JP3230762B2 - 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 a solid catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst. More specifically, the present invention is applicable to a suspension polymerization method or a gas phase polymerization method and has a high polymerization efficiency. The present invention relates to a solid catalyst for olefin polymerization capable of producing an active olefin polymer having excellent particle properties, and a method for polymerizing olefin using the catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a catalyst for producing an α-olefin polymer, for example, an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst comprising a titanium compound and an organoaluminum compound or a vanadium compound has been used. There is known a vanadium-based catalyst comprising an organic aluminum compound.

In recent years, a new Ziegler-type olefin polymerization catalyst comprising a zirconium compound and an organoaluminum oxy compound has been developed as a catalyst capable of producing an ethylene / α-olefin copolymer with high polymerization activity. Ethylene ・ α- using new catalyst
A method for producing an olefin copolymer is disclosed in
-19309, JP-A-60-35005,
JP-A-60-35006, JP-A-60-3500
No. 7, JP-A-60-35008, and the like.

[0004] The catalyst formed from a transition metal compound and an organoaluminum oxy compound proposed in these prior arts is a catalyst formed from a transition metal compound and an organoaluminum compound which has been known before the appearance of this catalyst. Although the polymerization activity, especially ethylene polymerization activity, is superior, most of them are soluble in the reaction system, and in most cases, the production process is limited to the solution polymerization system, and it is intended to produce a polymer with a high molecular weight. Then, the viscosity of the solution containing the polymer becomes extremely high, which causes a problem that productivity is lowered, or a polymer obtained after the post-polymerization has a low bulk specific gravity and produces a spherical olefin polymer having excellent particle properties. There is a problem that it is difficult to do.

On the other hand, using a catalyst in which at least one component of a transition metal compound and an organoaluminum oxy compound is supported on a porous inorganic oxide carrier such as silica, alumina or silica-alumina, a suspension polymerization system or a gas phase is used. Attempts have also been made to polymerize olefins in polymerization systems.

For example, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35007
JP-A-35008 discloses that a transition metal compound and an organoaluminum oxy compound are formed of silica, alumina, silica.
It is described that a catalyst supported on alumina or the like can be used.

[0007] JP-A-60-106808 and JP-A-60-106809 disclose that a highly active catalyst component containing a titanium compound and / or a zirconium compound soluble in a hydrocarbon solvent is contacted with a filler in advance. A composition comprising a polyethylene-based polymer and a filler by copolymerizing ethylene or ethylene and an α-olefin in the presence of a product obtained by the treatment, an organoaluminum compound, and a filler having a polyolefin affinity. A method for making an article is described.

Japanese Patent Application Laid-Open No. 61-31404 discloses that in the presence of a mixed catalyst comprising a product obtained by reacting a trialkylaluminum with water in the presence of silicon dioxide or aluminum oxide and a transition metal compound. A method for polymerizing or copolymerizing ethylene or ethylene with an α-olefin is described.

Japanese Patent Application Laid-Open No. 61-276805 discloses a reaction in which a zirconium compound and a reaction mixture obtained by reacting aluminoxane with trialkylaluminum are further reacted with an inorganic oxide having a surface hydroxyl group such as silica. It is described that an olefin is polymerized in the presence of a catalyst comprising a mixture.

JP-A-61-108610 and JP-A-61-296008 disclose olefins in the presence of a catalyst in which a transition metal compound such as a metallocene and an aluminoxane are supported on a carrier such as an inorganic oxide. Are described.

However, when an olefin is polymerized or copolymerized in a suspension polymerization system or a gas phase polymerization system using a solid catalyst component supported on a carrier described above, the polymerization activity is higher than that in the solution polymerization system. It was remarkably reduced, and the bulk specific gravity of the produced polymer was not sufficiently satisfactory.

Further, JP-A-63-280703 describes a method of prepolymerizing an olefin in the presence of a carrier such as a zirconocene compound, an aluminoxane, an organoaluminum compound and silica. In this method, although the polymerization activity is high and the particle properties of the produced polymer are excellent, there is a problem that a prepolymerized catalyst adheres to a reaction wall or the like during prepolymerization.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and can be applied to a suspension polymerization method or a gas phase polymerization method, and has high polymerization activity and excellent particle properties. It is an object of the present invention to provide a solid catalyst for olefin polymerization which can produce a spherical olefin polymer and which gives a copolymer having a narrow composition distribution when two or more monomers are copolymerized. Another object of the present invention is to provide a method for polymerizing an olefin using a catalyst having such good properties.

[0014]

The solid catalyst for olefin polymerization according to the present invention comprises [A] (a-1) (i) an oxide of at least one element selected from the group II, group III and group IV; ii) the amount of adsorbed water is less than 1.0% by weight, and (iii) 2.0-3.5% by weight of a fine particle carrier having a surface hydroxyl group, wherein (a-2) an organic aluminum oxy compound is supported A solid catalyst component comprising: component (a-1)
The molar ratio (OH / Al _a-2 ) of the surface hydroxyl group (OH) of (a) to the aluminum (Al _a-2 ) of the component ( _a-2 ) is 0.15 to 0.15.
0.4, a solid catalyst component obtained by mixing and contacting, and [B] a IVB group transition metal compound containing a ligand having a hydrocarbon group-substituted cyclopentadienyl skeleton; [C] a catalyst component comprising an organoaluminum compound,
When the component [C] is used at a ratio such that the atomic ratio (Al / transition metal) of aluminum of the component (a-2) to the transition metal in the component [B] is in the range of 20 to 200, the component [ C] and the atomic ratio (Al _c / Al) between the aluminum atom (Al _c ) and the aluminum atom (Al _a-2 ) of the component (a-2).
_a-2 ) is used in such a ratio as to be in the range of 0.02 to 3,
In suspension or in the gas phase, it is formed by prepolymerizing olefin.

The olefin polymerization method according to the present invention is characterized in that the olefin is polymerized or copolymerized in the presence of the solid catalyst as described above.

[0016]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the solid catalyst for olefin polymerization according to the present invention and a method for polymerizing olefin using the catalyst will be described in detail.

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. It may be used with the incorporation of coalescence.

The (a-1) particulate carrier (hereinafter sometimes referred to as "component (a-1)") used in the present invention is at least one selected from Group II, Group III and Group IV. A particulate inorganic compound composed of an oxide of an element is used.

As such a particulate inorganic compound, a porous oxide is preferable, and specifically, SiO ₂ , Al
₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, Z
nO, BaO, ThO _{2 and the} like, or a mixture containing them, such as SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO _2-
TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO _2-
TiO ₂ -MgO can be exemplified. Among them, those containing at least one component selected from the group consisting of SiO ₂ , Al ₂ O ₃ and Mg are preferred.

[0020] (a-1) particulate carrier is desirably an average particle diameter of <br/> through normal 1 0～200Myuemu, specific surface area
Is preferably 100 to 700 m ² / g, and the pore volume is preferably 0.3 to 2.5 cm ³ / g.

In such a (a-1) particulate carrier, the amount of adsorbed water is less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl groups are 1.0% by weight or more, preferably It is desirable that the content be 0.5 to 4.0% by weight, particularly preferably 2.0 to 3.5% by weight.

Here, the amount of adsorbed water (% by weight) and the surface hydroxyl groups (% by weight) are determined as follows. [Amount of adsorbed water] at a temperature of 200 ° C. under normal pressure and nitrogen flow
The weight loss when dried for a period of time is defined as the amount of adsorbed moisture. [Surface hydroxyl group] The carrier obtained by drying at a temperature of 200 ° C. under normal pressure under a stream of nitrogen for 4 hours was defined as X (g), and the carrier was calcined at 1000 ° C. for 20 hours. The weight of the fired product from which the surface hydroxyl groups have disappeared is calculated as Y (g) by the following formula.

Surface hydroxyl group (% by weight) = {(XY) / X} × 100 By using such a finely divided carrier having a specific amount of adsorbed water and a surface hydroxyl group, it has high polymerization activity and excellent particle properties. Thus, a solid catalyst component for olefin polymerization capable of producing an olefin polymer can be obtained.

The (a-2) organoaluminum oxy compound (hereinafter sometimes referred to as "component (a-2)") used in the present invention may be a conventionally known aluminoxane. It may be a benzene-insoluble organic aluminum oxy compound.

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension to recover a hydrocarbon solution.

(2) A method in which an organic aluminum compound such as trialkylaluminum is directly reacted with water, ice or water vapor in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover as a hydrocarbon solution.

(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 an organometallic component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-
Trialkylaluminum such as butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricyclohexylaluminum, tricyclooctylaluminum Tricycloalkylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; dimethylaluminum methoxide, diethylaluminum ethoxy Like dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide; dialkylaluminum alkoxides such as.

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred.
Further, isoprenyl aluminum represented by the following general formula [I] can also be used as the organic aluminum compound.

(I-C ₄ H ₉ ) _X Al _y (C ₅ H ₁₀ ) _Z ... [I] (where x, y, and z are positive numbers and z ≧ 2x). Such organoaluminum compounds are used alone or in combination.

Solvents used in the production of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Hydrocarbons, cyclopentane, cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclopentane, gasoline, kerosene, petroleum fractions such as light oil or the above aromatic hydrocarbons, aliphatic hydrocarbons,
A hydrocarbon solvent such as an alicyclic hydrocarbon halide, especially a chlorinated product or a brominated product, may be used. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound used in the present invention may be prepared, for example, by contacting a solution of aluminoxane with water or an active hydrogen-containing compound, or by contacting the above-mentioned organoaluminum with water. It can be obtained by a method or the like.

In the first method for obtaining a benzene-insoluble organoaluminum oxy compound, a solution of aluminoxane is brought into contact with water or an active hydrogen-containing compound. Active hydrogen-containing compounds include methanol, ethanol, n-
Alcohols such as propanol and isopropanol,
Diols such as ethylene glycol and hydroquinone, and organic acids such as acetic acid and propionic acid are used. Of these, alcohols and diols are preferred, and alcohols are particularly preferred.

The water or active hydrogen-containing compound to be brought into contact with the aluminoxane solution is dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene, hexane, etc., an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or It can be used in vapor, solid or solid form. In addition, as water, crystallization water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, cerous chloride, etc., or inorganic compounds or polymers such as silica, alumina, aluminum hydroxide and the like are adsorbed. Adsorbed water or the like can also be used.

The contact reaction between the aluminoxane solution and water or an active hydrogen-containing compound is usually carried out in a solvent, for example, a hydrocarbon solvent. Examples of the solvent used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; cyclopentane and cyclohexane , Cyclooctane, methylcyclohexane and other alicyclic hydrocarbons; hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene and light oil, and the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbon halides And halogenated hydrocarbons such as chlorinated products and brominated products, and ethers such as ethyl ether and tetrahydrofuran.

Among these media, aromatic hydrocarbons are particularly preferred. The water or active hydrogen-containing compound used in the catalytic reaction is used in an amount of 0.1 to 5 mol, preferably 0.2 to 3 mol, based on Al atoms in the aluminoxane solution. The concentration in the reaction system is usually in the range of 1 × 10 ^{−3 to} 5 g atom / l, preferably 1 × 10 ^{−2 to} 3 g atom / l, in terms of aluminum atom. The concentration of water in the system is usually 2 × 10 ^{−4 to} 5 mol / L, preferably 2 × 10 ^{−4 to} 5 mol / L.
It is desirable that the concentration be from × 10 ^{−3 to} 3 mol / l.

As a method for bringing the aluminoxane solution into contact with water or an active hydrogen-containing compound, the following method is specifically mentioned. (1) A method in which a solution of aluminoxane is brought into contact with water or a hydrocarbon solvent containing an active hydrogen-containing compound.

(2) A method in which water or an active hydrogen-containing compound vapor is blown into a solution of aluminoxane, thereby bringing the aluminoxane into contact with the vapor. (3) A method in which a solution of aluminoxane is brought into direct contact with water, ice or an active hydrogen-containing compound.

(4) A solution of aluminoxane is mixed with a hydrocarbon suspension of a compound containing adsorbed water or a compound of crystallization or a hydrocarbon suspension of a compound to which an active hydrogen-containing compound is adsorbed. A method in which aluminoxane is brought into contact with adsorbed water or water of crystallization.

The aluminoxane solution as described above may contain other components as long as the reaction between the aluminoxane and water or an active hydrogen-containing compound is not adversely affected.

The contact reaction between the solution of aluminoxane and water or an active hydrogen-containing compound is usually carried out at -50 to 150
° C, preferably 0 to 120 ° C, more preferably 20 to 1 ° C.
It is performed at a temperature of 00 ° C. The reaction time varies greatly depending on the reaction temperature, but is usually 0.5 to 300 hours.
Preferably, it is about 1 to 150 hours.

In a second method for obtaining a benzene-insoluble organoaluminum oxy compound, organoaluminum is contacted with water. Water is used in such an amount that the organic aluminum atoms dissolved in the reaction system become 20% or less based on all the organic aluminum atoms.

The water to be brought into contact with the organoaluminum compound is used by dissolving or dispersing it in a hydrocarbon solvent such as benzene, toluene or hexane, an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or in the form of steam or ice. be able to. As water, it was adsorbed on water of crystallization of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerous chloride, or on inorganic compounds or polymers such as silica, alumina and aluminum hydroxide. Adsorbed water or the like can also be used.

The reaction between the organoaluminum compound and water is usually carried out in a hydrocarbon solvent. Examples of the hydrocarbon solvent used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; and cyclopentane. , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclohexane, petroleum fractions such as gasoline, kerosene, and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorinated products And hydrocarbon solvents such as bromides. In addition, ethers such as ethyl ether tetrahydrofuran can be used. Of these media, aromatic hydrocarbons are particularly preferred.

The concentration of the organoaluminum compound in the reaction system is usually in the range of 1 × 10 ^{−3 to} 5 g atoms / l, preferably 1 × 10 ^{−2 to} 3 g atoms / l in terms of aluminum atoms. The concentration of water in the reaction system is usually 1 × 10 ^{−3 to} 5 mol / l, preferably 1 × 10 ^{−2 to} 3 mol / l. At this time, the organic aluminum atoms dissolved in the reaction system are desirably 20% or less, preferably 10% or less, more preferably 0 to 5% based on all the organic aluminum atoms.

As a method for bringing the organoaluminum compound into contact with water, the following method is specifically mentioned. (1) A method in which a hydrocarbon solution of an organic aluminum is brought into contact with a hydrocarbon solvent containing water.

(2) A method in which steam is blown into a hydrocarbon solution of organoaluminum to bring the organoaluminum into contact with steam. (3) A method in which a hydrocarbon solution of an organic aluminum is mixed with a hydrocarbon suspension of a compound containing adsorbed water or a compound containing water of crystallization, and the organic aluminum is brought into contact with the adsorbed water or the water of crystallization.

(4) A method of bringing a hydrocarbon solution of an organoaluminum into contact with ice. The organic aluminum hydrocarbon solution as described above may contain other components as long as the reaction between the organic aluminum and water is not adversely affected.

The contact reaction between the organoaluminum compound and water is usually carried out at -100 to 150 ° C., preferably at -70 to 10 ° C.
It is carried out at a temperature of 0 ° C, more preferably -50 to 80 ° C. The reaction time varies greatly depending on the reaction temperature, but is usually about 1 to 200 hours, preferably about 2 to 100 hours.

Such a benzene-insoluble organoaluminum oxy compound is obtained by dissolving Al in a benzene solution at 60 ° C.
The component is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, and is insoluble or hardly soluble in benzene. The solubility of the organoaluminum oxy compound in benzene was determined by suspending the organoaluminum oxy compound corresponding to 100 milligram atoms of Al in 100 ml of benzene, mixing the mixture at 60 ° C. with stirring for 6 hours, and adding a jacketed G-5. A hot filter was performed at 60 ° C. using a glass filter, and the solid portion separated on the filter was washed four times with 50 ml of benzene at 60 ° C., and the amount of Al atoms present in the entire filtrate was determined. x mmol) (x mmol)
%).

When the benzene-insoluble organoaluminum oxy compound as described above is analyzed by infrared spectroscopy (IR), the absorbance (D ₁₂₂₀ ) around ₁₂₂₀ cm ⁻¹ is obtained.
And the absorbance (D ₁₂₆₀ / D ₁₂₂₀ ) at around ₁₂₆₀ cm ⁻¹ (D ₁₂₆₀ / D ₁₂₂₀ ) is 0.09 or less, preferably 0.09 or less.
8 or less, particularly preferably in the range of 0.04 to 0.07.

The infrared spectroscopic analysis of the organic aluminum oxy compound is performed as follows. First, the organic aluminum oxy compound and nujol are ground in an agate mortar in a nitrogen box to form a paste. Next, the paste-form sample is sandwiched between KBr plates, and an IR spectrum is measured by IR-810 manufactured by JASCO Corporation under a nitrogen atmosphere. From the IR spectrum thus obtained, D
₁₂₆₀ / _D1220 is obtained, and the value of _D1260 / _D1220 is obtained as follows.

(B) Around 1280 cm ^-1 and 1240 cm
^-1 bear maximum point in the vicinity, which is the baseline L _1. (B) Transmittance at the minimum absorption point near 1260 cm ^-1 (T
%) And a perpendicular to the wave number axis (horizontal axis) is drawn from this minimum point, the transmittance (T ₀ %) at the intersection of the perpendicular and the baseline L ₁ is read, and the absorbance (D near 1260 cm ⁻¹ ) is determined. ₁₂₆₀ = log T ₀ / T) is calculated.

(C) Similarly, around 1280 cm ^-1 and 118
The maximum point near 0 cm ^-1 is connected, and this is connected to the baseline L ₂
And (D) The transmittance (T ′) at the minimum absorption point near 1220 cm ⁻¹
%) And a perpendicular to the wave number axis (horizontal axis) is drawn from this minimum point, and the transmittance (T ₀ '%) at the intersection of the perpendicular and the base line L ₂ is read, and the absorbance around 1220 cm ⁻¹ ( D ₁₂₂₀ = log T ₀ '/ T').

(E) From these values, D₁₂₆₀/ D₁₂₂₀Total
Calculate. Benzene-soluble organoaluminum oxy compounds
Things are D₁₂₆₀/ D₁₂₂₀Value is between approximately 0.10 and 0.13
Benzene-insoluble organic aluminum oxy compound
The product is a conventionally known benzene-soluble organic aluminum oxide.
Xy compound and D₁₂₆₀/ D ₁₂₂₀Clearly different in value
You.

The above-mentioned benzene-insoluble organoaluminum oxy compound is presumed to have an alkyloxyaluminum unit represented by the following formula [II].

[0058]

Embedded image

(In the formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms.) In the above formula [II], R ¹ is specifically a methyl group, an ethyl group, an n-propyl group, Examples thereof include isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl, cyclohexyl, and cyclooctyl. In these, methyl group,
Ethyl groups are preferred, and methyl groups are particularly preferred.

This benzene-insoluble organoaluminum oxy compound contains an oxyaluminum unit (ii) represented by the following formula [III] in addition to the alkyloxyaluminum unit (i) represented by the above formula [II]. May be.

[0061]

Embedded image

(Wherein, R ² is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms,
Aryloxy group, hydroxyl group, halogen or hydrogen. R ² and R ¹ in the above formula [II] represent different groups. In this case, an organoaluminum oxy compound having an alkyloxyaluminum unit containing at least 30 mol%, preferably at least 50 mol%, particularly preferably at least 70 mol% of the alkyloxyaluminum unit (i) is desirable.

The [B] group IVB transition metal compound containing a ligand having a cyclopentadienyl skeleton (hereinafter sometimes referred to as “component [B]”) used in the present invention is represented by the following formula: The compound represented by [IV] can be exemplified.

ML _X ... [IV] In the general formula [IV], M is a transition metal of Group IVB of the periodic table, and specifically, zirconium, titanium or hafnium, and L is a transition metal. A ligand to be coordinated, at least one L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton has 1 to 12 carbon atoms. hydrocarbon group, an alkoxy group, an aryloxy group, a halogen atom, trialkylsilyl group, -SO ₃ R (wherein, R is a hydrocarbon group of carbon atoms which may 1-8 have a substituent such as a halogen .) Or a hydrogen atom, and x is the valence of the transition metal.

Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, and a tetramethylcyclopentadienyl group. Group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclo Examples thereof include an alkyl-substituted cyclopentadienyl group such as a pentadienyl group and a hexylcyclopentadienyl group, an indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferred. When the compound represented by the general formula [IV] contains two or more groups having a cyclopentadienyl skeleton, two of the groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene. It may be bonded via a substituted alkylene group such as isopropylidene or diphenylmethylene, or a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group.

The ligands other than those having a cyclopentadienyl skeleton include the following. Specifically as a hydrocarbon group having 1 to 12 carbon atoms,
Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and pentyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; An aralkyl group is exemplified.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a butoxy group. Examples of the aryloxy group include a phenoxy group.

As the halogen, fluorine, chlorine, bromine,
Examples include iodine. Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.

The compound represented by the above general formula [IV] is an example
For example, when the valence of the transition metal is 4, more specifically,
It is represented by the following general formula [IV ′]. R¹ _aR^Two _bR^Three _cR^Four _dM ... [IV '] (In the formula [IV'], M is zirconium, titanium or Hough
And R¹Has a cyclopentadienyl skeleton
R^Two, R^ThreeAnd R^FourIs cyclopentadie
A group having a nyl skeleton, an alkyl group, a cycloalkyl group,
Aryl group, aralkyl group, alkoxy group, aryloxy
Si group, halogen atom, trialkylsilyl group, -SO_Three
R is a hydrogen atom, a is an integer of 1 or more;
+ B + c + d = 4. In the present invention, the above general formula [I
V ']^Two, R^ThreeAnd R^FourOne of them is cyclo
Transition metal compound which is a group having a pentadienyl skeleton,
For example, R¹And R ^TwoHas a cyclopentadienyl skeleton
The transition metal compound which is a group to be used is preferably used. This
These groups having a cyclopentadienyl skeleton are
Alkylene groups such as ethylene and propylene, diphenylmethylene
Substituted alkylene groups such as isopropylidene, etc.
Alkylidene group, silylene group or dimethylsilylene,
Substitution of phenylsilylene, methylphenylsilylene, etc.
They may be bonded via a silylene group or the like. Also,
R^ThreeAnd R^FourHas a cyclopentadienyl skeleton
Group, alkyl group, cycloalkyl group, aryl group, ara
Alkyl group, alkoxy group, aryloxy group, halogen source
, Trialkylsilyl group, SO_ThreeR or hydrogen atom
is there.

The following are specific examples of the transition metal compound in which M is zirconium. Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium Dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dibromide, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) Zirconium bis (methanesulfonato), ethylenebis (indenyl) zirconiumbis (p-toluenesulfonato), ethylenebis (indenyl) zirconi Umbis (trifluoromethanesulfonato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentane) Dienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclo) (Pentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl)
Zirconium bis (trifluoromethanesulfonate),
Dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) zirconium dichloride , Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentane Dienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl Benzalkonium monochloride,
Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methyl zirconium monohydride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadiene) (Enyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl)
Zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, Bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadiene) Le) zirconium dichloride, bis (methyl-butylcyclopentadienyl) zirconium dichloride, bis (methyl-butylcyclopentadienyl)
Zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride,
Bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples, disubstituted cyclopentadienyl ring includes 1,2- and 1,3-substituted, and trisubstituted 1,2-, 3- and 1,2,4- Including substitutions. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
And isomers.

In the present invention, a transition metal compound in which zirconium metal is replaced with titanium metal or hafnium metal in the zirconium compound as described above can also be used.

As the [C] organoaluminum compound (hereinafter sometimes referred to as “component [C]”) used in the present invention, for example, an organoaluminum compound represented by the following formula [V] is exemplified. Can be.

R ⁷ _n AlX _3-n ... [V] (wherein, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms;
Is halogen or hydrogen, and n is 1 to 3. ) In the above formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, methyl, ethyl, n-propyl, isopropyl Group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

As such an organoaluminum compound, specifically, the following compounds are used. Trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum; alkenylaluminum such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutyl Dialkylaluminum halides such as aluminum chloride and dimethylaluminum bromide; alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

Further, [C] is an organoaluminum compound.
Thus, a compound represented by the following formula [VI] can also be used.
You. R⁷ _nAlY_3-n ... [VI] (wherein, R⁷Is the same as above, and Y is -OR⁸Group,-
OSiR⁹ _ThreeGroup, -OAlR^Ten _TwoGroup, -NR¹¹ _TwoGroup,-
SiR¹² _ThreeGroup or -N (R¹³) AlR¹⁴ _TwoGroup,
n is 1-2, R⁸, R⁹, R^TenAnd R¹⁴Is meth
Group, ethyl group, isopropyl group, isobutyl group, cycle
Rohexyl group, phenyl group, etc. ¹¹Is hydrogen,
Chill, ethyl, isopropyl, phenyl, tri
A methylsilyl group or the like;¹²And R¹³Is methyl
And an ethyl group. ) Such organic aluminum
Specifically, the following compounds may be used.
Used.

(I) Compounds represented by R ⁷ _n Al (OR ⁸ ) _3-n , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like.

[0079] _{^{(ii) R 7 n Al (}} OSi R 9 3) compounds represented by _3-n, e.g., _{Et 2 Al (OSi Me 3)} (iso-Bu) 2 Al (OSi Me 3) (iso-Bu ) ₂ Al (OSi Et ₃ ).

(Iii) Compounds represented by R ⁷ _n Al (OAlR ¹⁰ ₂ ) _3-n , such as Et ₂ AlOAlEt ₂ (iso-Bu) ₂ AlOAl (iso-Bu) ₂ .

[0081] _{^{(iv) 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 (Si Me 3) 2 (iso-Bu) 2 AlN (SiMe ₃ ) _{2 and the} like.

[0082] _{^{(v) R 7 n Al (}} Si R 12 3) a compound represented by _3-n, e.g., (iso-Bu) such as ₂ AlSi Me _3.

[0083]

Embedded image

[0084] The above general formula [V], in an organic aluminum compound represented by [VI] _{^{is, R 7 3 Al, R 7}} n Al (OR
⁸ ) _3-n , organoaluminum compounds represented by R ⁷ _n Al (OAlR ¹⁰ ₂ ) _3-n can be mentioned as preferred examples,
R ⁷ is preferably an isoalkyl group, and n = 2 is particularly preferred. These organoaluminum compounds can be used as a mixture of two or more kinds.

The solid catalyst for olefin polymerization according to the present invention comprises (a-1) a particulate carrier, (a-2) an organoaluminum oxy compound, [B] a IVB group transition metal compound having a cyclopentadienyl skeleton, It can be prepared by further mixing [C] an organoaluminum compound in an inert hydrocarbon solvent, introducing an olefin into the mixture, and performing preliminary polymerization, if necessary.

At this time, the mixing order is arbitrarily selected. Preferably, the component (a-1) and the component (a-2) are mixed and contacted, and then mixed in the order of the component [B], or a-1) and component (a-2) are mixed and contacted, and then component [B] and component [C] are mixed in that order, or component (a-1) and component (a-2) are mixed. Are mixed and contacted, and then component [C] and component [B] are mixed in this order.

FIG. 1 shows a process for preparing the olefin polymerization catalyst according to the present invention. As the inert hydrocarbon medium used for preparing the solid catalyst for olefin polymerization according to the present invention, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene Cyclopentane, cyclohexane,
Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

Component (a-1), component (a-2), component [B]
When mixing the component [C] if necessary, the component (a-2) is used in an amount of usually 5 × 10 ^-4 to 1 g of the component (a-1).
It is used in an amount of 2 × 10 ^-2 mol, preferably 10 ^-3 to 10 ^-2 mol, and the concentration of the component (a-2) is about 5 × 10 ^-2 to 2 mol / l, preferably 0.1. １1 mol / liter. Further, the surface hydroxyl group (OH) of the component (a-1)
The molar ratio of aluminum (Al _a-2) component (a-2) (OH / Al a-2) is in the range of usually 0.15 to 0.4.

The atomic ratio (Al / transition metal) between aluminum of the component (a-2) and the transition metal in the component [B] is as follows:
Through, which is a normally-2 0 to 200. Atomic ratio of aluminum atoms (Al _a-2) of the aluminum atoms in the component [C] used if necessary (Al _C) and the component _{(a-2) (Al C} / Al
_a-2 ) is usually 0.02 to 3, preferably 0.05 to 1.5.
Range.

Component (a-1), component (a-2), component [B]
The mixing temperature at the time of mixing the component [C] and, if necessary, is usually -50 to 150 ° C, preferably -20 to 120 ° C.
C. and a contact time of 1 to 1000 minutes, preferably 5 to 1000 minutes.
~ 600 minutes. In particular, component (a-1) and component (a-
The reaction temperature with 2) is usually 50 to 150 ° C, preferably 60 to 120 ° C. The contact time is 0.5 to 100
Hours, preferably 1 to 50 hours.

In the present invention, as described above, component (a-1), component (a-2), component [B] and, if necessary, component [C]
Are mixed in an inert hydrocarbon medium, and prepolymerization is carried out by introducing olefin thereto. In the prepolymerization, the transition metal compound is usually used in an amount of 10 ⁻⁵ to 2 × 10 ⁻² mol / l, preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / l, and the prepolymerization temperature is -20. ~ 80 ° C,
The temperature is preferably 0 to 50 ° C., and the prepolymerization time is 0.1.
It is about 5 to 100 hours, preferably about 1 to 50 hours.

As an olefin used in the prepolymerization,
Is selected from olefins used during polymerization
However, the main component is preferably ethylene. Above
The solid catalyst for olefin polymerization of the present invention thus obtained
Is about 5 × 10 per gram of component (a-1)^-6~ 5 × 10^-FourThe
Lamb atom, preferably 10^-Five~ 2 × 10 ^-FourGram atom
A transition metal atom is supported, and about 10^-3~ 5 × 10^-2The
Ram atom, preferably 2 × 10^-3~ 2 × 10^-2Gram Hara
It is desirable that aluminum atoms
No. Furthermore, the amount of polymer produced by prepolymerization depends on the components
(A-1) About 0.1 to 500 g, preferably 0.3 g per gram
To 300 g, particularly preferably 1 to 100 g.
It is desirable.

[0093] In the olefin as described above performs the polymerization of olefins using the prepolymerized solid catalyst component [B] is usually in terms of 1 liter of the polymerization volume transition metal atom is 10 ^- It is desirable that it be used in an amount of ⁸ to 10 ^-3 gram atoms, preferably 10 ^-7 to 10 ^-4 gram atoms. At this time, an organic aluminum compound or an aluminoxane may be used as necessary. As the organoaluminum compound used at this time, the same compounds as the above-mentioned organoaluminum compound [C] can be mentioned. The amount used is desirably in the range of 0 to 500 mol, preferably 5 to 200 mol, per gram atom of the transition metal atom.

Examples of the olefin that can be polymerized with such an olefin polymerization catalyst include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, -Methyl
1-pentene, 1-octene, 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl 1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be used.

In the present invention, 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 in the catalyst preparation method can be used, and the olefin itself can be used as the solvent.

The polymerization temperature of olefin using such an olefin polymerization catalyst is usually in the range of -50 to 150 ° C, preferably 0 to 100 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² .
kg / cm ² , and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages under different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

In the present invention, the catalyst for olefin polymerization may contain other components useful for olefin polymerization in addition to the above components.

[0098]

The solid catalyst for olefin polymerization according to the present invention has (a-1) an amount of adsorbed water of less than 1.0% by weight, and
(A-2) a solid catalyst component comprising an organoaluminum oxy compound supported on a particulate carrier having 2.0 to 3.5% by weight of surface hydroxyl groups, wherein the component (a-1) has surface hydroxyl groups ( OH) and aluminum (A) of component (a-2)
la _-2 ) in a molar ratio (OH / Ala _-2 ) of 0.15 to 0.5.
4, a solid catalyst component [A] obtained by mixing and contacting, a group IVB transition metal compound [B] containing a ligand having a hydrocarbon group-substituted cyclopentadienyl skeleton,
If necessary, a catalyst component comprising an organoaluminum compound [C] is used as a component (a-2) of aluminum and a transition metal in component [B] at a specific ratio. It is formed by preliminarily polymerizing an olefin in a suspension or in a gas phase by using the aluminum atom of a-2) in a specific ratio.

Such a solid catalyst for olefin polymerization includes:
Spherical olefin polymer with high polymerization activity and excellent particle properties can be produced, and when two or more monomers are copolymerized, a copolymer having a narrow composition distribution can be obtained, and prepolymerization can be performed. Sometimes, the prepolymerized catalyst does not adhere to the reaction wall and the like.

[0100]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

The amount of the n-decane-soluble component of the ethylene copolymer obtained according to the present invention (the smaller the soluble amount, the narrower the composition distribution) is that about 3 g of the copolymer is mixed with 450 ml of n-decane.
In addition, after melting at 145 ℃, cooled to 23 ℃
The measurement was performed by removing the n-decane-insoluble portion by filtration and recovering the n-decane-soluble portion from the filtrate.

The density was 2.16 k at 190 ° C.
Strand obtained at the time of MFR measurement with g load is 120
After heat treatment at 1 ° C. for 1 hour and cooling to room temperature over 1 hour, measurement was carried out using a density gradient tube.

The average particle size of the polymer and
The amount of fine powder of m or less was measured by a sieve.

[0104]

[Example 1] [Preparation of solid catalyst (zirconium catalyst)] Silica (manufactured by Fuji Devison, TG-20643) was dried at 200 ° C for 6 hours in a nitrogen stream in a 400 ml glass flask sufficiently purged with nitrogen ( 18.0 g of an adsorbed water amount of 0.1% by weight or less and a hydroxyl group content of 2.7% by weight) and 200 ml of toluene were put into a suspension and cooled to 0 ° C. A toluene solution of an organic aluminum oxy compound in this suspension (Methylaluminoxane manufactured by Schering Co., Ltd., dried and then redissolved in toluene, Al: 1.465 mol / l)
70.3 ml was added dropwise over 45 minutes. At this time, the temperature in the system was kept at 0 ° C. Thereafter, the reaction was carried out at 0 ° C. for 1.5 hours, at room temperature for 2 hours, and further at 80 ° C. for 4 hours.

30 ml of the suspension thus obtained was transferred to another 400 ml glass flask, and 100 ml of decane and 3.0 ml of a triisobutylaluminum decane solution (Al; 1 mol / l) were added.
Stirred for minutes.

Next, 2.2 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr; 0.0451 mol / l) was added to the suspension.
Was added and stirred for 15 minutes.

Thereafter, 100 ml of decane was added, ethylene gas (normal pressure) was continuously introduced, and preliminary polymerization was carried out at 30 ° C. for 9 hours. At this time, no adhesion of the prepolymerized catalyst to the reactor wall was observed.

After the prepolymerization, the solvent was removed by decantation, and the resultant was washed with 150 ml of hexane. By performing this washing six times, a solid catalyst containing 4.4 mg of zirconium, 164 mg of aluminum and 40 g of polyethylene per 1 g of silica was obtained. The solid catalyst was resuspended in hexane for polymerization.

[Polymerization] 150 g of sodium chloride (special grade of Wako Pure Chemical Industries, Ltd.) was charged into a 2-liter stainless steel autoclave sufficiently purged with nitrogen, and dried under reduced pressure at 90 ° C. for 1 hour. Thereafter, the pressure was returned to normal pressure by introducing a mixed gas of ethylene and 1-butene (1-butene content: 7.2 mol%), and the inside of the system was heated to 70 ° C.

Next, the solid catalyst prepared as described above was added to an autoclave containing 0.003 milligram atoms in terms of zirconium atoms and 0.5 millimoles of triisobutylaluminum.

Thereafter, 30 N ml of hydrogen was introduced, and a mixed gas of the above ethylene and 1-butene was introduced.
The polymerization was started at kg / cm ² -G. Immediately 7
The temperature rose to 5 ° C.

Thereafter, only the mixed gas was supplied, and the total pressure was increased to 8%.
While maintaining the pressure at kg / cm ² -G, polymerization was carried out at 75 ° C. for 1 hour. After completion of the polymerization, sodium chloride was removed by washing with water, the remaining polymer was washed with methanol, and then dried at 80 ° C. overnight under reduced pressure. As a result, the MFR measured under a load of 2.16 kg at 190 ° C. was 1.79 g / 10 min, the density was 0.903 g / cm ³ , and the amount of the decane-soluble component at 23 ° C. was 3.4. % By weight and a bulk specific gravity of 0.40 g / c.
m ³ , the average polymer particle size is 700 μm,
192 g of an ethylene / 1-butene copolymer in which the amount of fine polymer having a particle size of 00 μm or less was 0% by weight was obtained.

[0113]

Example 2 [Preparation of solid catalyst (zirconium catalyst)] 17.8 g of the same silica as in Example 1 and 225 ml of toluene were put into a suspension and cooled to 0 ° C. 88. A toluene solution of an organic aluminum oxy compound (Methylaluminoxane manufactured by Schering Co., Ltd., dried and redissolved in toluene, Al: 1.157 mol / l) in this suspension.
3 ml was added dropwise over 75 minutes.
Kept. Thereafter, the reaction was carried out at 0 ° C. for 1 hour, at room temperature for 1.5 hours, and further at 80 ° C. for 4 hours.

30 ml of the suspension thus obtained was transferred to another 400 ml glass flask, and 100 ml of decane and 2.77 ml of a decane solution of triisobutylaluminum (Al; 1 mol / l) were added.
Stir for 5 minutes.

Next, 3.54 m of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr; 0.0348 mol / l) was added to the suspension.
1 was added and stirred for 10 minutes.

Thereafter, 50 ml of decane was added, ethylene gas (normal pressure) was continuously introduced, and prepolymerization was performed at 30 ° C. for 9 hours. At this time, no adhesion of the prepolymerized catalyst to the reactor wall was observed.

After this prepolymerization, the solvent was removed by decantation, and the residue was washed with 150 ml of hexane. By performing the washing six times, 6.9 mg of zirconium, 200 mg of aluminum and 200 mg of polyethylene were added to 1 g of silica. A solid catalyst containing 33 g was obtained. The solid catalyst was resuspended in hexane for polymerization.

[Polymerization] In the polymerization of Example 1, using the solid catalyst prepared above, the 1-butene content in the mixed gas was 9.0 mol%, the hydrogenation amount was 20 Nml, and the polymerization temperature was 6
The same procedure as in Example 1 was carried out except that the temperature was 5 ° C., and the MFR was 1.
46 g / 10 min, a density of 0.890 g / cm ³ , a bulk specific gravity of 0.42 g / cm ³ , a polymer average particle size of 870 μm, and an amount of fine polymer of 100 μm or less being 0% by weight. Certain ethylene / 1-butene copolymer 2
36 g were obtained.

[0119]

Example 3 [Polymerization] The polymerization of Example 2 was repeated except that the content of 1-butene in the mixed gas was 5.5 mol%, the amount of hydrogenation was 30 Nml, and the polymerization temperature was 80 ° C. Do the same, M
FR is 2.68 g / 10 min and density is 0.906 g /
cm ³ , the amount of decane-soluble components at 23 ° C. is 1.4% by weight, the bulk specific gravity is 0.42 g / cm ³ , the polymer average particle size is 800 μm, and the amount of fine powder polymer is 100 μm or less. Was 0% by weight to obtain 201 g of an ethylene / 1-butene copolymer.

[0120]

Example 4 [Polymerization] The same procedure as in Example 2 was carried out except that the polymerization temperature was changed to 85 ° C., the MFR was 3.95 g / 10 min, the density was 0.906 g / cm ³ , and the temperature was 23 ° C. Is 3.2% by weight, and the bulk specific gravity is 0.42 g / cm ^3.
And the average polymer particle size is 800 μm,
Ethylene with an amount of fine polymer of 0 μm or less
158 g of 1-butene copolymer was obtained.

[0121]

Example 5 [Polymerization] The autoclave dried in the same manner as in Example 1 was returned to normal pressure by introducing ethylene, and the inside of the system was heated to 70 ° C. Next, the solid catalyst prepared in Example 2 was added to a 0.005 mg atom in terms of zirconium atom and triisobutylaluminum to a 0.5 mmol autoclave. Then, 1 ml of 1-pentene and 30 ml of hydrogen
After introducing Nml, the total pressure was increased to 8 kg / cm ² -G with ethylene to initiate polymerization. Thereafter, ethylene and 1-pentene were continuously supplied to maintain the total pressure at 8 kg / cm ² -G, and polymerization was carried out at 80 ° C. for 1 hour. In addition, the supply amount of 1-pentene is 29 ml.
Met.

Subsequent operations were performed in the same manner as in Example 1.
FR is 2.38 g / 10 min and density is 0.922 g /
cm ³ , the amount of the decane-soluble component at 23 ° C. is 0.1% by weight, the bulk specific gravity is 0.39 g / cm ³ , the average polymer particle diameter is 650 μm, and the amount of fine powder polymer is 100 μm or less. 182 g of an ethylene / 1-pentene copolymer having 0.1% by weight was obtained.

[0123]

Example 6 [Polymerization] 1-hexene in a total amount of 30 ml (3 ml + 27
ml) except that it was used, the MFR was 2.60 g / 10 min, and the density was 0.919 g / cm ^3.
111 g of an ethylene / 1-hexene copolymer having a bulk specific gravity of 0.42 g / cm ³ , a polymer average particle size of 580 μm, and an amount of fine powder polymer of 100 μm or less of 0.1% by weight was obtained. .

[0124]

Example 7 [Preparation of solid catalyst (zirconium catalyst)] 3 under nitrogen flow
Silica dried at 00 ° C for 6 hours (adsorbed water amount 0.1 wt%
Hereinafter, 6.8 g of a hydroxyl group content of 2.1% by weight)
The suspension was suspended in 0 ml and cooled to 0 ° C. Thereafter, a toluene solution of an organic aluminum oxy compound (Al; 1.465 mol / l) prepared in the same manner as in Example 1
1.8 ml were added dropwise over 20 minutes. At this time, the temperature in the system was kept at 0 ° C. Then, 1 hour at 0 ° C., 1 hour at room temperature,
Further, the reaction was performed at 80 ° C. for 4 hours.

40 ml of the suspension thus obtained was transferred to another glass flask, and 100 ml of decane and 2.23 ml of a decane solution of triisobutylaluminum (Al; 1 mol / l) were added, followed by stirring for 10 minutes. . Next, 1.65 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr; 0.0451 mol / l) was added to the suspension, followed by stirring for 10 minutes.

Thereafter, 100 ml of decane was added, ethylene gas (normal pressure) was continuously introduced, and preliminary polymerization was carried out at 30 ° C. for 6 hours. At this time, no adhesion of the prepolymerized catalyst to the reactor wall was observed.

The subsequent operation was carried out in the same manner as in Example 1, except that 3.9 mg of zirconium, 137 mg of aluminum and 137 mg of polyethylene were added to 1 g of silica.
A solid catalyst containing 9 g was obtained. The solid catalyst was resuspended in hexane for polymerization.

[Polymerization] The procedure of Example 1 was repeated except that the solid catalyst prepared above was used, and the MFR was 1.60 g / g.
10 minutes, the density is 0.904 g / cm ³ , 23
The decane-soluble component amount at 3.1 ° C. is 3.1% by weight, the bulk specific gravity is 0.41 g / cm ³ , and the polymer average particle size is 660.
μm, and the amount of finely divided polymer of 100 μm or less is 0.1
203 g of a 1% by weight ethylene / 1-butene copolymer was obtained.

[0129]

Comparative Example 1 [Preparation of solid catalyst (zirconium catalyst)] 7 under nitrogen flow
Silica calcined at 00 ° C for 6 hours (0.1% by weight of adsorbed water)
Hereinafter, 3.9 g of a hydroxyl group content (0.5% by weight) was added to toluene 10
The suspension was suspended in 0 ml and cooled to 0 ° C. To this suspension, 16.4 ml of a toluene solution (Al; 1.365 mol / l) of an organoaluminum oxy compound synthesized in the same manner as in Example 1 was added dropwise over 30 minutes. At this time, the temperature in the system was kept at 0 ° C. Thereafter, the reaction was carried out at 0 ° C. for 1 hour, at room temperature for 1 hour, and further at 80 ° C. for 4 hours.

50 ml of the suspension thus obtained was transferred to another glass flask, and 100 ml of decane was further added.
And triisobutylaluminum in decane solution (Al; 1)
(Mol / l) and stirred for 10 minutes. Next, 4.00 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr; 0.0320 mol / l) was added to the suspension, followed by stirring for 10 minutes. After that, ethylene gas (normal pressure)
Was preliminarily polymerized at 30 ° C. for 2 hours.
At this time, adhesion of white matter was observed on the reactor wall.

After this prepolymerization, the solvent was removed by decantation, and the resultant was washed with 150 ml of hexane.
By repeating this operation four times, 6.2 mg of zirconium and 14 mg of aluminum were added to 1 g of silica.
A solid catalyst containing 7 milligrams and 4 g of polyethylene was obtained. The solid catalyst was resuspended in hexane for polymerization.

[Polymerization] The polymerization of Example 3 was repeated except that the solid catalyst prepared above was used, the 1-butene content in the mixed gas was changed to 4.6 mol%, and the hydrogenation amount was changed to 10 Nml. Similarly, the MFR was 2.60 g / 10 min, the density was 0.912 g / cm ³ , and the bulk specific gravity was 0.4.
0 g / cm ³ , the average polymer particle diameter is 650 μm, and the amount of finely divided polymer of 100 μm or less is 0.4% by weight.
150 g of an ethylene / 1-butene copolymer was obtained.

[0133]

[Comparative Example 2] [Polymerization] In the polymerization of Example 3, instead of the solid catalyst, the silica-supported organoaluminum oxy compound prepared in Example 2 was added with 0.30 milligram atoms in terms of aluminum atoms and bis (n-butylcyclohexane). 1 ml of a toluene solution of (pentadienyl) zirconium dichloride (Zr; 0.003 mol / l) was individually added to the autoclave,
The MFR was 5.1 except that the 1-butene content in the mixed gas was 4.6 mol% and the hydrogenation amount was 10 Nml.
Was 0 g / 10 min, density of 0.916 g / cm ^3, bulk density was obtained ethylene-1-butene copolymer 47g is 0.21 g / cm ^3.

At this time, adhesion of the polymer was observed on the autoclave wall, and the amount of the coarse polymer was large.

[0135]

Comparative Example 3 [Preparation of Solid Catalyst (Zirconium Catalyst)] 3.6% by weight of water was added to silica dried in the same manner as in Example 1 and uniformly dispersed. 9.6 g of this silica is mixed with 150 ml of toluene.
And the temperature in the system was set to 0 ° C. To this suspension, 65.4 ml of a toluene solution of an organoaluminum oxy compound (Al; 1.465 mol / l) prepared in the same manner as in Example 1 was added dropwise over 45 minutes. At this time, the temperature in the system was kept at 0 to 1 ° C. Then at 0 ° C for 1 hour and at room temperature for 1 hour
The reaction was further carried out at 80 ° C. for 4.5 hours.

30 ml of the suspension thus obtained was transferred to another glass flask, and 100 ml of decane was further transferred.
And triisobutylaluminum in decane solution (Al; 1)
(Mol / liter) 4.03 ml and stirred for 10 minutes.

Then, 4.29 m of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr; 0.0313 mol / l) was added to the suspension.
1 was added and stirred for 5 minutes.

Thereafter, ethylene gas (normal pressure) was continuously introduced, and prepolymerization was performed at 30 ° C. for 2 hours. On this occasion,
Adherence of white matter was observed on the reactor wall. After this pre-polymerization, the solvent was removed by decantation, and washed with 150 ml of hexane. By performing the washing six times, 9.0 mg of zirconium was added to 1 g of silica.
A solid catalyst containing 281 mg of aluminum and 5 g of polyethylene was obtained. The solid catalyst was resuspended in hexane for polymerization.

[Polymerization] In the polymerization of Example 3, the solid catalyst prepared above was used, the content of 1-butene in the mixed gas was 6.0 mol%, and the polymerization temperature was 85 ° C. And the MFR is 3.07 g / 10 min.
The density is 0.909 g / cm ³ , the amount of decane-soluble components at 23 ° C. is 2.9% by weight, and the bulk specific gravity is 0.41 g / c.
m ³ , the average polymer particle size is 400 μm, and 1
82 g of an ethylene / 1-butene copolymer having an amount of fine powder polymer of not more than 00 μm of 1.1% by weight was obtained.

[0140]

Example 8 [Preparation of solid catalyst (zirconium catalyst)] 1.4 g of the same silica as in Example 1 was suspended in 20 ml of toluene.
Cooled to 0 ° C. 7.3 ml of a toluene solution (Al; 1.465 mol / l) of an organoaluminum oxy compound prepared in the same manner as in Example 1 was added to 10 parts of this suspension.
In minutes. The subsequent reaction was performed in the same manner as in Example 1.

Next, 100 ml of hexane and a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr; 0.0313 mol / liter) 4.5
6 ml was added and stirred for 10 minutes. Thereafter, 3.13 ml of a decane solution of triisobutylaluminum (Al; 1 mol / l) was added, and then ethylene gas (normal pressure) was introduced to start prepolymerization. Preliminary polymerization was performed at 35 ° C. for 9 hours while continuously introducing ethylene gas.
At this time, adhesion of the prepolymerized catalyst to the reactor wall was not recognized.

The subsequent operation was performed in the same manner as in Example 1, except that 9.0 mg of zirconium, 206 mg of aluminum and 4 mg of polyethylene were added to 1 g of silica.
A solid catalyst containing 3 g was obtained. The solid catalyst was resuspended in hexane for polymerization.

[Polymerization] In the polymerization of Example 1, using the solid catalyst prepared above, the content of 1-butene in the mixed gas was 5.8 mol%, the hydrogenation amount was 20 Nml, and the polymerization temperature was 8
The same procedure as in Example 1 was carried out except that the temperature was 0 ° C., and the MFR was 3.
34 g / 10 min, a density of 0.903 g / cm ³ , a decane-soluble component amount at 23 ° C. of 4.3% by weight, a bulk specific gravity of 0.44 g / cm ³ , and a polymer average Ethylene / 1-butene copolymer 247 having a particle size of 900 μm and an amount of fine polymer of 100 μm or less of 0% by weight
g was obtained.

[0144]

Example 9 [Preparation of solid catalyst (zirconium catalyst)] The procedure of Example 1 was repeated, except that the Zr compound was changed to bisindenyl zirconium dichloride. 4.2 mg of zirconium and 1 g of aluminum were added to 1 g of silica. A solid catalyst containing 160 milligrams and 36 g of polyethylene was obtained.
At this time, adhesion of the prepolymerized catalyst to the reactor wall was not recognized.

[Polymerization] The procedure of Example 1 was repeated except that the solid catalyst prepared above was used, and the MFR was 3.50 g / g.
10 min, a density of 0.905 g / cm ^3, a bulk specific gravity of 0.39 g / cm ^3, the polymer average particle size of 66
0 μm, and the amount of finely divided polymer of 100 μm or less is 0.3
178 g of a 1% by weight ethylene / 1-butene copolymer was obtained.

[0146]

Example 10 [Polymerization] The same procedure as in Example 1 was carried out except that triisobutylaluminum was not used, and the MFR was 2.91 g / 1.
0 minutes, a density of 0.906 g / cm ^3, bulk density 0.39 g / cm ^3, and a polymer average particle size of 470μ
m and an ethylene / 1-butene copolymer (77 g) having a polymer content of 0.2% by weight under 100 μm was obtained.

[0147]

Example 11 [Preparation of solid catalyst (zirconium catalyst)] Silica 1 was prepared in the same manner as in Example 1 except that the prepolymerization time was changed to 2 hours.
A solid catalyst containing 4.3 mg of zirconium, 159 mg of aluminum and 5 g of polyethylene was obtained. At this time, adhesion of the prepolymerized catalyst to the reactor wall was not recognized.

[Polymerization] The procedure of Example 1 was repeated except that the solid catalyst prepared above was used, and the MFR was 2.01 g / g.
10 min, a density of 0.902 g / cm ^3, a bulk specific gravity of 0.39 g / cm ^3, the polymer average particle size of 68
0 μm, and the amount of finely divided polymer of 100 μm or less is 0.3
189 g of 1% by weight ethylene / 1-butene copolymer was obtained.

[0149]

[Example 12] [Preparation of solid catalyst (zirconium catalyst)] In Example 1, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was used instead of bis (n-butylcyclopentadienyl) zirconium dichloride. 0.12 mmol, silica and organoaluminum oxy compound were used in amounts of 1.4 g and 8.24 mmol, respectively.
By setting the pre-polymerization time to 2 hours, 1 g of silica
A solid catalyst containing 6.1 mg of zirconium, 157 mg of aluminum and 4 g of polyethylene was obtained. At this time, no adhesion of the prepolymerized catalyst to the reactor wall was observed.

[Polymerization] In Example 1, 0.005 milligram atom of zirconium atom and 0.63 millimol of triisobutylaminium were used as the solid catalyst prepared above, and the 1-butene content in the mixed gas was determined. 5.9 mol%, the amount of hydrogenation was 50 Nml, and the polymerization temperature was 80 ° C.
187 g of an ethylene / 1-butene copolymer having a bulk specific gravity of 0.44 g / cm ³ , a polymer average particle diameter of 600 μm, and an amount of fine powder polymer of 100 μm or less of 0.1% by weight is 10 minutes. Was.

[0151]

[Example 13] [Preparation of solid catalyst (zirconium catalyst)] In a 400 ml glass flask sufficiently purged with nitrogen, silica (TG-40209 manufactured by Fuji Devison, 0.3% by weight of adsorbed water, 2.7% by weight of hydroxyl group). %) And 300 ml of toluene were suspended in the suspension, and cooled to 0 ° C. To this suspension, 33.6 ml of a toluene solution of an organoaluminum oxy compound (Methylaluminoxane manufactured by Schering Co., Ltd. was dried and then redissolved. Al: 4.16 mol / l) was added in 1 hour. It was dropped. At this time, the temperature in the system was kept at 0 ° C. Thereafter, the reaction was carried out at 0 ° C. for 30 minutes and further at 95 ° C. for 24 hours. After the completion of the reaction, the resultant was cooled to 60 ° C., and the solvent was removed by decantation. Then, it was washed three times with 300 ml of hexane.

4.05 g of the solid component obtained above was suspended in 150 ml of hexane, and a decane solution of triisobutylaluminum (Al; 1 mol / liter) 1 was added thereto.
5 mmol and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride in toluene solution (Zr;
(0.0291 mol / l) 5.2 ml were added. Thereafter, ethylene gas (normal pressure) was continuously introduced, and 35 ° C
For 2 hours. At this time, no adhesion to the reactor wall was observed.

After the prepolymerization, the solvent was removed by decantation, and the residue was washed with 150 ml of hexane.
By performing this washing four times, 4.6 milligrams of zirconium and 195 milligrams of aluminum were added to 1 g of silica.
A solid catalyst containing milligrams and 4.2 grams was obtained.

[Polymerization] 150 g of sodium chloride (special grade of Wako Pure Chemical Industries) was charged into a 2-liter stainless steel autoclave which had been sufficiently purged with nitrogen, and dried at 90 ° C. for 1 hour under reduced pressure. Thereafter, the pressure was returned to normal pressure by introducing a mixed gas of ethylene and 1-butene (1-butene content: 5.1 mol%), and the inside of the system was brought to 75 ° C. Next, 0.004 mg atom of the solid catalyst prepared as described above in terms of zirconium atom and 1 mmol of triisobutylaluminum were added to the autoclave.

Thereafter, 50 N ml of hydrogen was introduced, and a mixed gas of the above-mentioned ethylene and 1-butene was further introduced to start polymerization at a total pressure of 8 kg / cm ² -G. The temperature in the system immediately rose to 85 ° C. Thereafter, only the mixed gas was supplied, and the total pressure was kept at 8 kg / cm ² -G at 85 ° C. and 1.5%.
Polymerization was carried out for hours.

After completion of the polymerization, sodium chloride was removed by washing with water, and the remaining polymer was washed with methanol.
It dried under reduced pressure at ° C overnight. As a result, at 190 ° C., 2.16
The MFR measured under a load of kg is 0.01 g / 10 min or less, the bulk specific gravity is 0.45 g / cm ³ , the average particle size of the polymer is 860 μm, and the amount of fine powder polymer of 100 μm or less is 0 wt. % And an ethylene / 1-butene copolymer of 422 g are shown in Tables 1 and 2, respectively.

[0157]

[Table 1]

[0158]

[Table 2]

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-2-131488 (JP, A) JP-A-63-152608 (JP, A) JP-A-63-280703 (JP, A) JP-A-61- 296008 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (8)

(57) [Claims] 1. [A] (a-1) (i) an oxide of at least one element selected from the group II, group III and group IV, and (ii) the amount of adsorbed water is less than 1.0% by weight. And (iii) a solid catalyst component comprising (a-2) an organoaluminum oxy compound supported on a particulate carrier having 2.0 to 3.5% by weight of a surface hydroxyl group, wherein the component (a) -1)
The molar ratio (OH / Al _a-2 ) of the surface hydroxyl group (OH) of (a) to the aluminum (Al _a-2 ) of the component ( _a-2 ) is 0.15 to 0.15.
A solid catalyst component obtained by mixing and contacting with a range of 0.4, and a catalyst component comprising: [B] a transition metal compound of the IVB group containing a ligand having a hydrocarbon group-substituted cyclopentadienyl skeleton; The atomic ratio (Al / transition metal) of aluminum of the component (a-2) to the transition metal in the component [B] is 20 to 20.
A solid catalyst for olefin polymerization, wherein the solid catalyst is formed by prepolymerizing an olefin in a suspension or in a gaseous phase in such a ratio as to be in the range of 0. 2. (A) (a-1) (i) an oxide of at least one element selected from the group II, group III and group IV, and (ii) the amount of adsorbed water is less than 1.0% by weight. And (iii) a solid catalyst component comprising (a-2) an organoaluminum oxy compound supported on a particulate carrier having 2.0 to 3.5% by weight of a surface hydroxyl group, wherein the component (a) -1)
The molar ratio (OH / Al _a-2 ) of the surface hydroxyl group (OH) of (a) to the aluminum (Al _a-2 ) of the component ( _a-2 ) is 0.15 to 0.15.
A solid catalyst component obtained by mixing and contacting in the range of 0.4; [B] a group IVB transition metal compound containing a ligand having a hydrocarbon group-substituted cyclopentadienyl skeleton; [C] an organoaluminum The catalyst component consisting of the compound
The aluminum atom (A) of the component [C] is used at such a ratio that the atomic ratio (Al / transition metal) of aluminum of the component (a-2) to the transition metal in the component [B] is in the range of 20 to 200.
l _C) and the atomic ratio of component (a-2) aluminum atoms _{(Al a-2) (Al} C / Al a-2) is used in a proportion such that the range of 0.02-3, suspended A solid catalyst for olefin polymerization, which is formed by prepolymerizing an olefin in a liquid or a gas phase. 3. The (a-1) particulate carrier has an average particle size of 10 to 200 μm and a specific surface area of 100 to 700 m.
² / g, and an olefin polymerization solid catalyst according to claim 1 or claim 2 pore volume is 0.3~2.5cm ³ / g. 4. The method according to claim 1, wherein the transition metal compound [B] is of the following formula [I]
ML _X ... [IV] (wherein M is a transition metal of Group IVB of the periodic table, L is a ligand that coordinates to the transition metal, and at least one L
Is a ligand having an alkyl-substituted cyclopentadienyl skeleton, and L other than a ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom. , A trialkylsilyl group, or a hydrogen atom, and x is the valence of a transition metal. ). 5. The method according to claim 1, wherein the transition metal compound (B) is represented by the following formula (I):
V ′]; the solid catalyst for olefin polymerization according to any one of claims 1 to 3; R ¹ _a R ² _b R ³ _c R ⁴ _d M ... [IV ′] (wherein M Is zirconium, titanium or hafnium; R ¹ is a group having an alkyl-substituted cyclopentadienyl skeleton; R ² , R ³ and R ⁴ are a group having an alkyl-substituted cyclopentadienyl skeleton; an alkyl group; Group, aryl group, aralkyl group, alkoxy group, aryloxy group, halogen atom, trialkylsilyl group or hydrogen atom, a is an integer of 1 or more;
a + b + c + d = 4. ). 6. The solid catalyst for olefin polymerization according to claim 1, wherein the organoaluminum compound [C] is represented by the following general formula [V]: R ⁷ _n AlX _3-n . V] (wherein, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms;
Is halogen or hydrogen, and n is 1 to 3. ). 7. A solid catalyst for olefin polymerization comprising the solid catalyst for olefin polymerization according to claim 1 and an organoaluminum compound. 8. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the solid catalyst for olefin polymerization according to any one of claims 1 to 7.