering to the inside of the autoclave.

Example 7 [Preparation of carrier] The same procedure as in Example 6 was repeated except that 16.2 ml of a toluene solution of methylalumoxane (20 wt%) was used instead of 10 ml of a toluene solution of dimethylaluminum chloride (20 wt%). It was Al in the carrier
Was contained in an amount of 6.0 wt%.

[Preparation of solid catalyst component] A solid catalyst component was obtained in the same manner as in Example 6 except that the carrier prepared in [Preparation of carrier] was used as the carrier. Zr is 0.7 wt%, B is 0.11 wt% and Al in the solid catalyst.
Was contained in an amount of 5.8 wt%.

[Polymerization] Example 1 except that 11 mg of the solid catalyst component obtained in the above [Preparation of solid catalyst component] was used.
The reaction was performed in the same manner as in. The polyethylene obtained is 48
It was g. The MI of the obtained polyethylene is 0.00
It was 1 g / 10 minutes.

Example 8 [Polymerization] 500 ml of hexane was added to a 2 l autoclave.
25 ml of 1,1-hexene and 0.15 mmol of triisobutylaluminum were added and stirred for 10 minutes. A reaction was performed in the same manner as in Example 7 except that 11 mg of the solid catalyst component obtained in [Preparation of solid catalyst component] of Example 7 was used in this solution. As a result, 27 g of ethylene / 1-hexene copolymer was obtained. The MI of the obtained ethylene / 1-hexene copolymer was 7.9 g / 10 minutes. Also,
Almost no adhesion of polymer was observed in the autoclave.

Example 9 [Polymerization] A 2 l autoclave was charged with sodium chloride (2
190 g (dried at 00 ° C. for 24 hours) and 1.5 mmol of triisobutylaluminum were added and stirred for 10 minutes.
105 mg of the solid catalyst component obtained in [Preparation of solid catalyst component] of Example 7 and 1.5 mmol of triisobutylaluminum were charged into an autoclave as a 10 ml hexane solution, and the inside of the autoclave was filled with ethylene to 8 kg / cm ² G. Polymerization was carried out at 80 ° C. for 30 minutes while maintaining As a result, 8 g of polyethylene was obtained. The MI of the obtained polyethylene was 2.02 g / 10 minutes.

Example 10 [Preparation of carrier] 5.0 g of silica (surface area 126 m ² / g, pore diameter 282 Å, pore volume 1.13 cc / g, 800 ° C., 5 hours calcination) was placed in a 300 ml glass container. And 10 ml of a toluene solution of trimethylaluminum (20 wt%) and 50 ml of toluene were added, and they were contacted at room temperature for 1 hour. Furthermore, after heating at 80 ° C. and continuing contact for 1 hour, decantation was performed. The obtained solid was washed with toluene. At this time, washing was performed until no unreacted trimethylaluminum was found in the washing liquid. The carrier contained 1.9 wt% of Al.

[Preparation of solid catalyst component] 14 m of dimethylsilylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride was placed in a 300 ml glass container.
g, [NH (Me) ₂ Ph] [B (C ₆ F ₅ ) ₄ ] 170 m
g, 1.0 g of the carrier prepared in the above [Preparation of carrier] and 40 ml of toluene were added, and the mixture was reacted at room temperature for 60 minutes. After decanting, it was washed with 80 ml of hexane. The obtained solid was dried under reduced pressure to obtain a solid catalyst component.
Zr is 0.21 wt% and B is 0.07 w in the solid catalyst.
t% and 3.1 wt% of Al were contained.

[Polymerization] To a 2-liter autoclave, 500 ml of toluene and 0.2 mmol of triisobutylaluminum were added and stirred for 10 minutes. To this solution, 20 mg of 32 mg of the solid catalyst component obtained in the above [Preparation of solid catalyst component] and 0.2 mmol of triisobutylaluminum were added.
Was charged into an autoclave as a toluene solution of and the polymerization was carried out at 80 ° C. for 30 minutes while keeping the inside of the autoclave at 4 kg / cm ² G with ethylene. As a result, 2
1.1 g of polyethylene was obtained. In addition, almost no polyethylene adhered to the inside of the autoclave.

Example 11 [Polymerization] Propylene 1400 was added to a 2-liter autoclave.
ml and triethylaluminum 0.15 mmol were added and stirred for 10 minutes. To this solution, 48 mg of the solid catalyst component obtained in [Preparation of solid catalyst component] of Example 10 and 0.15 mmol of triethylaluminum were made into 10 ml of a toluene solution and pressed into an autoclave.
Polymerized for 0 minutes. As a result, 186 g of polypropylene was obtained. The polypropylene obtained has a bulk density of 0.20 g.
/ Cm ³ . Further, there was almost no adhesion of polypropylene in the autoclave.

[0051]

INDUSTRIAL APPLICABILITY According to the present invention, a solid catalyst component comprising a metallocene compound, an ionizable ionic compound and a particulate carrier and a catalyst comprising an organometallic compound as constituent components can be stably stored. Further, by using this catalyst system, it is possible to efficiently produce a polyolefin having excellent physical properties in a regular powder state.

Claims (2)

[Claims] 1. An olefin polymerization catalyst comprising (a) a solid catalyst component and (b) an organometallic compound as constituent components, wherein (a) the solid catalyst component is represented by the general formula (1) Cp ₂ MX ₂ (1). (In the formula, Cp is each independently a cyclopentadienyl group or a substituted cyclopentadienyl group, and Cp's may be bonded to each other. M is titanium, zirconium or hafnium, and X is each independently. halogen, an alkoxy group, an amino group, a metallocene compound represented by an amide group), the following general formula ^{(2) [C +] [} a -] (2) ( where, a [C ^+] is cation, [ A ⁻ ] is an anion), and (b) the organometallic compound has the general formula (3) M′R _n (3) (wherein M ′ is the above). M-X bond of metallocene compound A metal capable of forming an M′-R bond having reactivity with
R is each independently a hydrocarbon group, halogen, hydrogen, an amido group, an alkoxy group or an aryl group, and at least one R is a hydrocarbon group, and n is an integer of 1 to 4) Olefin polymerization catalyst. 2. A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 1.