JPH05155930A - Catalyst for polymerization of olefin and polymerization of olefin - Google Patents

Abstract

PURPOSE:To obtain an olefin polymer having excellent particle properties in high polymerization activity by prepolymerizing an olefin in the presence of a specified catalyst component in a suspension or a vapor phase. CONSTITUTION:A particulate carrier comprising an oxide of at least one element selected from the elements of groups II, III and IV and having a mean particle diameter of 1-300mum, a specific surface area of 50-1000m<2>/g, a pore volume of 0.3-2.5cm<3>/g, an adsorbed water content of below 1.0wt.% and a surface hydroxyl content of 1.0wt.% or above is impregnated with an organoaluminumoxy compound to obtain a solid catalyst component. An olefin is prepolymerized at -20 to 80 deg.C for 0.5-100hr in the presence of a catalyst component comprising the obtained component, a group IV transition metal compound containing ligands each having a cyclopentadienyl skeleton and optionally an organolauminum compound in a suspension or a vapor phase to obtain the objective catalyst for the polymerization of an olefin. An olefin is polymerized at -50 to 150 deg.C under a pressure of atmospheric pressure to 100kg/cm<2> in the presence of this catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a solid catalyst for olefin polymerization and a method for polymerizing an olefin using this catalyst, and more specifically, it can be applied to a suspension polymerization method or a gas phase polymerization method and has a high polymerization rate. The present invention relates to a solid catalyst for olefin polymerization capable of producing an olefin polymer which is active and has excellent particle properties, and a method for polymerizing olefins using this catalyst.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a catalyst for producing an α-olefin polymer such as an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst or a vanadium compound composed of a titanium compound and an organoaluminum compound is used. Vanadium-based catalysts composed of and an aluminum compound are known.

In recent years, a new Ziegler type olefin polymerization catalyst composed of 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, and such a catalyst is also available. Ethylene / α-using a new catalyst
A method for producing an olefin copolymer is described in, for example, JP-A-58 / 58
-19309, JP-A-60-35005,
JP-A-60-35006, JP-A-60-3500
No. 7, Japanese Patent Laid-Open No. 60-35008, and the like.

The catalyst formed from the transition metal compound and the organoaluminum oxy compound proposed in these prior arts is a catalyst formed from the transition metal compound and the organoaluminum compound known before the appearance of this catalyst. Although it has excellent polymerization activity, especially ethylene polymerization activity, most of it is soluble in the reaction system, and in most cases, the production process is limited to the solution polymerization system, and it is attempted to produce a polymer having a high molecular weight. Then, the viscosity of the solution containing the polymer becomes extremely high, which causes the disadvantage of decreasing productivity, and the bulk specific gravity of the polymer obtained after the post-treatment of polymerization is small, and a spherical olefin polymer having excellent particle properties is produced. 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 system 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-
-35008, transition metal compounds and organoaluminum oxy compounds, silica, alumina, silica.
It is described that a catalyst supported on alumina or the like can be used.

In JP-A-60-106808 and JP-A-60-106809, 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 obtained 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 affinity for polyolefin. A method of making an article is described.

JP-A-61-31404 discloses that a product obtained by reacting a trialkylaluminum with water in the presence of silicon dioxide or aluminum oxide and a transition metal compound in the presence of a mixed catalyst. , Ethylene or a method of polymerizing or copolymerizing ethylene and an α-olefin.

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

JP-A-61-108610 and JP-A-61-296008 disclose that an olefin is present in the presence of a catalyst in which a transition metal compound such as metallocene and aluminoxane are supported on a carrier such as an inorganic oxide. A method for polymerizing is described.

However, when the olefins are polymerized or copolymerized in the suspension polymerization system or the gas phase polymerization system using the solid catalyst component supported on the 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, the polymerization activity is high and the particle properties of the produced polymer are excellent, but there is a problem that the prepolymerization catalyst adheres to the reaction wall during prepolymerization.

[0013]

DISCLOSURE 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. Another object of the present invention is to provide a solid catalyst for olefin polymerization capable of producing a spherical olefin polymer and capable of producing a copolymer having a narrow composition distribution when two or more kinds of monomers are copolymerized. Another object of the present invention is to provide a method for polymerizing olefins using a catalyst having such good properties.

[0014]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises [A] (a-1) (i) an oxide of at least one element selected from Group II, Group III and Group IV, and (ii) ) A solid catalyst component comprising (a-2) an organoaluminum oxy compound supported on a particulate carrier having an adsorbed water content of less than 1.0% by weight and (iii) having a surface hydroxyl group of 1.0% by weight or more. And [B] a ligand having a cyclopentadienyl skeleton
It is formed by prepolymerizing an olefin in a suspension or in a gas phase using a catalyst component consisting of a Group IVB transition metal compound and, if necessary, a [C] organoaluminum compound. I am trying.

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

[0016]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization solid catalyst according to the present invention and the olefin polymerization method using the catalyst will be specifically described below.

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" may be used not only as a homopolymer but also as a copolymer. May be used to mean coalesce.

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

A porous oxide is preferable as such a fine-particle inorganic compound, and specifically, SiO ₂ , Al
₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, Z
nO, BaO, ThO _2, etc., or a mixture containing these, 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-
Examples thereof include TiO ₂ -MgO. Among these, those containing as a main component at least one component selected from the group consisting of SiO ₂ , Al ₂ O ₃ and Mg are preferable.

The fine particle carrier (a-1) has an average particle size of usually 1 to 300 μm, preferably 10 to 200 μm, and a specific surface area of 50 to 1000 m ² /
g, 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) fine particle carrier, the amount of adsorbed water is less than 1.0% by weight, preferably less than 0.5% by weight, and the surface hydroxyl group is 1.0% by weight or more, preferably. It is desired to 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 group (% by weight) are determined as follows. [Amount of adsorbed water] 4 at normal temperature and nitrogen flow at a temperature of 200 ° C
The weight loss after drying for an hour is defined as the amount of adsorbed water. [Surface hydroxyl group] It was obtained by drying the carrier at 200 ° C. under normal pressure and under nitrogen flow for 4 hours, the weight of the carrier being X (g), and calcining the carrier at 1000 ° C. for 20 hours. The weight is calculated by the following formula, where Y (g) is the weight of the baked product from which the surface hydroxyl groups have disappeared.

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

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 organoaluminum oxy compound.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same.

(2) A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it 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 organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used in the production of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum and tri-n-.
Trialkyl aluminum such as butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum; tricyclohexyl aluminum, tricyclooctyl aluminum, etc. Tricycloalkyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dimethyl aluminum methoxide, diethyl aluminum ethoxy Like dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide; dialkylaluminum alkoxides such as.

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

[0031] _{(i-C 4 H 9)} X Al y (C 5 H 10) Z ... [I] ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Above Such organoaluminum compounds are used alone or in combination.

The solvent used for the production of aluminoxane includes 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, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, and methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons,
Alicyclic hydrocarbon halides, especially hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

The benzene-insoluble organoaluminum oxy compound used in the present invention is, for example, a method in which a solution of aluminoxane is brought into contact with water or a compound containing active hydrogen, or the above-mentioned organoaluminum is brought into contact 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. As the active hydrogen-containing compound, 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 preferable, and alcohols are particularly preferable.

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

The catalytic reaction between the solution of aluminoxane and water or the compound containing active hydrogen is usually carried out in a solvent, for example, a hydrocarbon solvent. As the solvent used at this time, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane; cyclopentane, cyclohexane , Cyclooctane, alicyclic hydrocarbons such as methylcyclohexane; hydrocarbon solvents such as petroleum fractions such as gasoline, kerosene, and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, etc. It is also possible to use halogenated hydrocarbons such as chlorinated compounds and brominated compounds, and ethers such as ethyl ether and tetrahydrofuran.

Of these media, aromatic hydrocarbons are especially preferred. Water or an 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 the Al atom in the aluminoxane solution. The concentration in the reaction system is preferably in the range of 1 × 10 ^{−3 to} 5 gram atom / liter, preferably 1 × 10 ^{−2 to} 3 gram atom / liter, in terms of aluminum atom. The concentration of water in the system is usually 2 × 10 ^{−4 to} 5 mol / liter, preferably 2
It is desirable that the concentration is × 10 ^{-3 to} 3 mol / liter.

Specific examples of the method for bringing the aluminoxane solution into contact with water or the active hydrogen-containing compound include the following methods. (1) A method of bringing a solution of aluminoxane into contact with water or a hydrocarbon solvent containing an active hydrogen-containing compound.

(2) A method of bringing the aluminoxane and the vapor into contact with each other by, for example, blowing water or a vapor of an active hydrogen-containing compound into a solution of the aluminoxane. (3) A method of directly contacting a solution of aluminoxane with water or ice or a compound containing active hydrogen.

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

The aluminoxane solution as described above may contain other components as long as it does not adversely affect the reaction between the aluminoxane and water or the compound containing active hydrogen.

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

In the second method for obtaining a benzene-insoluble organoaluminum oxy compound, organoaluminum and water are brought into contact with each other. Water is used in an amount such that the amount of organic aluminum atoms dissolved in the reaction system is 20% or less based on the total amount of organic aluminum atoms.

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

The catalytic reaction between the organoaluminum compound and water is usually carried out in a hydrocarbon solvent. As the hydrocarbon solvent used at this time, benzene, toluene, xylene, cumene, aromatic hydrocarbons such as cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane and other aliphatic hydrocarbons, cyclopentane , Cyclohexane, cyclooctane, methylcyclohexane, and other alicyclic hydrocarbons, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbon halides, especially chlorinated compounds And hydrocarbon solvents such as bromide. In addition, ethers such as ethyl ether tetrahydrofuran can also be used. Of these media, aromatic hydrocarbons are especially preferred.

The concentration of the organoaluminum compound in the reaction system is usually in the range of 1 × 10 ^{−3 to} 5 gram atom / liter, preferably 1 × 10 ^{−2 to} 3 gram atom / liter in terms of aluminum atom. It is desirable that the concentration of water in the reaction system is usually 1 × 10 ^{−3 to} 5 mol / liter, preferably 1 × 10 ^{−2 to} 3 mol / liter. At this time, it is desirable that the amount of organic aluminum atoms dissolved in the reaction system is 20% or less, preferably 10% or less, and more preferably 0 to 5% with respect to the total amount of organic aluminum atoms.

Specific examples of the method of bringing the organoaluminum compound into contact with water include the following methods. (1) A method of bringing a hydrocarbon solution of organoaluminum into contact with a hydrocarbon solvent containing water.

(2) A method of bringing organic aluminum and steam into contact with each other by blowing steam into a hydrocarbon solution of organic aluminum. (3) A method in which a hydrocarbon solution of organoaluminum and a hydrocarbon suspension of an adsorbed water-containing compound or a crystal water-containing compound are mixed to bring the organoaluminum into contact with adsorbed water or crystal water.

(4) A method of bringing a hydrocarbon solution of organoaluminum into contact with ice. The above-mentioned organic aluminum hydrocarbon solution may contain other components as long as it does not adversely affect the reaction between the organic aluminum and water.

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

Such a benzene-insoluble organoaluminum oxy compound is an Al that dissolves in benzene at 60 ° C.
The component is 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atom, and it is insoluble or hardly soluble in benzene. Regarding the solubility of the organoaluminum oxy compound in benzene, the organoaluminum oxy compound corresponding to 100 mg of Al was suspended in 100 ml of benzene, mixed with stirring at 60 ° C. for 6 hours, and then with a jacketed G-5. The amount of Al atoms present in the whole filtrate after filtration was performed at 60 ° C. with a glass filter while hot, and the solid portion separated on the filter was washed 4 times with 50 ml of benzene at 60 ° C. ( x mmol) to determine (x
%).

When the above-mentioned benzene-insoluble organoaluminum oxy compound is analyzed by infrared spectroscopy (IR), the absorbance (D ₁₂₂₀ ) around ₁₂₂₀ cm ^-1 is obtained.
And the absorbance (D ₁₂₆₀ ) near ₁₂₆₀ cm ^-1 (D ₁₂₆₀ / D ₁₂₂₀ ) is 0.09 or less, preferably 0.0.
It is preferably 8 or less, particularly preferably in the range of 0.04 to 0.07.

The infrared spectroscopic analysis of the organoaluminum oxy compound is carried out as follows. First, an organoaluminum oxy compound and Nujol are ground in a nitrogen box in an agate mortar to form a paste. Next, the paste-like 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 calculated, and this _D1260 / _D1220 value is _calculated as follows.

(A) Near 1280 cm ^-1 and 1240 cm
The maximum points near ^-1 are connected and this is set as the baseline L ₁ . (B) Transmittance (T of the absorption minimum point near 1260 cm ^-1
%) And a perpendicular line is drawn from this minimum point to the wave number axis (horizontal axis), the transmittance (T ₀ %) at the intersection of this perpendicular line and the base line L ₁ is read, and the absorbance (D) near 1260 cm ^−1. Calculate ₁₂₆₀ = log T ₀ / T).

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

(E) From these values, D₁₂₆₀/ D₁₂₂₀Total
Calculate Benzene-soluble organoaluminum oxy compound
The thing is D₁₂₆₀/ D₁₂₂₀The value is between about 0.10 and 0.13
Benzene-insoluble organoaluminum oxy compound
The product is a conventionally known benzene-soluble organoaluminum derivative.
Xy compound and D₁₂₆₀/ D ₁₂₂₀Obviously different in value
It

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

[0058]

[Chemical 1]

(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 group, n-butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group and cyclooctyl group. Among these, the methyl group,
An ethyl group is preferable, and a methyl group is particularly preferable.

The 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]. You may.

[0061]

[Chemical 2]

(In the formula, R ² is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or 6 to 20 carbon atoms.
Is an aryloxy group, a hydroxyl group, halogen or hydrogen. R ² and R ¹ in the above formula [II] represent groups different from each other. In this case, an organoaluminumoxy compound having an alkyloxyaluminum unit containing the alkyloxyaluminum unit (i) in an amount of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more is desirable.

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

ML _X [IV] In the above general formula [IV], M is a transition metal of Group IVB of the periodic table, specifically, zirconium, titanium or hafnium, and L is a transition metal. It is a ligand that coordinates, 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.

Of these ligands which coordinate to the transition metal, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula [IV] contains two or more groups having a cyclopentadienyl skeleton, the two 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, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group.

Examples of the ligand other than the ligand 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; benzyl group, neofil group etc. An aralkyl group is exemplified.

Examples of the alkoxy group include methoxy group, ethoxy group, butoxy group and the like. A phenoxy group etc. are illustrated as an aryloxy group.

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

Examples of the compound represented by the above general formula [IV] include
For example, when the valence of the transition metal is 4, more specifically,
It is represented by the following general formula [IV ′]. R¹ _aR² _bR³ _cR^Four _dM ... [IV '] (In the formula [IV'], M is zirconium, titanium or huff.
N, R¹Has a cyclopentadienyl skeleton
R group², R³And R^FourIs cyclopentadier
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, -SO₃
R or a hydrogen atom, a is an integer of 1 or more, a
+ B + c + d = 4. ) In the present invention, the above general formula [I
R in V ']², R³And R^FourOne of them is cyclo
A transition metal compound which is a group having a pentadienyl skeleton,
For example R¹And R ²Has a cyclopentadienyl skeleton
A transition metal compound, which is a group, is preferably used. This
The groups having these cyclopentadienyl skeletons are
Alkylene groups such as amine and propylene, diphenylmethyl
Substituted alkylene groups such as
Rukylidene group, silylene group or dimethylsilylene, di
Substitution of phenylsilylene, methylphenylsilylene, etc.
It may be bonded via a silylene group or the like. Also,
R³And R^FourHas a cyclopentadienyl skeleton
Group, alkyl group, cycloalkyl group, aryl group, ara
Alkyl group, alkoxy group, aryloxy group, halogen atom
Child, trialkylsilyl group, SO₃R or hydrogen atom
is there.

Specific examples of transition metal compounds in which M is zirconium will be shown below. 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, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) Zirconium bis (methane sulfonate), ethylene bis (indenyl) zirconium bis (p-toluene sulfonate), ethylene bis (indenyl) zirconium Umbis (trifluoromethanesulfonato), ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopenta) Dienyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclo) Pentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl)
Zirconium bis (trifluoromethane sulfonate),
Dimethyl silylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethyl silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenyl silylene bis (indenyl) zirconium dichloride, methylphenyl silylene bis (indenyl) zirconium dichloride , Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopenta Dienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl Benzalkonium monochloride,
Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadiene) (Enyl) dibenzyl zirconium, bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl)
Zirconium bis (p-toluene sulfonate), bis (cyclopentadienyl) zirconium bis (trifluoromethane sulfonate), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl) zirconium ethoxy chloride, 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 example, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product is 1,2,3- and 1,2,4-. Including substitutes. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

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

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

R ⁷ _n AlX _3-n [V] (In the formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms, and X is
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 specific examples include a methyl group, an ethyl group, an n-propyl group and isopropyl group. 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, the following compounds are specifically used. Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, and tri-2-ethylhexyl aluminum; alkenyl aluminum such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; methyl 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.

[C] Organoaluminum compound
Therefore, a compound represented by the following formula [VI] can also be used.
It R⁷ _nAlY_3-n … [VI] (In the formula, R⁷Is the same as above, and Y is -OR⁸Group,-
OSiR⁹ ₃Group, -OAlR^Ten ₂Group, -NR¹¹ ₂Group,-
SiR¹² ₃Group or -N (R¹³) AlR¹⁴ ₂The base,
n is 1 to 2 and R⁸, R⁹, R^TenAnd R¹⁴Is meth
Group, ethyl group, isopropyl group, isobutyl group, cyclo
R is a hexyl group, phenyl group, etc. ¹¹Is hydrogen,
Cyl group, ethyl group, isopropyl group, phenyl group, tri
Such as a methylsilyl group, R¹²And R¹³Is methyl
Group, ethyl group and the like. ) Such an organic aluminum
Specifically, the following compounds are
Used.

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

(Ii) a compound represented by R ⁷ _n Al (OSi R ⁹ ₃ ) _3-n , for example, Et ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Me ₃ ) (iso-Bu ) ₂ Al (OSi Et ₃ ), etc.

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

(Iv) A compound represented by R ⁷ _n Al (NR ¹¹ ₂ ) _3-n , for example, Me ₂ AlNEt ₂ Et ₂ AlNHMe Me ₂ AlNHEt Et ₂ AlN (Si Me ₃ ) ₂ (iso-Bu) ₂ AlN (SiMe ₃ ) ₂ etc.

(V) A compound represented by R ⁷ _n Al (Si R ¹² ₃ ) _3-n , such as (iso-Bu) ₂ AlSi Me ₃ .

[0083]

[Chemical 3]

Among the organoaluminum compounds represented by the above general formulas [V] and [VI], R ⁷ ₃ Al and R ⁷ _n Al (OR
Preferred examples include organoaluminum compounds represented by ⁸ ) _3-n and R ⁷ _n Al (OAlR ¹⁰ ₂ ) _3-n ,
It is particularly preferable that R ⁷ is an isoalkyl group and n = 2. These organoaluminum compounds may 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, a transition metal compound of Group IVB having a [B] cyclopentadienyl skeleton, And, if necessary, the [C] organoaluminum compound is further mixed in an inert hydrocarbon solvent, an olefin is introduced therein, and preliminary polymerization is carried out.

At this time, the mixing order is arbitrarily selected, but preferably the component (a-1) and the component (a-2) are mixed and brought into contact with each other, and then the component [B] is mixed in this order, or the component (B) is mixed. a-1) and the component (a-2) are mixed and brought into contact with each other, and then the component [B] and then the component [C] are mixed in this order, or the component (a-1) and the component (a-2) are mixed. Are mixed and contacted, and then the component [C] and then the component [B] are mixed in this order.

FIG. 1 shows the steps for preparing the olefin polymerization catalyst according to the present invention. Examples of the inert hydrocarbon medium used in the preparation of the solid catalyst for olefin polymerization according to the present invention include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene. Cyclopentane, cyclohexane,
Examples thereof include 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 the component [C] is mixed as necessary, the component (a-2) is 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 component (a-2) is about 5 × 10 ^-2 to 2 mol / liter, preferably 0.1. The range is from 1 to 1 mol / liter. Further, the surface hydroxyl group (OH) of the component (a-1)
The molar ratio of aluminum (Al _a-2) component (a-2) and (OH / Al _a-2) is usually 0.1 to 0.5, preferably in the range of 0.15 to 0.4 is there.

The atomic ratio (Al / transition metal) between the aluminum of the component (a-2) and the transition metal in the component [B] is
It is usually 10 to 500, preferably 20 to 200. The aluminum atom (Al _C ) of the component [C] and the aluminum atom (A-2) of the component (a-2) which are used as necessary.
l _a-2) and the atomic ratio of _{(Al C / Al a-2} ) is usually 0.0
It is in the range of 2-3, preferably 0.05-1.5.

Component (a-1), component (a-2), component [B]
And the mixing temperature at the time of mixing the component [C] according to need is usually −50 to 150 ° C., preferably −20 to 120.
℃, the contact time is 1 to 1000 minutes, preferably 5
~ 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 0.5-100
The time is preferably 1 to 50 hours.

In the present invention, as described above, the component (a-1), the component (a-2), the component [B] and, if necessary, the component [C].
Are mixed in an inert hydrocarbon medium, and olefin is introduced therein to carry out prepolymerization. In the prepolymerization, the transition metal compound is usually used in an amount of 10 ⁻⁵ to 2 × 10 ⁻² mol / liter, preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / liter, 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 for prepolymerization
Is selected from the olefins used during polymerization
However, ethylene is preferably the main component. Above
The solid catalyst for olefin polymerization of the present invention thus obtained
Is about 5 × 10 per 1 g of component (a-1).^-6~ 5 x 10^-FourGu
Lamb atom, preferably 10^-Five~ 2 x 10 ^-FourGram atom
A transition metal atom is supported, and about 10^-3~ 5 x 10^-2Gu
Lamb atom, preferably 2 × 10^-3~ 2 x 10^-2Gram Hara
It is desirable that the aluminum atom of the child is supported.
Yes. Furthermore, the amount of polymer produced by prepolymerization is
(A-1) About 0.1 to 500 g, preferably 0.3 per 1 g
To 300 g, particularly preferably 1 to 100 g
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 to use it in an amount of ⁸ to 10 ^-3 gram atom, preferably 10 ^-7 to 10 ^-4 gram atom. At this time, an organoaluminum compound or aluminoxane may be used if necessary. Examples of the organoaluminum compound used at this time include the same compounds as the organoaluminum compound [C] described above. The amount used is 0 to 500 mol, preferably 5 to 200 mol, per gram atom of transition metal atom.

Examples of olefins which can be polymerized by 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 and 4 -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, Examples thereof include 3,4,4a, 5,8,8a-octahydronaphthalene. 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 used in the catalyst preparation method can be used, and the olefin itself can also be used as the solvent.

The olefin polymerization temperature 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 atmospheric pressure to 100 kg / cm ² , preferably atmospheric pressure to 50.
It is under the condition of kg / cm ² , and the polymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method. It is also possible to carry out the polymerization in two or more stages under different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.

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

[0098]

EFFECT OF THE INVENTION The solid catalyst for olefin polymerization according to the present invention comprises (a-1) a specific fine particle carrier having an adsorbed water content of less than 1.0% by weight and having a surface hydroxyl group of 1.0% by weight or more. And (a-2) a solid catalyst component [A] on which an organoaluminum oxy compound is supported, a Group IVB transition metal compound [B] containing a ligand having a cyclopentadienyl skeleton, and, if necessary, It is formed by prepolymerizing an olefin in a suspension or in a gas phase using a catalyst component composed of an organoaluminum compound [C].

Such a solid catalyst for olefin polymerization is
A spherical olefin polymer with high polymerization activity and excellent particle properties can be produced, and when two or more kinds of monomers are copolymerized, a copolymer having a narrow composition distribution can be obtained, and prepolymerization Sometimes the prepolymerization catalyst does not adhere to the reaction wall.

[0100]

EXAMPLES 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-based copolymer obtained by the present invention (the smaller the soluble amount, the narrower the composition distribution) is about 3 g of the copolymer and 450 ml of n-decane.
In addition to melting at 145 ° C., cooling to 23 ° C.,
The n-decane-insoluble portion was removed by filtration, and the n-decane-soluble portion was recovered from the filtrate for measurement.

The density is 2.16 k at 190 ° C.
The strand obtained during MFR measurement under g load is 120
After heat treatment at 1 ° C for 1 hour and cooling to room temperature over 1 hour, measurement was performed with a density gradient tube.

The average particle size of the polymer and 100 μ
The amount of fine powder of m or less was measured with a sieve.

[0104]

[Example 1] [Preparation of solid catalyst (zirconium catalyst)] Silica (manufactured by Fuji Devison Co., TG-20643) was dried at 200 ° C for 6 hours under nitrogen flow in a 400-ml glass flask sufficiently purged with nitrogen ( 18.0 g of adsorbed water amount of 0.1% by weight or less and hydroxyl group content of 2.7% by weight and 200 ml of toluene were put into a suspension state and cooled to 0 ° C. A toluene solution of an organoaluminum oxy compound in this suspension (methylaluminoxane manufactured by Schering Co., which was dried and then re-dissolved in toluene, Al; 1.465 mol / liter)
70.3 ml was added dropwise over 45 minutes, keeping the temperature in the system at 0 ° C. Thereafter, the reaction was carried out at 0 ° C for 1.5 hours, 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 decane solution of triisobutylaluminum (Al; 1 mol / l) were added, and the mixture was added to 10 ml.
Stir for minutes.

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

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

After this preliminary polymerization, the solvent was removed by decantation, and then 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 was obtained with respect to 1 g of silica. The solid catalyst was resuspended in hexane for polymerization.

[Polymerization] 150 g of sodium chloride (Wako Pure Chemical Industries, Ltd.) was charged into a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen, and dried under reduced pressure at 90 ° C for 1 hour. After that, 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.

Then, 0.003 milligram atom of zirconium atom and triisobutylaluminum of the solid catalyst prepared as described above were added to a 0.5 mmol autoclave.

Then, 30 Nml of hydrogen was introduced, and further the mixed gas of ethylene and 1-butene was introduced, and the total pressure was adjusted to 8
Polymerization was initiated at kg / cm ² -G. Immediately 7
Raised to 5 ° C.

Then, only the mixed gas is replenished, and the total pressure is adjusted to 8
Polymerization was carried out at 75 ° C. for 1 hour while keeping it at kg / cm ² -G. After completion of the polymerization, sodium chloride was removed by washing with water, the remaining polymer was washed with methanol, and then dried under reduced pressure at 80 ° C. overnight. As a result, the MFR measured at 190 ° C. under a load of 2.16 kg was 1.79 g / 10 min, the density was 0.903 g / cm ³ , and the amount of decane-soluble components at 23 ° C. was 3.4. % By weight and bulk specific gravity of 0.40 g / c
m ³ , the average particle size of the polymer is 700 μm, and 1
192 g of an ethylene / 1-butene copolymer having a fine polymer amount of not more than 00 μm and 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 state and cooled to 0 ° C. 88. Toluene solution of organoaluminum oxy compound in this suspension (methyl aluminoxane manufactured by Schering Co., which was dried and then redissolved in toluene, Al; 1.157 mol / liter) 88.
3 ml was added dropwise over 75 minutes, at which time the temperature in the system was 0 ° C.
Kept at. Then, the reaction was carried out at 0 ° C. for 1 hour, 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 thereto, and
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 this 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 carried out at 30 ° C. for 9 hours. At this time, no adhesion of the prepolymerization catalyst to the reactor wall was observed.

After this prepolymerization, the solvent was removed by decantation, and then washed with 150 ml of hexane. By performing this washing 6 times, 6.9 mg of zirconium, 200 mg of aluminum and 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 performed except that the temperature was changed to 5 ° C, and the MFR was 1.
46 g / 10 min, density is 0.890 g / cm ³ , bulk specific gravity is 0.42 g / cm ³ , polymer average particle size is 870 μm, and fine polymer amount of 100 μm or less is 0% by weight. An ethylene / 1-butene copolymer 2
36 g were obtained.

[0119]

Example 3 [Polymerization] The same as Example 2 except that the 1-butene content in the mixed gas was 5.5 mol%, the hydrogenation amount was 30 Nml, and the polymerization temperature was 80 ° C. in the polymerization of Example 2. Do the same, M
FR is 2.68 g / 10 minutes 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 average particle size of the polymer is 800 μm, and the amount of fine powder polymer is 100 μm or less. Was obtained 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 85 ° C., the MFR was 3.95 g / 10 min, the density was 0.906 g / cm ³ , and the temperature was 23 ° C. The amount of decane-soluble component was 3.2% by weight, and the bulk specific gravity was 0.42 g / cm ^3.
And the average particle size of the polymer is 800 μm, and 100
Ethylene containing 0% by weight of finely divided polymer having a particle size of 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 with 0.005 milligram atom in terms of zirconium atom and triisobutylaluminum to a 0.5 mmol autoclave. Continuously, 1-pentene 3 ml, hydrogen 30
After introducing N ml, the polymerization was started by pressurizing with ethylene to a total pressure of 8 kg / cm ² -G. Thereafter, ethylene and 1-pentene were continuously replenished to maintain the total pressure at 8 kg / cm ² -G, and polymerization was carried out at 80 ° C. for 1 hour. The supply amount of 1-pentene is 29 ml.
Met.

Subsequent operations were performed in the same manner as in Example 1, and M
FR is 2.38 g / 10 minutes and density is 0.922 g /
cm ³ , the amount of decane-soluble component at 23 ° C. is 0.1% by weight, the bulk specific gravity is 0.39 g / cm ³ , the polymer average particle size is 650 μm, and the amount of finely divided polymer is 100 μm or less. Was obtained to obtain 182 g of an ethylene / 1-pentene copolymer having a content of 0.1% by weight.

[0123]

Example 6 [Polymerization] The total amount of 1-hexene was 30 ml (3 ml + 27).
The same procedure as in Example 5 was repeated, except that MFR was 2.60 g / 10 min and the density was 0.919 g / cm ^3.
111 g of ethylene / 1-hexene copolymer having a bulk specific gravity of 0.42 g / cm ³ , a polymer average particle diameter of 580 μm, and a fine polymer amount of 100 μm or less of 0.1% by weight are obtained. ..

[0124]

Example 7 [Preparation of Solid Catalyst (Zirconium Catalyst)] Under Nitrogen Flow 3
Silica dried at 00 ° C for 6 hours (Adsorbed water amount 0.1% by weight
Below, hydroxyl group content 2.1% by weight) 6.8 g of toluene 15
It was suspended in 0 ml and cooled to 0 ° C. Thereafter, a toluene solution of an organoaluminum oxy compound prepared in the same manner as in Example 1 (Al; 1.465 mol / liter) 2
1.8 ml was added dropwise over 20 minutes. At this time, the temperature in the system was kept at 0 ° C. After that, at 0 ℃ for 1 hour, at room temperature for 1 hour,
Further, the reaction was carried out at 80 ° C. for 4 hours.

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

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

Subsequent operations were carried out in the same manner as in Example 1, and 3.9 mg of zirconium, 137 mg of aluminum and 2 g 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 same procedure as in Example 1 was carried out except that the solid catalyst prepared above was used, and the MFR was 1.60 g /
10 minutes, the density is 0.904 g / cm ³ , 23
The amount of decane-soluble component at ℃ was 3.1% by weight, the bulk specific gravity was 0.41 g / cm ³ , and the average particle size of polymer was 660.
μm and the amount of finely divided polymer of 100 μm or less is 0.1
203 g of an ethylene / 1-butene copolymer having a weight percentage was obtained.

[0129]

Comparative Example 1 [Preparation of Solid Catalyst (Zirconium Catalyst)] Under Nitrogen Flow 7
Silica calcined at 00 ° C for 6 hours (Adsorbed water amount 0.1% by weight
Below, hydroxyl group content 0.5% by weight) 3.9 g of toluene 10
It was suspended in 0 ml and cooled to 0 ° C. 16.4 ml of a toluene solution of an organoaluminum oxy compound (Al; 1.365 mol / l) synthesized in the same manner as in Example 1 was added dropwise to this suspension in 30 minutes. At this time, the temperature in the system was kept at 0 ° C. Then, the reaction was carried out at 0 ° C. for 1 hour, 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 added.
And decane solution of triisobutylaluminum (Al; 1
2.88 ml (mol / l) was added and stirred for 10 minutes. Then, 4.00 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr; 0.0320 mol / liter) was added to this suspension, and the mixture was stirred for 10 minutes. After that, ethylene gas (normal pressure)
Was continuously introduced, and prepolymerization was carried out at 30 ° C. for 2 hours.
At this time, adhesion of white matter was recognized on the reactor wall.

After this preliminary polymerization, the solvent was removed by decantation, and then washed with 150 ml of hexane.
By repeating this operation 4 times, 6.2 g of zirconium and 14 g of aluminum are 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] In the polymerization of Example 3, the same procedure as in Example 3 was conducted except that the solid catalyst prepared as described above was used and the 1-butene content in the mixed gas was 4.6 mol% and the hydrogenation amount was 10 Nml. The same procedure is performed, the MFR is 2.60 g / 10 minutes, the density is 0.912 g / cm ³ , and the bulk specific gravity is 0.4.
0 g / cm ³ , the average particle size of the polymer 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, the silica-supported organoaluminum oxy compound prepared in Example 2 was used in place of the solid catalyst, and 0.30 mg of aluminum atom and bis (n-butylcyclohexyl) 1 ml of a toluene solution of pentadienyl) zirconium dichloride (Zr; 0.003 mol / l) was added individually 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 recognized on the autoclave wall, and a large amount of coarse-grained polymer was found.

[0135]

Comparative Example 3 [Preparation of Solid Catalyst (Zirconium Catalyst)] 3.6% by weight of water was added to the dried silica as in Example 1 and uniformly dispersed. 9.6 g of this silica was added to 150 ml of toluene.
Was suspended, and the temperature inside the system was set to 0 ° C. 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 to this suspension over 45 minutes. At this time, the temperature in the system was kept at 0 to 1 ° C. Then 1 hour at 0 ° C, 1 at room temperature
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 added.
And decane solution of triisobutylaluminum (Al; 1
(Mole / liter) 4.03 ml was added and stirred for 10 minutes.

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

After that, ethylene gas (normal pressure) was continuously introduced, and prepolymerization was carried out at 30 ° C. for 2 hours. On this occasion,
Adhesion of white matter was observed on the reactor wall. After this prepolymerization, the solvent was removed by decantation and then washed with 150 ml of hexane. This washing was repeated 6 times to obtain 9.0 mg of zirconium per 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, Example 3 was repeated except that the solid catalyst prepared above was used, the 1-butene content in the mixed gas was 6.0 mol% and the polymerization temperature was 85 ° C. And the MFR is 3.07g / 10min.
The density was 0.909 g / cm ³ , the decane-soluble component amount at 23 ° C. was 2.9% by weight, and the bulk specific gravity was 0.41 g / c.
m ³ , the average particle size of the polymer is 400 μm, and 1
82 g of an ethylene / 1-butene copolymer having a fine polymer content of 100 μm or less 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 of an organoaluminum oxy compound (Al; 1.465 mol / liter) prepared in the same manner as in Example 1 was added to this suspension in an amount of 10 ml.
Dropped 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 / l) 4.5
6 ml was added and stirred for 10 minutes. Then, 3.13 ml of a decane solution of triisobutylaluminum (Al; 1 mol / liter) was added, and then ethylene gas (normal pressure) was introduced to start prepolymerization. Preliminary polymerization was carried out at 35 ° C. for 9 hours while continuously introducing ethylene gas.
At this time, no adhesion of the prepolymerization catalyst to the reactor wall was observed.

Subsequent operations were carried out in the same manner as in Example 1, and 9.0 g of zirconium, 206 mg of aluminum and 4 g 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 1-butene content in the mixed gas was 5.8 mol%, the hydrogenation amount was 20 Nml, and the polymerization temperature was 8
Example 1 was repeated except that the temperature was 0 ° C, and the MFR was 3.
34 g / 10 min, density was 0.903 g / cm ³ , decane-soluble component amount at 23 ° C. was 4.3% by weight, bulk specific gravity was 0.44 g / cm ³ , and polymer average Ethylene / 1-butene copolymer 247 having a particle size of 900 μm and an amount of finely divided polymer of 100 μm or less of 0% by weight
g was obtained.

[0144]

[Example 9] [Preparation of solid catalyst (zirconium catalyst)] The same procedure as in Example 1 was carried out except that the Zr compound was replaced with bisindenylzirconium dichloride, and 4.2 mg of zirconium and aluminum were added to 1 g of silica. A solid catalyst containing 160 mg and 36 g polyethylene was obtained.
At this time, no adhesion of the prepolymerization catalyst to the reactor wall was observed.

[Polymerization] The same procedure as in Example 1 was repeated except that the solid catalyst prepared above was used, and the MFR was 3.50 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.
178 g of an ethylene / 1-butene copolymer having a concentration of 1% by weight 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 77 g of an ethylene / 1-butene copolymer having a finely divided polymer amount 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 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, no adhesion of the prepolymerization catalyst to the reactor wall was observed.

[Polymerization] The same procedure as in Example 1 was repeated except that the solid catalyst prepared above was used, and the MFR was 2.01 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.
189 g of an ethylene / 1-butene copolymer having a concentration of 1% by weight 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. The amount of silica and the organoaluminum oxy compound used were changed to 1.4 g and 8.24 mmol, respectively.
And the prepolymerization time is set to 2 hours to obtain 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 prepolymerization catalyst to the reactor wall was observed.

[Polymerization] In Example 1, the solid catalyst prepared as described above was used in an amount of 0.005 milligram atom in terms of zirconium atom and 0.63 mmol of triisobutylaminium, and the 1-butene content in the mixed gas was adjusted. 5.9 mol%, hydrogenation amount 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 finely divided polymer of 100 μm or less of 0.1% by weight is obtained. It was

[0151]

[Example 13] [Preparation of solid catalyst (zirconium catalyst)] Silica (TG-40209 manufactured by Fuji Devison Co., amount of adsorbed water: 0.3% by weight, hydroxyl group content: 2.7% by weight) was placed in a 400-ml glass flask sufficiently purged with nitrogen. %) 18.2 g and 300 ml of toluene were added to form a suspension, and the suspension was cooled to 0 ° C. 33.6 ml of a toluene solution of an organoaluminum oxy compound (a solution of methylaluminoxane manufactured by Schering Co., which was dried and redissolved in toluene; Al; 4.16 mol / liter) was added to this suspension in 1 hour. Dropped. At this time, the temperature in the system was kept at 0 ° C. Then, the reaction was carried out at 0 ° C. for 30 minutes and further at 95 ° C. for 24 hours. After the reaction was completed, it was cooled to 60 ° C. and the solvent was removed by decantation. Then, it was washed 3 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 / l) was added thereto.
A solution of 5 mmol and bis (1,3-dimethylcyclopentadienyl) zirconium dichloride in toluene (Zr;
5.2 ml (0.0291 mol / l) were added. Then, ethylene gas (atmospheric pressure) was continuously introduced, and the temperature was 35 ° C.
Was preliminarily polymerized for 2 hours. At this time, adhesion to the reactor wall was not recognized.

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

[Polymerization] 150 g of sodium chloride (Wako Pure Chemical Industries, Ltd.) was placed in a stainless steel autoclave having an internal volume of 2 liters, which was sufficiently replaced with nitrogen, and dried under reduced pressure at 90 ° C. for 1 hour. After that, 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 heated to 75 ° C. Next, 0.004 milligram atom of zirconium atom and 1 mmol of triisobutylaluminum were added to the autoclave of the solid catalyst prepared as described above.

Then, 50 Nml of hydrogen was introduced, and further the mixed gas of ethylene and 1-butene was introduced, and the total pressure was 8 kg / cm ² -G to start the polymerization. The temperature in the system immediately rose to 85 ° C. After that, only the mixed gas was replenished and the total pressure was maintained at 8 kg / cm ² -G, while maintaining the total pressure at 85 ° C. for 1.5
Polymerization was carried out for a time.

After completion of the polymerization, sodium chloride was removed by washing with water, and the remaining polymer was washed with methanol.
It was dried under reduced pressure at 0 ° C overnight. As a result, 2.16 at 190 ℃
The MFR measured under a load of kg is 0.01 g / 10 minutes 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 weight. % Of ethylene / 1-butene copolymer was obtained, and the catalyst preparation and polymerization results are shown in Table 1 and Table 2, respectively.

[0157]

[Table 1]

[0158]

[Table 2]

[Brief description of drawings]

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

Claims (9)

[Claims] 1. [A] (a-1) (i) An oxide of at least one element selected from Group II, Group III and Group IV, and (ii) Adsorbed water content of 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 a surface hydroxyl group of 1.0% by weight or more, and a [B] cyclopentadienyl skeleton. Including a ligand having
A solid catalyst for olefin polymerization, which is formed by prepolymerizing an olefin in a suspension or in a gas phase using a catalyst component composed of a Group IVB transition metal compound. 2. [A] (a-1) (i) An oxide of at least one element selected from Group II, Group III and Group IV, and (ii) Adsorbed water content of less than 1.0% by weight. And (iii) a solid catalyst component in which (a-2) an organoaluminum oxy compound is supported on a particulate carrier having a surface hydroxyl group of 1.0% by weight or more, and [B] cyclopentadienyl skeleton Including a ligand having
It is formed by prepolymerizing an olefin in a suspension or in a gas phase using a catalyst component consisting of a Group IVB transition metal compound and a [C] organoaluminum compound. Solid catalyst. 3. The transition metal compound [B] contains a ligand having a hydrocarbon group-substituted cyclopentadienyl group IV
The olefin polymerization catalyst according to claim 1 or 2, which is a Group B transition metal compound. 4. An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 1. 5. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 2. 6. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 3. 7. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 1 and an organoaluminum compound. 8. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 2 and an organoaluminum compound. 9. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the solid catalyst for olefin polymerization according to claim 3 and an organoaluminum compound.