KR940010334B1 - Solid catalyst for olefin polymerization, catalyst for olefin polymerization and olefin polymerization method using the same - Google Patents

Abstract

No content.

Description

Solid catalyst for olefin polymerization, catalyst for olefin polymerization and olefin polymerization method using the same

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram of a method for producing a catalyst for polymerizing olefins according to the present invention.

2 is another schematic view of a method for producing a catalyst for first olefin polymerization according to the present invention.

3 is a schematic view of a method for producing a catalyst for second olefin polymerization according to the present invention.

4 is another schematic view of a method for producing a catalyst for second olefin polymerization according to the present invention.

The present invention relates to a solid catalyst for olefin polymerization, a catalyst for olefin polymerization, and an olefin polymerization method using these catalysts. More specifically, the present invention is applicable to suspension polymerization and gas phase polymerization, and a solid catalyst for olefin polymerization, an olefin polymerization catalyst, and an olefin using the catalysts, which can produce spherical olefin polymers having excellent particle characteristics with high polymerization activity. It relates to a polymerization reaction.

Conventionally, titanium-based catalysts made of titanium compounds and organic aluminum compounds or vanadium catalysts made of vanadium compounds and organic aluminum compounds are known as catalysts for producing α-olefin polymers such as ethylene polymers or ethylene / α-olefin copolymers. have.

Recently, a novel Ziegler-type catalyst composed of a zirconium compound and an organoaluminum oxy compound has been developed as a catalyst for producing an ethylene / α-olefin copolymer with high polymerization activity, and an ethylene / α-olefin copolymer using such a catalyst Has been recently proposed, for example, in JP-A-58-19309, 60-35005, 50-35006, 60-35007 60-35008.

The catalyst formed from the transition metal compound and the organoaluminum oxy compound proposed in the prior art is significantly superior in ethylene polymerization activity to the catalyst formed from the transition metal compound and the organoaluminum compound known before the new catalyst generation. Most of the catalysts proposed in the art are soluble in the reaction systems in which they are used, and in general, the process for producing ethylene / a-olefin copolymers using these novel catalysts is applicable only to solution polymerization systems.

When using these catalysts to produce polymers of high molecular weight, the solution viscosity containing the polymer is significantly increased, resulting in a decrease in productivity, or the resulting polymer obtained by post-treatment has a low density, which is a spherical olefin having excellent particle characteristics. It becomes difficult to obtain a polymer.

On the other hand, olefin polymerization is carried out in a suspension polymerization system or a gas phase polymerization system using a catalyst composed of the transition metal compound and the organoaluminum oxy compound, at least one of which is supported on a porous inorganic oxide carrier such as silica, silica alumina, or alumina. There was an attempt to do so.

For example, Japanese Patent Application Laid-Open No. 60-35006, Japanese Patent Application Laid-Open No. 60-35007, and Japanese Patent Application Laid-Open No. 60-35008 disclose a catalyst having a transition metal compound and an organoaluminum compound supported on silica, silica alumina, alumina, or the like. The effect used to prepare an ethylene / α-olefin copolymer is described.

Japanese Unexamined Patent Publication Nos. 60-106808 and 60-106809 disclose ethylene in the presence of a product which is obtained in advance by contacting a high activity catalyst containing a hydrocarbon-soluble titanium compound and / or a zirconium compound with a filler, an organic aluminum compound and a polyolefin-compatible filler. A method for producing a composition containing a polyethylene polymer and a filler which polymerizes or copolymerizes ethylene with another α-olefin is disclosed.

Japanese Patent Application Laid-Open No. 61-31404 discloses the polymerization or copolymerization of ethylene or ethylene and α-olefin in the presence of a mixed catalyst of a product and a transition metal compound obtained by reacting trialkyl aluminum and water in the presence of silicon dioxide or aluminum oxide. A method is proposed.

Japanese Patent Application Laid-Open No. 61-276805 discloses polymerization of olefins in the presence of a catalyst made of a reaction mixture obtained by reacting a reaction mixture of a zirconium compound, an aminooxane and trialkylaluminum, and an inorganic oxide containing a surface hydroxyl group such as silica. The method of making is disclosed.

Japanese Patent Application Laid-Open No. 61-108610 and Japanese Patent Laid-Open No. 61-296008 disclose a method of polymerizing olefins in the presence of a catalyst in which a transition metal such as metallocene and aluminoxane are supported on a carrier such as an inorganic oxide. .

However, when the olefin is polymerized or copolymerized in the suspension or gas phase polymerization system in the presence of the solid catalyst component supported on the carrier as described above, the polymerization activity achieved in the reaction system is much lower than that of the solution polymerization system, and the polymer formed The density of is insufficient.

Japanese Patent Laid-Open No. 63-280703 discloses prepolymerization of olefins in the presence of a carrier such as a zirconium compound, an aluminoxane, an organic aluminum compound, and silica. This method has a high polymerization activity and good particle characteristics of the produced polymer, but there is a problem that the prepolymerization catalyst adheres to the reactor wall during the prepolymerization.

In addition, in the prior art, olefin polymers prepared using the catalyst generally have a narrow molecular weight distribution, and thus the catalysts have been used to prepare polymers having a narrow molecular weight distribution.

However, the olefin polymers may have limited molding conditions when their molecular weight distribution is narrow, and therefore, the polymers are required to have a wide molecular weight distribution depending on the molding method or the purpose of use thereof.

In addition, when the expanded film is molded at a high speed from the polymer prepared above, the polymer used has a large melt tension with respect to its molecular weight in order to perform stable molding at high speed without flickering or bubble bursting. The polymer to be used must be selected from those having. Similar properties are needed to radiate sag or rupture of the polymer during blow molding or to minimize the shortage of the film during T-die extrusion.

The present invention has been completed in order to solve the above problems of the prior art, and an object of the present invention is applicable to suspension polymerization and gas phase polymerization, and it is possible to prepare spherical olefin polymers having excellent particle characteristics with high polymerization activity. The present invention also relates to a solid catalyst for olefin polymerization, an olefin polymerization catalyst, and an olefin polymerization method using these catalysts, which can provide an olefin polymer having a narrow molecular weight distribution upon polymerization of two or more monomers.

Another object of the present invention can be applied to suspension polymerization and gas phase polymerization, to prepare spherical olefin polymers having excellent particle characteristics with high polymerization activity, to provide an olefin polymer having excellent melt tension, and to have a wide molecular weight distribution. And a solid catalyst for olefin polymerization and a catalyst for olefin polymerization capable of providing an olefin polymer having excellent moldability, and an olefin polymerization method using these catalysts for olefin polymerization.

The solid catalyst for the first olefin polymerization according to the present invention comprises (a-1) (iii) an oxide of at least one element selected from those belonging to group II, III and IV of the periodic table, and (II) 1.0 wt% of water To the periodic table group IVB containing less than and (III) a granular carrier containing 1.0 wt% or more of a surface hydroxyl group, and a ligand having (a-2) an organoaluminum oxy compound and (a-3) a cyclopentadienyl skeleton. A solid catalyst component comprising a transition metal compound of a metal belonging to said organic aluminum oxy compound (a-2) and a transition metal compound (a-3) supported on said particulate carrier (a-1). A-1].

The solid catalyst for olefin polymerization according to the present invention can form a catalyst for olefin polymerization as the solid catalyst component [A-1] together with the catalyst component [C-2] which is an organic aluminum compound.

The solid catalyst for olefin polymerization according to the present invention can form a catalyst for olefin polymerization as the solid catalyst component [A-1] together with the catalyst component [C-2] which is an organic aluminum compound.

The solid catalyst for the first olefin polymerization according to the present invention may contain a polyolefin prepolymerized in suspension or gas phase.

The solid catalyst for the first olefin polymerization according to the present invention can be applied to suspension polymerization and gas phase polymerization, and it is possible to prepare spherical olefin polymers having excellent particle characteristics with high polymerization activity, and to polymerize two or more kinds of monomers. Olefin polymers with narrow molecular weight distribution can be provided.

Further, according to the solid catalyst for olefin polymerization of the present invention, when the transition metal compound (a-3) contains two or more transition metal compounds, the solid catalyst is applicable to suspension polymerization and gas phase polymerization, A spherical olefin polymer having excellent particle characteristics can be produced by high polymerization activity, and an olefin polymer having excellent melt tension, wide molecular weight distribution, and excellent moldability can be provided.

The solid catalyst for the second olefin polymerization according to the present invention comprises (a-1) (iii) an oxide of at least one element selected from those belonging to groups II, III and IV of the periodic table, and (II) 1.0 wt% of water A granular carrier containing less than 1.0 wt% or more of (III) surface hydroxyl group, and (a-2) an organoaluminum oxy compound, wherein the organoaluminum oxy compound (a-2) comprises the granular carrier (a-1). Prepolymerization of olefins in the presence of a catalyst component which is a transition metal compound of a metal belonging to Group IVB of the Periodic Table containing a solid catalyst component [A-2] supported on the a) and a ligand having a [B] cyclopentadienyl skeleton It is characterized by being manufactured by.

The solid catalyst for polymerization of the second olefin according to the present invention can be prepared by prepolymerizing olefin in the presence of the solid catalyst component [A-2] and the catalyst component [B] together with the catalyst component [C-1] which is an organic aluminum compound. Can be.

The solid catalyst for second olefin polymerization according to the present invention can constitute a catalyst for olefin polymerization together with the catalyst component [C-2] which is an organoaluminum compound.

The solid catalyst for the second olefin polymerization according to the present invention can be applied to suspension polymerization and gas phase polymerization, to prepare spherical olefin polymers having excellent particle characteristics with high polymerization activity, and at the time of polymerization of two or more kinds of monomers. Olefin polymers with narrow molecular weight distribution can be provided.

According to the second solid olefin polymerization catalyst of the present invention, when the catalyst component [B] contains two or more kinds of transition metal compounds, the solid catalyst is applicable to suspension polymerization and gas phase polymerization, and the particle characteristics An excellent spherical olefin polymer can be produced with high polymerization activity, and an olefin polymer having excellent melt tension, wide molecular weight distribution and excellent moldability can be provided.

The solid catalyst for olefin polymerization, the catalyst for olefin polymerization and the polymerization method using these catalysts are used in detail.

In the present invention, the term "polymerization" may include both homopolymerization and copolymerization, and the term "polymer" may include both homopolymer and copolymer.

In the present invention, the composition comprises (a-1) (iii) an oxide of at least one element selected from those belonging to groups II, III and IV of the periodic table, and (ii) a predetermined amount of water and (iii) a predetermined amount of surface hydroxyl group. A solid catalyst component carrying a transition metal compound of a metal belonging to group IVB of the periodic table containing (a-2) an organoaluminum oxy compound and (a-3) a ligand having a cyclopentadienyl skeleton on a granular carrier [ A-1] and (a-1) (iii) Oxides of at least one element selected from those belonging to groups II, III and IV of the periodic table, (ii) predetermined amount of water and (iii) predetermined amount of surface hydroxyl group On the granular carrier containing (a-2), a solid catalyst component [A-2] carrying the organoaluminum oxy compound is used.

In the present invention, the particulate carrier (a-1) used for the solid catalyst components [A-1] and [A-2] is an oxide of at least one element selected from those belonging to group II, III and IV of the periodic table. Configured granular inorganic compounds.

Preferably, the particulate inorganic compound is specifically a porous oxide such as SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or a mixture of porous oxides, For example, 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, and SiO ₂ -TiO ₂ -MgO. Among these particulate inorganic compounds, those having as a main component at least one component selected from the group consisting of SiO ₂ , Al ₂ O ₃ , and MgO are preferable.

The average particle diameter of the granular carrier (a-1) is usually 1 to 300 µm, preferably 10 to 200 µm, and the specific surface area is 50 to 1000 m ² / g, preferably 100 to 700 m ² / g, and the pore volume is , 0.3 to 2.5 m ³ / g.

The granular carrier (a-1) used in the present invention contains water of less than 1.0% by weight, preferably less than 0.5% by weight, and is 1.0% by weight or more, preferably 1.0 to 4.0% by weight, in particular 2.0 to 3.5. It contains by weight of surface hydroxyl groups.

In the following method, the water content and the surface hydroxyl group content of the particulate carrier can be obtained.

[Adsorbed water amount of the carrier]

In the present invention, the weight loss of the granular carrier obtained by drying the carrier for 4 hours under nitrogen circulation at 200 ° C. is taken as the adsorption water amount of the carrier.

[Surface Hydroxyl Content of the Carrier]

The weight of the granular carrier obtained by drying the carrier under a circulation of 200 ° C. for 4 hours at X (g), and by sintering the dried carrier at 1000 ° C. for 20 hours to remove the surface hydroxyl group. When Y is (g), the surface hydroxyl content of the carrier is calculated by the following formula.

Surface hydroxyl group (wt%) =

By using a granular carrier containing a specific amount of adsorbed water and a surface hydroxyl group as described above, an olefin polymerization catalyst component capable of producing an olefin polymer having excellent particle characteristics with high polymerization activity can be obtained.

The organoaluminum oxy compound (a-2) used in the present invention may be a conventional aluminoxane or a benzene insoluble organoaluminum oxy compound.

The conventional aluminoxane can be produced, for example, by the following method.

(1) Hydrocarbon solvent suspensions such as compounds containing adsorbed water or salts containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate and cerium chloride Reaction with an organic aluminum compound such as, and recovering the desired aluminoxane as a hydrocarbon solution containing it

(2) Treatment of organic aluminum compounds such as trialkylaluminum directly with water, ice or steam in a solvent such as benzene, toluene, ethyl ether or tetrahydrofuran

(3) A method in which an organic aluminum compound such as trialkyl aluminum is reacted with an organic tin oxide in a solvent such as decane, benzene or toluene.

Such aluminoxane may contain a small amount of organometallic components. From the solution containing the recovered aluminoxane, the solvent or unreacted organoaluminum compound can be distilled off, and the remaining aluminoxane can be redissolved in the solvent.

As an organoaluminum compound used for the said aluminoxane solution preparation, Specifically; Trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-sec-butyl aluminum, tri-t-butyl aluminum, tripentyl aluminum, trihexyl aluminum, Trialkyl aluminums such as trioctyl aluminum and tridecyl aluminum; Tricycloalkyl aluminums such as tricyclohexyl aluminum and tricyclo octyl aluminum; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide or diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride or diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide or diethyl aluminum ethoxide; And dialkyl aluminum aryl oxides such as diethyl aluminum phenoxide.

Among these, trialkyl aluminum is particularly preferable.

In addition, as the organic aluminum compound, a general formula

(iC ₄ H ₉ ) _x , Al _y (C ₅ H ₁₀ ) _z , [Ⅰ]

Isoprenyl aluminum represented by (x, y, z are each a positive number and z≥2x) can also be used.

Such organoaluminum compounds are used alone or in combination.

Examples of the solvent used in the aluminoxane solution include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; Aromatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; Petroleum oils such as gasoline, kerosene and gas oil; Or halogenated hydrocarbons such as halides such as chlorides and bromide, especially of the aromatic, aliphatic and alicyclic hydrocarbons. In addition to these, ethers, such as ethyl ether and tetrahydrofuran, can also be used. Of the solvents exemplified above, aromatic hydrocarbons are particularly preferred.

The first method for preparing the benzene insoluble organoaluminum oxy compound is characterized in that the aluminoxane solution is brought into contact with water or an active hydrogen-containing compound, and the second method is such that the organic aluminum is directly contacted with water. Let's do it.

Examples of the active hydrogen-containing compounds used in the present invention include alcohols such as methanol, ethanol, n-prepanol and isopropanol; Diols such as ethylene glycol and hydroquinone; Organic acids such as acetic acid and propionic acid are used.

Among them, alcohols and diols are preferable, and alcohols are particularly preferable.

The water or active hydrogen compound in contact with the solution of aluminoxane is dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene, hexane, ether solvent such as tetrahydrofuran, amine solvent such as triethylamine, or in a vapor or solid state. Can be used as The water in contact with the aluminoxane may be crystalline water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and first cerium chloride, or inorganic compounds or polymers such as silica, alumina, aluminum hydroxide, and the like. Adsorbed water or the like can also be used.

The contact reaction between a solution of aluminoxane and water or active hydrogen-containing compounds is usually carried out in a solvent. The solvent includes the solvents which are inert solvents, and hydrocarbon solvents such as aromatic hydrocarbons; Aliphatic hydrocarbons, cycloaliphatic hydrocarbons, petroleum fractions, halogenated hydrocarbons and ethers. Of these solvents, aromatic hydrocarbons are particularly preferred.

The water or the active hydrogen-containing compound used in the contact reaction is used in an amount of 0.1 to 5 moles, preferably 0.2 to 3 moles per mole of Al atoms in the solution of aluminoxane. The concentration in the reaction system is usually in the range of 1 × 10 ^{−3 to} 5 gram atoms / L, preferably 1 × 10 ⁻² to 3 gram atoms / L in terms of aluminum atoms. Moreover, it is preferable that the density | concentration of the water in a reaction system is 2 x 10 <^{-4> -5} mol / l normally, Preferably it is a concentration of 2 x 10 <^{-3> -3} mol / l.

For example, the method of contacting a solution of aluminoxane with water or an active hydrogen-containing compound is carried out in the following manner.

(1) A method of contacting a solution of aluminoxane with a hydrocarbon solvent containing water or an active hydrogen-containing compound

(2) A method in which aluminoxane and vapor are brought into contact with each other by injecting steam or a vapor of an active hydrogen-containing compound into a solution of aluminoxane.

(3) A method of directly contacting a solution of aluminoxane with water or ice or an active hydrogen-containing compound

(4) A method of contacting aluminoxane with adsorbed or crystalline water by mixing a solution of aluminoxane with a hydrocarbon suspension of an adsorbed water-containing compound or a crystalline water-containing compound or a hydrocarbon suspension of a compound adsorbed with an active hydrogen-containing compound.

Such a solution of aluminoxane may contain other components as long as it does not adversely affect the reaction of the aluminoxane with water or an active hydrogen-containing compound.

The contact reaction between the solution of the aluminoxane and water or the active hydrogen-containing compound is usually carried out at a temperature of -50 to 150 ° C, preferably 0 to 120 ° C, more preferably 20 to 100 ° C. The reaction time varies greatly depending on the reaction temperature, but is usually 0.5 to 300 hours, preferably about 1 to 150 hours.

The production method for producing a benzene-insoluble organoaluminum oxy compound is to bring the above-mentioned organoaluminum directly into water.

In this case, water is used in an amount such that the amount of organoaluminum atoms dissolved in the reaction system is 20% or less with respect to all organoaluminum atoms.

Water to be brought into contact with the organoaluminum compound may be dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene, hexane, ether solvent such as tetrahydrofuran, amine solvent such as triethylamine, or the like in the form of steam or ice. As water to be in contact with the organic aluminum compound, crystal water of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerium chloride, or inorganic compounds or polymers such as silica, alumina, aluminum hydroxide, and the like Adsorbed water or the like adsorbed on the surface may also be used.

The contact reaction between the organic aluminum compound and water is usually carried out in a solvent such as a compound which is an inert compound. Of these solvents, aromatic hydrocarbons are particularly preferred.

In the reaction system, the concentration of the organoaluminum compound is 1 × 10 ^{−3 to} 5 mol / l, preferably 1 × 10 ⁻² to 3 mol / l, in terms of aluminum atom, and the concentration of water in the reaction system is usually 1 × 10 ^−3. It is preferable that it is -5 mol / L, Preferably it is the density | concentration of 1 * 10 <^{-2> -3} mol / L.

In this reaction, it is preferable that the organic aluminum atom dissolved in the reaction system is 20% or less, preferably 10% or less, more preferably 0 to 5% with respect to all organic aluminum atoms.

For example, the organic aluminum compound can be brought into contact with water by the following method.

(1) A method of bringing a hydrocarbon solution of organic aluminum into contact with a hydrocarbon solvent containing water.

(2) Method of contacting organic aluminum with water vapor by blowing water vapor into hydrocarbon solution of organic aluminum.

(3) A method of bringing organic aluminum into contact with adsorbed or crystalline water by mixing a hydrocarbon solution of organic aluminum with a hydrocarbon suspension of an adsorbed water-containing compound or a crystalline water-containing compound.

(4) A method of directly contacting a hydrocarbon solution of organic aluminum with ice

The hydrocarbon solution of the organic aluminum as described above may have other components as long as it does not adversely affect the reaction between the organic aluminum and water.

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

The benzene-insoluble organic aluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C of 10% or less, preferably 5% or less, particularly 2% or less, in terms of Al atoms, and is insoluble in benzene. Or poorly soluble in water. The solubility in benzene of such organoaluminum oxycompound was suspended in 100 ml of benzene, which was equivalent to 100 mg of Al, and then mixed for 6 hours at 60 ° C under stirring, followed by the jacketed G- Filtration at 60 ° C. using a 5 glass filter, and washing the solid part separated on the filter 4 times with 50 ml of benzene at 60 ° C., measured the amount of Al atoms present in the total filtrate (x millimoles). Obtain it by

When analyzed by the benzene-insoluble organic aluminum oxy-compound according to the present invention, the infrared spectroscopy (IR), the absorbance (D _1220), and absorbance (D ₁₂₆₀₎ in the vicinity of about 1220cm ^-1 in the vicinity of about 1220cm ^-1 The ratio D ₁₂₂₀ / D ₁₂₆₀ is preferably 0.09 or less, preferably 0.08 or less, and particularly preferably in the range of 0.04 to 0.07.

Infrared spectroscopic analysis of the organic aluminum oxy compound is performed as follows.

First, the organoaluminum oxy compound and Nujol are pulverized in agate mortar in a nitrogen box to form a paste. Next, the sample in the form of a paste is placed on a KBr plate, and the IR spectrum is measured by IR-810 manufactured by Nippon Shoko Co., under a nitrogen atmosphere.

D ₁₂₆₀ / D ₁₂₂₀ is obtained from the IR spectrum thus obtained, and this D ₁₂₆₀ / D ₁₂₂₀ value is obtained as follows.

(a) 1280cm ^-1 connecting the maximum point in the vicinity of 1240cm ^-1 and near them to the baseline L _1.

(b) Draw a vertical line (T%) of the absorption minimum point near 1260cm ^-1 and the vertical line with respect to the wave contraction (horizontal axis) at this minimum point, and the transmittance (T _o %) of the intersection point between this vertical line and the baseline L ₁ . Read and calculate the absorbance near ₁₂₆₀ cm ^-1 (D ₁₂₆₀ = logT _o / T).

(c) As above, the maximum point near 1280 cm ⁻¹ and 1180 cm ⁻¹ are connected to each other, and this is referred to as the base line L ₂ .

(d) The transmittance (T '%) of the absorption minimum point near 1220 cm ^-1 and the vertical line is drawn from the minimum point with respect to the wave contraction (horizontal axis), and the transmittance (T _O '% of the intersection point between the vertical line and the baseline L ₂ ). ) And calculate the absorbance near ₁₂₂₀ cm ^-1 (D ₁₂₂₀ = log T _O '/ T').

(e) Calculate D ₁₂₆₀ / D ₁₂₂₀ from these values.

The organic aluminum compound is of the benzene-soluble D ₁₂₆₀ / D ₁₂₂₀ value of about 0.10 to 0.13, and between, the organic aluminum oxy compound insoluble in benzene according to the present invention and an organic aluminum oxy compound in benzene is soluble in the conventional D ₁₂₆₀ The value of / D ₁₂₂₀ is clearly different.

The benzene-insoluble organoaluminum oxy compound in the present invention is represented by Formula (II)

It is assumed to have an alkyloxy aluminum unit represented by.

In said alkyloxyaluminum unit, R <^1> is a C1-C9 hydrocarbon group, specifically a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, pentyl group, hexyl group , An octyl group, a decyl group, a cyclohexyl group, a cyclooctyl group, etc. are illustrated. Of these, methyl and ethyl groups are preferred, and methyl groups are particularly preferred.

The benzene-insoluble organoaluminum oxy compound according to the present invention may contain one or more alkyloxy aluminum units in the benzene-insoluble organoaluminum oxy compound represented by formula (ii).

In addition to the alkyloxyaluminum unit of Formula (II), The oxyaluminum unit (wherein R ² is a C10-12 hydrocarbon group, a C1-12 alkoxy group, a C6-20 aryloxy group, a hydroxyl group, a halogen or hydrogen) may be contained.

In this case, the said organoaluminum oxy compound contains the said alkyloxy aluminum unit (i) and the alkyloxy aluminum unit (ii), and the said alkyloxy aluminum unit (iii) is 30 mol% or more, Preferably it is 50 mol%. As mentioned above, it is especially preferable that it is 70 mol% or less.

Solid catalyst component [A-2] used by this invention is manufactured using said component (a-1) and (a-2).

The solid catalyst component [A-1] used in the present invention is a transition metal compound of metal belonging to group IVB of the periodic table having a cyclopentadienyl skeleton in addition to the components (a-1) and (a-2). Manufactured by 3).

The transition metal compound (a-3) of a metal belonging to group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton used in the present invention is represented by the following formula [IV].

ML _x ... … … … … … … … … … … … … … … … … … … … … … … … [IV]

Wherein L is a ligand coordinated to the transition metal, at least one of L has a cyclopentadienyl skeleton, and L other than a ligand having a cyclopentadienyl skeleton is a hydrocarbon group, alkoxy group, or aryl having 1 to 12 carbon atoms. Oxy group, halogen, trialkylsilyl group SO ₃ R (wherein R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen) or hydrogen, and X is the valence of the transition metal.

Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, Alkyl substitution, such as an ethyl cyclopentadienyl group, methyl ethyl cyclopentadienyl, propyl cyclopentadienyl, methyl propyl cyclopentadienyl, butyl cyclopentadienyl, methyl butyl cyclopentadienyl, and a hexyl cyclopentadienyl group Cyclopentadienyl group, indenyl group, 4,5,6,7-tetrahydroindenyl group and furoenyl group. These may be substituted by halogen atoms or trialkylsilyl groups.

Alkyl-substituted cyclopentadienyl groups are most preferred among the ligands coordinated to the transition metal.

When the compound represented by the formula ML _x [IV] has two or more ligands having a cyclopentadienyl skeleton, at least two ligands having a cycloalkadienyl skeleton are selected from ethylene, propylene, isopropylidene groups, and the like. The alkylene group may be bonded to each other through a substituted alkylene group such as diphenylmethylene and a silylene group or a substituted silylene group such as dimethylsilylene, diphenylsilylene, methylphenylsilylene, and the like.

A ligand 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 trialkylsilyl group, SO ₃ R, or hydrogen.

As a C1-C12 hydrocarbon group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, etc. can be illustrated; Specifically, alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group and pentyl group; As said cycloalkyl group, a cyclopentyl group, a cyclohexyl group, etc. are illustrated; As an aryl group, a phenyl group, a tolyl group, etc. are illustrated; Examples of the allalkyl group include a benzyl group and a neofill group.

As an alkoxy group, a methoxy group, an ethoxy group, butoxy group etc. are illustrated, and a phenoxy group etc. are illustrated as an allyloxy group.

Examples of the halogen include fluorine, chlorine, bromine and iodine.

Examples of the ligand represented by SO ₃ R and the like include p-toluene sulfonate, methanesulfonate and trifurmethanesulfonate.

In the present invention, a ligand having a cyclopentadienyl skeleton used in the preparation of the solid catalyst component [A-1] is a tetravalent transition metal, for example, a transition metal compound (a-3) of a metal belonging to group IV. There is this. Specifically, the transition metal compound (a-3) can be represented by the following formula [IV '].

R _a ¹ R _b ² R _c ³ R _d ⁴ M... … … … … … … … … … … … … … … … … … … … … [IV ']

M is zirconium, titanium, or hafnium, R ¹ is a group having a cyclopentadienyl skeleton, and R ² , R ³ and R ⁴ are each a group having a cyclopentadienyl skeleton, alkyl, cycloalkyl, aryl, aral A kill, alkoxy or aryloxy group, halogen trialkylsilyl group, SO ₃ R or hydrogen, a is an integer of at least 1 and a + b + c + d = 4.

Of the transition metal compounds of the formula [IV '], at least one of R ² , R ^3, and R ⁴ preferably has a cyclopentadienyl skeleton, that is, R ¹ and R ² each represent a cyclopentadienyl skeleton. It is group which has. Groups having such a cyclopentadienyl skeleton include alkylene groups such as ethylene and propylene, substituted alkylene groups such as diphenylmethylene and alkylidene groups such as isopropylidene, silylene groups, or dimethylsilylene and diphenylsilyl. And silane, and substituted silylene groups such as methylphenylsilylene. R ³ and R ⁴ are each a cyclopentadienyl skeleton, alkyl, cycloalkyl, aryl, aralkyl, alkoxy group, or aryloxy group, halogen, trialkylsilyl group, SO ₃ R or hydrogen.

Representative examples of the transition metal compound (a-3) having a cyclopentadienyl skeleton represented by the formula ML _x (M is zirconium) are as follows.

Bis (indenyl) zirconium dichloride,

Bis (indenyl) zilconium dibromide,

Bis (indenyl) zirconium bis (p-toluenesulfonate),

Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Bis (fluoroenyl) zirconium dichloride,

Ethylenebis (indenyl) zirconium dichloride,

Ethylenebis (indenyl) zirconium dibromide,

Ethylenebis (indenyl) dimethylzylconium,

Ethylenebis (indenyl) diphenylzylconium,

Ethylenebis (indenyl) methylzylconium monochloride,

Ethylenebis (indenyl) zirconium bis (methanesulfonate),

Ethylenebis (indenyl) zirconium bis (p-toluenesulfonate),

Ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonate),

Ethylenebis (4,5,6,7-tetrahydro indenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl- fluorenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zylconium dichloride,

Dimethylsilylenebis (cyclopentadienyl) zylconium dichloride,

Dimethylsilylenebis (methylcyclopentadienyl) zylconium dichloride,

Dimethylsilylenebis (dimethyl cyclopentadienyl) zylconium dichloride,

Dimethylsilylenebis (trimethyl cyclopentadienyl) zylconium dichloride,

Dimethylsilylenebis (indenyl) zirconium dichloride,

Dimethylsilylenebis (indenyl) zilconium bis (trifluoromethanesulfonate),

Dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,

Dimethylsilylene (cyclopentadienyl-furorenyl) zirconium dichloride,

Diphenylsilylenebis (indenyl) zirconium dichloride,

Methylphenyldiphenylsilylenebis (indenyl) zylconium dichloride,

Bis (cyclopentadienyl) zirconium dichloride,

Bis (cyclopentadienyl) zylconium dibroide,

Bis (cyclopentadienyl) methylzylconium monochloride,

Bis (cyclopentadienyl) ethylzylconium monochloride,

Bis (cyclopentadienyl) cyclohexylsiliconium monochloride,

Bis (cyclopentadienyl) phenylzylconium monochloride,

Bis (cyclopentadienyl) benzylconiummonochloride,

Bis (cyclopentadienyl) zylconium monochloride monohydride,

Bis (cyclopentadienyl) methylzylconium monohydride,

Bis (cyclopentadienyl) dimethylzylconium,

Bis (cyclopentadienyl) diphenylzylconium,

Bis (cyclopentadienyl) dibenzylzirconium,

Bis (cyclopentadienyl) zylconium methoxy chloride,

Bis (cyclopentadienyl) zirconium ethoxy chloride,

Bis (cyclopentadienyl) zirconium bis (methanesulfonate),

Bis (cyclopentadienyl) zylconium bis (P-toluenesulfonate),

Bis (cyclopentadienyl) zirconium bis (tripurormethanesulfonate),

Bis (methylcyclopentadienyl) zylconium dichloride,

Bis (dimethylcyclopentadienyl) zirconium dichloride,

Bis (dimethylcyclopentadienyl) zylconium ethoxychloride,

Bis (dimethylcyclopentadienyl) zirconium bis (trifurmethanesulfonate),

Bis (ethylcyclopentadienyl) zirconium dichloride,

Bis (methylethylcyclopentadienyl) zirconium dichloride,

Bis (propylcyclopentadienyl) zirconium dichloride,

Bis (methylpropylcyclopentadienyl) zirconium dichloride,

Bis (butylcyclopentadienyl) zirconium dichloride,

Bis (methylbutylcyclopentadienyl) zirconium dichloride,

Bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate),

Bis (trimethylcyclopentadienyl) zirconium dichloride,

Bis (tetramethylcyclopentadienyl) zylconium dichloride,

Bis (pentamethylcyclopentadienyl) zylconium dichloride,

Bis (hexylcyclopentadienyl) zirconium dichloride,

Bis (trimethylcyclopentadienyl) zylconium dichloride.

In the transition metal compound, there are groups substituted with 1,2- and 1,3-substituted cyclopentadienyl groups, and the triple-substituted cyclopentadienyl groups include 1,2,3- and 1,2 , 4- substituted groups.

In addition, alkyl groups such as propyl and butyl include n-, i-, sec- and tert- isomers.

In addition, transition metal compounds obtained by substituting the titanium metal or the hafnium metal in the above-described examples of the zirconium compounds with titanium metal or hafnium metal may be used.

The transition metal compounds (a-3) may be used alone or in combination. When the transition metal compound (a-3) is used in combination, at least one selected from the group consisting of the following compounds (iii) and (ii), and at least one selected from the group consisting of the following compounds (iii) and (iii) It is desirable to.

The compound (iii), (ii), (iii) and (iii) are as follows.

(Iii) a transition metal compound having two ligands having a cyclopentadienyl skeleton, wherein these ligands are bonded to each other through substituted or unsubstituted alkylene groups, substituted or unsubstituted silylene groups, etc. Referred to as "crosslinked transition metal compounds"

(Ii) a transition metal compound containing two ligands having a cycloalkadienyl skeleton, wherein the ligands are not bonded to one another (hereinafter referred to as "non-crosslinked transition metal compounds"), the ligands having 2 to 5 substituents Have

(Iii) a transition metal compound containing a ligand having a cyclopentadienyl skeleton, wherein the ligand has no substituent (non-crosslinked transition metal compound)

(Iii) a transition metal compound containing a ligand having a cyclopentadienyl skeleton, the ligand having one substituent (non-crosslinked transition metal compound)

In the above combination, the ligand is a non-crosslinked transition metal compound (ii) containing a ligand having a cyclopentadienyl skeleton having 2 to 3 substituents, in particular, a ligand having a cyclopentadienyl skeleton having one substituent. It is most preferable to combine with the non-crosslinked transition metal compound (VIII) containing.

When mixing two types of compounds (a-3), the usage-amount of this one compound is 5-95 mol%, More preferably, it is 10-90 mol%, Most preferably, it is 20-80 mol%. When mixing 3 or more types of compounds (a-3), the mixing ratio is not specifically proposed, but the usage-amount of 1 type is 95 mol% or less and 5 mol% or more are good.

The solid catalyst for the first olefin polymerization is a solid catalyst component composed of the above-described components, that is, the particulate carrier (a-1), the organoaluminum oxy compound (a-2), and the transition metal compound (a-3).

When compound (a-3) is used alone in the preparation of the solid catalyst for first olefin polymerization, an olefin polymer having a narrow molecular weight distribution can be obtained. When two or more kinds of compounds (a-3) are used in the preparation of the solid catalyst for first olefin polymerization, an olefin polymer having a wide molecular weight distribution and excellent moldability can be obtained.

The solid catalyst for the first olefin polymerization can be used as it is for olefin polymerization, and can be used for olefin polymerization after prepolymerization in the presence of an organoaluminum compound [C-1] optionally in a suspension or a gas phase.

The catalyst for olefin polymerization of the present invention is composed of organoaluminum as the solid catalyst (solid catalyst component [A-1]) and catalyst component [C-2] for the first olefin polymerization, and is used for the olefin polymerization. do.

In the solid catalyst for the second olefin polymerization, the solid catalyst component [A-2] made of the particulate carrier (a-1) and the organoaluminum oxy compound (a-2) contains a cycloalkadienyl skeleton as a catalyst component. It is prepared by prepolymerizing an olefin in solution or gas phase in the presence of a transition metal compound [B] of a metal belonging to group IVB of the periodic table and optionally an organoaluminum compound as a catalyst component [C-1].

As the transition metal compound [B] belonging to group IVB of the periodic table containing a cycloalkadienyl skeleton used in the production of the catalyst for the second olefin polymerization, the transition metal compound used in the production of the solid catalyst for the first olefin polymerization. (A-3) can be illustrated. These transition metal compounds [B] can be used alone or in combination. When compound [B] is used independently for said solid catalyst manufacture for 2nd olefin polymerization, an olefin polymer with a narrow molecular weight distribution can be obtained.

When using 2 or more types of catalyst components [B], 2 or more types of transition metal compounds (a-3) used for the said solid catalyst for 1st olefin polymerization as a preferable combination are mentioned. The preferred combination ratio of the catalyst components [B] may be the same as the combination of the transition metal compound (a-3). When two or more compounds [B] are used for the preparation of the solid catalyst for the second olefin polymerization, an olefin polymer having a broad molecular weight distribution and excellent moldability can be obtained.

The organoaluminum compounds [C-1] and [C-2] used in the preparation of the first and second olefin polymerization solid catalysts and the first olefin polymerization catalyst are represented by the following formulas.

R _n ⁵ AlX _3-n ... … … … … … … … … … … … … … … … … … … … … [III]

In this formula, R <^5> is a C1-C12 hydrocarbon group, X is halogen or hydrogen, n is 1-3.

In formula, R <^5> is a C1-C12 hydrocarbon group, such as alkyl, cycloalkyl, or aryl, For example, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, Cyclohexyl, phenyl, tolyl and the like.

Specific examples of the organoaluminum compounds of the formula R _n ⁵ AlX _3-n are shown below.

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; Dialkyl aluminum halides such as dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl aluminum bromide; Alkyl aluminum seski halides, such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; Alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; The compounds represented by the formula R _n ⁵ AlY _3-n ... [IV] can also be used as the organoaluminum compounds [C-1] and [C-2]. In this formula, R ⁵ is as defined above, Y is -OR ⁵ , -OSiR ₃ , -OAlR ₂ ⁸ , -NR ₂ ⁸ , -SiR ₃ ¹⁰ , or -N (R ¹¹ ) AlR ₂ ¹² , n is 1-2, R ⁶ , R ⁷ , R ⁸ and R ¹² are methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl groups, and R ⁹ is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylyl Silyl group; R ¹⁰ and R ¹¹ are each methyl or ethyl groups.

Specific examples of the organoaluminum compound of the formula R ⁵ AlY _3-n ... [IV] include the following compounds.

(Iii) a compound of R _n ⁵ Al (OR ⁶ ) _3-n ;

Dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc .;

(Ii) a compound of R _n ⁵ Al (OSiR ₃ ⁷ ) _3-n ;

(C ₂ H ₅ ) ₂ AlOSi (CH ₃ ) ₃ , (iso-C ₄ H ₉ ) ₂ AlOSi (CH ₃ ) ₃ , (iso-C ₄ H ₉ ) ₂ AlOSi (C ₂ H ₅ ) _2, and the like;

(Iii) a compound of R _n ⁵ Al (OAlRR ₂ ⁸ ) _3-n ;

(C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (iso-C ₄ H ₉ ) ₂ AlOAl (iso-C ₄ H ₉ ), and the like;

(Iii) a compound of R _n ⁵ Al (NRl ₂ ⁹ ) _3-n ;

(CH ₃ ) ₂ AlN (C ₂ H ₅ ) ₂ , (C ₂ H ₅ ) ₂ AlNHCH ₃ , (CH ₃ ) ₂ AlNH (C ₂ H ₅ ), (C ₂ H ₅ ) ₂ AlN (Si (CH ₃ ) ₃ ) ₂ , (iso-C ₄ H ₉ ) ₂ AlN (Si (CH ₃ ) _2, etc .;

(Iii) a compound of R _n ⁵ Al (SiR ₃ ¹⁰ ) _3-n ;

(iso-C ₄ H ₉ ) ₂ AlSi (CH ₃ ) ₃ and the like;

(Iii) a compound of R _n ⁵ Al (N (R ¹¹ ) AlR ₂ ¹² ) _3-n ;

(C ₂ H ₅ ) ₂ AlN (CH ₃ ) Al (C ₂ H ₅ ) ₂ , (iso-C ₄ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (iso-C ₄ H ₉ ) _2, and the like.

Among the organoaluminum compounds of the above formulas [III] and [IV], represented by the formula R _n ⁵ Al, R _n ⁵ Al (OR ⁶ ) _3-n , or R _n ⁵ Al (OAlR ⁸ ) _3-n An organoaluminum compound is preferable, and it is especially preferable that R <^5> is isoalkyl group and n = 2. These organoaluminum compounds can be used individually or in combination.

In the method for producing the olefin polymerization, the solid catalyst and the catalyst for the olefin polymerization, the components (a-1) (a-2) and (a-3), the solid catalyst components [A-1] and [A- 2], the catalyst components [B] and [C-1] and [C-2] are used and will be described in detail below.

The first catalyst for olefin polymerization is a transition metal compound of a metal belonging to group IVB of the periodic table containing the organoaluminum oxy compound (a-2) and a ligand having a cyclopentadienyl skeleton (a-3). The solid catalyst component [A-1] is prepared by being supported on the particulate carrier (a-1), and the contact of each component can be performed in an inert hydrocarbon solvent.

The catalyst for olefin polymerization of the present invention can be produced by mixing the solid catalyst component [A-1] and the catalyst component [C-2] in an inert hydrocarbon solvent.

Specific examples of the inert hydrocarbon solvent used in the production of the solid catalyst for the first olefin polymerization and the catalyst for the first olefin polymerization include aliphatics such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene. hydrocarbon; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane, and mixtures thereof.

Component (a-1), (a-2) and (a-3) constituting the solid catalyst component [A-1] (solid catalyst for first olefin polymerization) and the catalyst component [C-2] The contact can be carried out in any order as long as the solid catalyst component [A-1] is produced as an intermediate product, thereby producing a catalyst for the first olefin polymerization. When two or more kinds of component (a-3) of the solid catalyst component [A-1] are used, it is preferable to mix the components (a-3) in advance with each other.

1 and 2 show a production diagram of the catalyst for the first olefin polymerization.

Preferred production methods of the catalyst for the first olefin polymerization are as follows;

The particulate carrier (a-1) and the organoaluminum oxy compound (a-2) are mixed and contacted, and then the transition metal compound (a-3) is mixed and brought into contact with each other. -2]; The granular carrier (a-1) is brought into contact with a mixture of the organoaluminum oxy compound (a-2) and the transition metal compound (a-3), and an organoaluminum compound [C-2] is mixed as necessary. .

When the compound (a-1), (a-2), and (a-3) which comprise the said solid catalyst component [A-1] are mixed and contacted, the said component (a-1), (a-2) ) And (a-3) when compound [C-2] is optionally added, the amount of the compound (a-3) to be used is usually 5 × 10 ^{−6 to} 5 to 1 g of the compound (a-1). × 10 ^-4 mol, its concentration is 10 ^-4 to 2 × 10 ^-2 mol / l, preferably 2 × 10 ^-4 to 10 ^-2 mol / l. The atomic ratio [OH / Al _a-2 ] of Al of the surface hydroxyl group of the said component (a-1) and Al of the said component (a-2) is 0.1-0.5 normally, Preferably it is 0.15-0.4.

In the component (a-2), the atomic ratio [Al / (transition metal)] of Al to transition metal in component (a-3) is usually 10 to 500, preferably 20 to 200.

The atomic ratio (Al _c / Al _a-2 ) of the aluminum atom (Al _c ) in the component [C-2] arbitrarily used to the aluminum atom (Al _a-2 ) in the component (a-3) is usually 0.02 to 3, Preferably it is 0.05-1.5. Compound (a-1), (a-2) and (a-3) and compound [C-2] as necessary, usually at a temperature of -50 to 150 ° C, preferably -20 to 120 ° C, It is made to contact for 1 to 1000 minutes, Preferably it is 5 to 600 minutes.

The component (a-2) is contacted with the component (a-2) for a contact time of 0.5 to 1000 hours, preferably 1 to 500 hours, at a temperature of usually 50 to 150 ° C, preferably 60 to 120 ° C. do.

The catalyst for olefin polymerization of this invention can be used after prepolymerizing an olefin in presence of this catalyst and component [C-1] as needed. The amount of the transition metal compound (a-3) used in this prepolymerization is 10 ⁻⁶ to 10 ⁻² mol / l. This prepolymerization is performed at a temperature of -20 to 80 ° C, preferably 0 to 50 ° C for 0.5 to 100 hours, preferably 1 to 50 hours.

The olefin used in the prepolymerization is selected from olefins for polymerization, but ethylene is preferably used as the main component olefin to be prepolymerized.

The amount of the prepolymerized polyolefin produced in the prepolymerization is about 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g with respect to 1 g of the compound (a-1). When the solid catalyst for the first olefin polymerization is prepolymerized as described above, the amount of transition metal supported is 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ atoms, preferably 10 ⁻⁵ to 2 × 10 ⁻⁴ atoms, and aluminum The supported amount is about 10 ^{−3 to} 5 × 10 ⁻² g atoms, preferably 2 × 10 ⁻³ to 2 × 10 ⁻² g atoms, all of which are relative to 1 g of the compound (a-1) will be.

In the present invention, the prepolymerization can be carried out in any manner such as batch, semi-continuous or continuous.

When the olefin is polymerized in the presence of the first solid catalyst containing the solid catalyst for polymerization of the first olefin and the prepolymerized polyolefin and the catalyst for polymerization of the first olefin of the present invention, the amount of the transition metal compound (a-3) used (polymerization The volume per liter) is usually 10 ^-8 to 10 ^-3 g atoms, preferably 10 ^-7 to 10 ^-4 g atoms in terms of transition metal. In the catalyst for the first olefin polymerization of the present invention, the organoaluminum compound [C-2] may be used in combination with the solid catalyst component [A-1], but the aluminum catalyst for the first olefin polymerization of the present invention may be used as needed. It can be used together with noxic acid compound. The use amount of the aluminoxane compound and the organic aluminum compound [C-2] is 0 to 500 moles, preferably 5 to 200 moles, relative to 1 g of the transition metal.

The solid catalyst for polymerizing the first olefin of the present invention is a ligand having a particulate carrier (a-1), an organoaluminum oxy compound (a-2), and a cyclopentadienyl skeleton constituting the solid catalyst component [A-2]. A transition metal compound [B] of a metal belonging to group IVB of the periodic table containing the compound and the compound [C-1], if necessary, are mixed in an inert hydrocarbon solvent, and olefins are introduced into the mixture and prepolymerized. Can be.

Examples of the inert hydrocarbons used in the production of the second polymerization solid catalyst include the same solvents as those exemplified in the production of the first polymerization solid catalyst.

The contact between the components (a-1) and (a-2) constituting the solid catalyst component [A-2] and the catalyst component [B] and [C-1] is the solid catalyst component [A-2]. As long as the intermediate product is produced, the catalyst for the first olefin polymerization can be produced in any order. In the case where two or more kinds of the transition metal compound [B] are used, it is preferable to mix these transition metal components [B] with each other in advance.

3 and 4 show a production diagram of the catalyst for the second olefin polymerization.

The preferable manufacturing method of the catalyst for 2nd olefin polymerization is as follows;

The particulate carrier (a-1) constituting the solid catalyst component [A-2] and the organoaluminum oxy compound (a-2) are mixed and contacted, followed by mixing and contacting the transition metal compound [B], and The method of mixing an organoaluminum compound [C-1] here according to;

The particulate carrier (a-1) constituting the solid catalyst component [A-2] and the organoaluminum oxy compound (a-2) are mixed and contacted thereto, whereby the transition metal compound [B] and an organic aluminum compound [ C-1] in this order;

The granular carrier (a-1) is mixed and contacted with the organoaluminum oxy compound (a-2), and the organoaluminum compound [C-1] and the transition metal compound [B] are mixed in this order.

When compound (a-1), (a-2) and catalyst component [B] constituting the solid catalyst component [A-2] and component [C-1] are mixed and contacted as necessary, the compound (a -2) the amount of the is normal, the compound (a-1) and with respect to ^{1g 5 × 10 -4 ~2 × 10} -2 mol, preferably 10 ^-3 to 10 ^-2 mole, the concentration is 5 × 10 ^-2 to 2 mol / ℓ, preferably from 0.1 to 1 mol / ℓ. The atomic ratio [OH / Al _a-2 ] of Al of the surface hydroxyl group of the said component (a-1) and Al of the said component (a-2) is 0.1-0.5 normally, Preferably it is 0.15-0.4.

The atomic ratio [Al / (transition metal)] of Al to the transition metal in component [B] in the component (a-2) is usually 10 to 500, preferably 20 to 200.

Of optional component [C-1] is used as the aluminum atom [Al _c] against the component (a-2) an atomic ratio _{(Al c / Al a-2} ) is usually 0.02 of the aluminum atoms (Al _a-2) -3, Preferably it is 0.05-1.5. Compound [C-1] as necessary for the compounds (a-1) and (a-2) and the catalyst component [B] constituting the solid catalyst component [A-2] is usually -50 to 150 ° C. Preferably it is made into contact for 0.5 to 1000 hours, Preferably it is 1 to 500 hours at the temperature of -20-120 degreeC. In particular, the components (a-1) and (a-2) are usually brought into contact at a temperature of 50 to 150 ° C, preferably 60 to 120 ° C for 0.5 to 1000 hours, preferably 1 to 500 hours.

In the present invention, the solid catalyst for the second olefin polymerization includes the solid catalyst component [A-2] obtained above, a transition metal compound [B] of a metal belonging to the group IVB group containing a ligand having a cyclopentadienyl skeleton and If necessary, the olefin can be prepared by prepolymerization in an inert hydrocarbon solvent. The amount of the transition metal compound [B] used in this prepolymerization is 10 ⁻⁵ to 2 × 10 ⁻² mol / l, preferably 5 × 10 ⁻⁵ to 10 ⁻² mol / l. This prepolymerization is performed at a temperature of -20 to 80 ° C, preferably 0 to 50 ° C for 0.5 to 100 hours, preferably 1 to 50 hours.

The olefin used in the prepolymerization is selected from olefins for polymerization, but ethylene is preferably used as the main component olefin to be prepolymerized.

In the solid catalyst for second olefin polymerization obtained as described above, the amount of transition metal supported is 5 x 10 ^{-6 to} 5 x 10 ^-4 g atoms, preferably 10 ^-5 to 2 x 10 ^-4 g atoms, and the amount of aluminum supported Is 10 ^{−3 to} 5 × 10 ⁻² g atoms, preferably 2 × 10 ⁻³ to 2 × 10 ⁻² g atoms, all of which are relative to 1 g of the compound (a-1).

In addition, the amount of prepolymerized polyolefin produced in the prepolymerization is about 0.1 to 500 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g, based on 1 g of the compound (a-1).

In the case where the olefin is polymerized in the presence of the solid catalyst for the second olefin polymerization of the present invention, the amount of the transition metal compound [B] used per liter of polymerization is usually 10 ^-8 to 10 ^-3 g atoms, preferably from 10 ^-7 to 10 ^-4 atom. In the polymerization, the solid catalyst for polymerization of the second olefin of the present invention may be used in combination with the organoaluminum compound [C-2] and / or the aluminoxane compound as necessary.

As said preferable organic aluminum compound, the compound similar to the said organic aluminum compound [C-1] can be illustrated.

The use amount of the aluminoxane compound and the organic aluminum compound [C-2] is 0 to 500 mol, preferably 5 to 200 mol, with respect to 1 g of the transition metal.

Examples of the olefin that can be polymerized with the solid catalyst for polymerizing the first and second olefins or the catalyst obtained using them include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, and 3 -Methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-denecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentenecycloheptene, norbornene, 5-methyl-2-norbornane, tetracyclododecene, 2-methyl-1,4,5,8-dimethano- 1,2,3,4a, 5,8,8a-octahydronaphthalene etc. are mentioned. In addition, styrene, vinylcyclohexane and dienes can be employed.

In the present invention, the polymerization of the olefin can be carried out by any of liquid phase polymerization methods such as suspension polymerization or gas phase polymerization.

When olefin polymerization is carried out by liquid phase polymerization, the same inert hydrocarbon solvent as used in the production of the catalyst can be used, and the olefin itself can also be used as a solvent.

The olefin polymerization is a walk, preferably a polymerization temperature of olefin is usually, -50~150 ℃, with preferably in the range of 0~100 ℃, polymerization pressure is usually atmospheric pressure -100kg / cm ^2, in the presence of a catalyst of the above-described bar Is under the condition of -50 kg / cm ² at atmospheric pressure, and the polymerization reaction can be carried out by any of batch, semi-continuous and continuous methods. It is also possible to divide the polymerization into two or more stages having different reaction conditions. The molecular weight of the obtained polyolefin can be adjusted by introducing hydrogen into the polymerization system or by changing the polymerization temperature.

In addition, the catalyst for olefin polymerization of this invention may contain other components useful for olefin polymerization other than the said components.

The solid catalyst for the first olefin polymerization according to the present invention comprises (a-1) (iii) an oxide of at least one element selected from those belonging to group II, III and IV of the periodic table, and (ii) 1.0 wt% of water. A periodic table group IVB containing (a-2) an organoaluminum octane compound and (a-3) a ligand having a cyclopentadienyl skeleton on a granular carrier containing (a) 1.0 wt% or more of surface hydroxyl groups. It consists of a solid catalyst component [A-1] carrying a transition metal compound of a metal belonging to.

The first olefin polymerization catalyst according to the present invention may be composed of the first solid catalyst component [A-1] together with the catalyst component [C-2] which is an organic aluminum compound.

The solid catalyst for the first olefin polymerization and the catalyst for the first olefin polymerization according to the present invention can be applied to suspension polymerization and gas phase polymerization, and a spherical olefin polymer having excellent particle characteristics can be produced with high polymerization activity. An olefin polymer having a narrow molecular weight distribution at the time of two or more monomer polymerizations can be provided.

According to the first solid catalyst for olefin polymerization of the present invention, when the transition metal compound (a-3) contains two or more kinds of transition metal compounds, the solid catalyst may be applied to suspension polymerization and gas phase polymerization. The spherical olefin polymer having excellent particle characteristics can be produced with high polymerization activity, and the olefin polymer having excellent melt tension, wide molecular weight distribution and excellent moldability can be provided.

The solid catalyst for the second olefin polymer according to the present invention contains a solid catalyst component in which the component (a-2) is supported on the component (a-1) and a ligand having a [B] cyclopentadienyl skeleton. It can be produced by prepolymerization of an olefin in the presence of a catalyst component which is a transition metal compound of a metal belonging to group IVB of the periodic table and a catalyst component [A-2] which is a [C-1] organoaluminum compound.

The catalyst for the second olefin polymerization according to the present invention may be composed of a solid catalyst component for the second olefin polymerization together with the catalyst component [C-2] which is an organoaluminum compound.

The solid catalyst for the second olefin polymerization and the second olefin catalyst according to the present invention can be applied to suspension polymerization and gas phase polymerization, and spherical olefin polymers having excellent particle characteristics can be produced with high polymerization activity, and at least two kinds of monomers can be used. It is possible to provide an olefin polymer having a narrow molecular weight distribution at the time of polymerization.

Further, according to the second catalyst for olefin polymerization of the present invention, when the transition metal compound (a-3) contains two or more transition metal compounds, the solid catalyst can be applied to suspension polymerization and gas phase polymerization. It is possible to produce a solid olefin polymer having excellent particle characteristics with high polymerization activity, and to provide an olefin polymer having excellent melt tension, wide molecular weight distribution, and excellent moldability.

Although the present invention will be described in detail with reference to Examples, the present invention is not limited to these Examples.

The physical properties of the resulting ethylene polymer are measured as follows.

[Amount of n-decane soluble part of the polymer]

The n-decane soluble amount of the ethylene copolymer obtained by the present invention (the smaller the n-decane soluble content is, the narrower the composition distribution of the copolymer) is, about 450 g of the ethylene copolymer in 450 ml of 145 ° C n-decane. It can be measured by dissolving, cooling this solution to 23 degreeC, filtering an n-decane insoluble part, and recovering an n-decane soluble part from the filtrate.

[density]

The density was measured by the density gradient of the strand prepared by heat-treating the strand at 120 ° C. for 1 hour and cooling it to room temperature for 1 hour, and the strand was measured by MFR at a load of 2.16 kg at 190 ° C. It was used for

The average particle diameter and amount of the fine powder of less than 100 μm is measured using a sieve.

[Melt tension (MT)]

The melt tension (MT) is measured by measuring the stress of the molten polymer while stretching the molten polymer at a constant speed. Using an MT measuring device (manufactured by Toyosei Seisakusho Co., Ltd.) with a nozzle diameter of 2.09 mm and a nozzle length of 8 mm, the resin temperature was 190 ° C, extrusion speed 10 mm / min, take-up speed 10-20 m / min. It measured on condition of.

During the measurement of the melt tension, the ethylene copolymer sample was premixed with 0.1% by weight of 2,6-di-t-butyl-p-cresol as a crosslinking stabilizer.

Example 1

[Production of Solid Catalyst (Zirconium Catalyst)]

13.1 g of silica (adsorbed water: 0.1% by weight or less, 2.7% by weight of hydroxyl group) obtained by drying silica (TG-20643, manufactured by Fuji-Davison) for 6 hours in a nitrogen-substituted 400 ml glass flask under 200 ° C nitrogen flow, and 150 ml of toluene Was charged to obtain a suspension and cooled to 0 ° C. To this suspension was added dropwise 55.1 ml of a toluene solution of an organoaluminum oxy compound (Al; 1.365 mol / l) prepared by dissolving dried methylaluminoxane manufactured by Selling Company in toluene over 1 hour while maintaining the temperature of the reaction system at 0 ° C. . Next, reaction was performed at 0 degreeC for 1 hour, room temperature for 1 hour, and 80 degreeC for 4 hours. After the reaction was completed, the suspension was cooled to 20 ° C, and 31.3 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr: 0.0380 mol / L) was added dropwise to the suspension over 45 minutes. After the end of the dropping, the temperature of the suspension was raised to 30 ° C., and the mixture was stirred for 2 hours at this temperature. Next, the solvent was decanted and thus removed, and the residue was washed with 250 ml of toluene.

The above washing treatment was sufficiently performed three times to obtain a solid catalyst containing 8.3 mg of Zr and 155 mg of Al with respect to 1 g of silica. This solid catalyst was dissolved in hexane and used for polymerization.

Ethylene / 1-Butyl Copolymerization

150 g of sodium chloride (made by Wako Junyaku Co., Ltd., special product) was put into the 2 L stainless steel autoclave sufficiently nitrogen-substituted, and it vacuum-dried at 90 degreeC for 1 hour. Next, a mixed gas containing ethylene and 1-butene (1-butene content is 5.0 mol%) was introduced into the autoclave to reduce the internal pressure of the reaction system to atmospheric pressure, and the reaction system temperature was lowered to 70 ° C.

Next, 0.5 mmol of triisobutyl aluminum and 0.003 mmol of the solid catalyst prepared above were added to the autoclave in terms of Zr atoms.

10 N ml of hydrogen were introduced into the autoclave, and then the mixed gas was introduced to initiate polymerization under a voltage of 8 kg / cm ² -G. The temperature of the polymerization system immediately increased to 80 ° C.

Next, only the mixed gas was charged and maintained at a voltage of 8 kg / cm ² -G and a reaction system temperature of 80 ° C. for polymerization for 1 hour.

After completion of the polymerization, the unreacted sodium chloride was washed with water, the remaining polymer was washed with methanol, and dried overnight at 80 /. MFR measured at 190 ° C and 2.16kg load was 4.92g / 10min, density 0.912g / cm ³ , 23 ° C n-decane soluble content 0.7% by weight, density 0.41g / cm ³ , polymer particles 237 g of ethylene / 1-butene copolymer having 0.8% by weight of fine powder having an average particle diameter of 850 µm and less than 100 µm was obtained.

Example 2

[Production of Solid Catalyst (Zirconium Catalyst)]

6.5 g of the same silica used in Example 1 and 125 ml of toluene were mixed to obtain a suspension and cooled to 0 ° C. 32.2 ml of a toluene solution of an organoaluminum oxy compound (Al: 1.157 mol / l) and toluene of bis (n-butylcyclopentadienyl) zylconium dichloride prepared by dissolving dry methylaluminoxane manufactured by Selling Company in toluene in this suspension. A mixture of 11.9 ml of solution (Zr: 0.0313 mol / l) was added dropwise over 50 minutes while maintaining the temperature of the reaction system at 0 ° C. Next, reaction was performed for 30 hours at 0 degreeC, 40 minutes at room temperature, and 3.5 hours at 80 degreeC.

After completion of the reaction, the solvent in the suspension was decanted and thus removed, and the residue was washed with 250 ml of toluene.

The washing process was sufficiently performed three times to obtain a solid catalyst containing 5.2 mg of Zr and 154 mg of Al with respect to 1 g of silica.

[Ethylene / 1-butene Copolymerization]

The ethylene of Example 1 was used except that the solid catalyst obtained above was used as it was, the 1-butene content of the mixed gas was 8.2 mol%, the amount of hydrogen introduced was 30N ml, and the polymerization temperature was 75 ° C. MFR of 4.92 g / 10 min, density of 0.900 g / cm ³ , 23 ° C. of n-decane soluble content of 4.6% by weight 190 g of an ethylene / 1-butene copolymer having 0.19% by weight of 0.39 g / cm ³ , and the average particle diameter of the polymer particles of less than 870 μm was obtained.

Example 3

[Production of Solid Catalyst (Zirconium Catalyst)]

7.4 g of silica (absorbed water: 0.1% by weight or less, 2.1% by weight of surface hydroxyl group) obtained by drying under 300 ° C nitrogen stream for 6 hours and 150 ml of toluene were mixed to obtain a suspension and cooled to 0 ° C.

Next, except that 34.8 mmol and 0.465 mmol of an organoaluminum oxy compound and bis (n-butyl cyclopentadienyl) zirconium chloride were used, respectively, were carried out in the same manner as in Example 1, with respect to 1 g of silica, Zr 5.7 mg, Al A solid catalyst containing 125 mg was obtained. This solid catalyst was dissolved in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

Except using the solid catalyst obtained above, it carried out similarly to the ethylene / 1-butene copolymerization of Example 1, and the MFR measured by the load of 190 degreeC 2.16kg is 4.10g / 10min, and the density is 0.910g / cm <^3> , 23 degreeC 211 g of ethylene / 1 butene copolymers having an soluble content of n-decane of 0.8% by weight, a density of 0.38 g / cm ³ , and an average diameter of polymer particles of 740 μm and fine particles of less than 100 μm of 0.6% by weight were obtained.

Example 4

[Production of Solid Catalyst (Zirconium Catalyst)]

The solid catalyst obtained in Example 1 was mixed with 0.119 mg atom and hexane 100 ml in terms of zirconium atom to obtain a suspension.

Trisobutyl aluminum 8.15 mmol was added to the suspension, and the mixture was stirred for 10 minutes. Next, ethylene gas was introduced continuously, and prepolymerization was performed at 35 degreeC for 80 minutes. As a result, a solid catalyst containing 4 g of polyethylene with respect to 1 g of silica was obtained. In this prepolymerization, the prepolymerized catalyst attached to the prepolymerization reactor wall was not rejected.

Hexane was added to the mixture obtained after completion of the prepolymerization to make 200 ml, and the mixture was used as it was for polymerization.

[Ethylene / 1-butene Copolymerization]

The MFR measured at 190 ° C. and a load of 2.16 kg was 4.11 g / 10 min and the density was carried out in the same manner as in Example 1 except that the 1-butene content of the mixed gas was changed to 4.3 mol%. Ethylene / 1-butene air with 0.912 g / cm ³ , 23 ° C n-decane soluble content of 0.4% by weight, density of 0.41 g / cm ³ , average particle size of polymer particles of 770 μm and less than 100 μm of 0.1 wt% 204 g of coal was obtained.

Example 5

[Production of Solid Catalyst (Zirconium Catalyst)]

It carried out similarly to Example 4 except having performed the said prepolymerization so that the polyethylene content of the produced solid catalyst might be 13 g with respect to 1 g of silica. In the prepolymerization, no prepolymerized catalyst attached to the prepolymerization reactor wall was observed.

[Ethylene / 1-butene Copolymerization]

Except for using the prepolymerized catalyst obtained above, 4.24 g / 10 min of MFR measured at 190 ° C. and a load of 2.16 kg, with a density of 0.911 g / cm ³ , carried out in the same manner as in Example 4 for ethylene / 1-butene copolymerization. , 255 g of an ethylene / 1-butene copolymer having a soluble content of 23 ° C n-decane, 0.8% by weight, density of 0.41 g / cm ³ , and polymer particles having an average diameter of 870 μm and less than 100 μm of 0% by weight of fine particles.

Example 6

[Production of Solid Catalyst (Zirconium Catalyst)]

It carried out similarly to Example 4 except having performed the said prepolymerization so that the polyethylene content of the produced solid catalyst might be 80 g with respect to 1 g of silica. In the prepolymerization, no prepolymerized catalyst attached to the prepolymerization reactor wall was observed.

[Ethylene / 1-butene Copolymerization]

Except using the prepolymerized catalyst obtained above, the MFR was 3.41 g / 10 min and the density was 0.912 g / cm ³ , measured at 190 ° C. and a load of 2.16 kg, in the same manner as in the ethylene / 1-butene copolymerization of Example 4. , 246 g of ethylene / 1-butene copolymer having a soluble content of 23 ° C n-decane, 0.7% by weight, density of 0.39 g / cm ³ , and polymer particles having an average diameter of 860 μm and less than 100 μm of 0% by weight of fine particles.

Example 7

[Production of Solid Catalyst (Zirconium Catalyst)]

The solid catalyst obtained in Example 2 was mixed with 0.116 mg atom and 100 ml of hexane in terms of zirconium atom to obtain a suspension.

10.1 mmol of triisobutyl aluminum was added to the suspension, followed by stirring for 5 minutes. Next, ethylene gas was continuously introduced and prepolymerization was performed at 30 ° C. for 5 hours.

After completion of the prepolymerization, the solvent was removed by decantation and the residue was washed with 150 ml of hexane. This washing treatment was sufficiently performed three times to obtain a solid catalyst containing 4.9 mg of Zr, 153 mg of Al, and 7 g of polyethylene with respect to 1 g of silica.

[Ethylene / 1-butene Copolymerization]

Except using the solid catalyst obtained above, it carried out similarly to the ethylene / 1-butene copolymerization of Example 2, and the MFR measured at 190 degreeC and the load of 2.16 kg was 3.36g / 10min, and the density was 0.898 / cm <^3> , 23 degreeC. 269 g of ethylene / 1-butene copolymers having a soluble content of n-decane of 6.1% by weight, a density of 0.43 g / cm ³ , and an average diameter of polymer particles of 830 μm and less than 100 μm of 0% by weight of fine particles were obtained.

Comparative Example 1

[Production of Solid Catalyst (Zirconium Catalyst)]

3.9 g of silica (adsorbed water: 0.1% by weight or less, 0.5% by weight of hydroxyl group) obtained by sintering for 6 hours under a nitrogen stream at 700 ° C and 100 ml of toluene were mixed to obtain a suspension, and cooled to 0 ° C. 16.4 ml of the organic aluminum oxy compound (Al: 1.365 mol / L toluene solution prepared in Example 1) was dripped at this suspension over 30 minutes, and the temperature of the reaction system was kept at 0 degreeC.

Next, reaction was performed at 0 degreeC for 1 hour, room temperature for 1 hour, and 80 degreeC for 4 hours. After the reaction was completed, the suspension was cooled to 20 ° C, and 9.32 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr: 0.0380 mol / L) was added dropwise to the suspension over 15 minutes. After the dropwise addition ended, the temperature of the suspension was raised to 30 ° C. and stirred at this temperature for 2 hours. Next, it carried out similarly to Example 1, and obtained the solid catalyst containing 8.1 mg of Zr and 150 mg of Al with respect to 1 g of silica. This solid catalyst was dissolved in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

Except using the suspension of the solid catalyst obtained above, it carried out similarly to the ethylene / 1-butene copolymerization of Example 1, the MFR measured at 190 degreeC and the load of 2.16 kg was 4.55g / 10min, and the density was 0.913g / cm <^3>. 195 g of ethylene / 1-butene copolymer having 6.1 wt% of 23 ° C n-decane soluble content, density of 0.40 g / cm ³ , and polymer particles having an average diameter of 720 μm and less than 100 μm of 1.6 wt%.

Comparative Example 2

[Ethylene / 1-butene Copolymerization]

Toluene solution (Zr: 0.003) of 0.19 mg atom of an organoaluminum oxy compound supported on silica instead of the solid catalyst in terms of Al atoms and bis (n-butylcyclopentadienyl) zirconium dichloride prepared in Example 1 Except for adding 1 ml of mmol / L) to each autoclave, MFR measured at 190 ° C and a load of 2.16 kg was performed in the same manner as in Example 1, with the ethylene / 1-butene copolymerization of ethylene 1 being 7.01 g / 10 min, density. 45g of ethylene / 1-butene copolymers having a 0.915 g / cm ³ and a density of 0.19 g / cm ³ . Polymers attached to the walls of the autoclave were observed and many of the polymer particles were in amorphous form.

Comparative Example 3

[Production of Solid Catalyst (Zirconium Catalyst)]

In Example 1, dry silica and 3.6% by weight of water were mixed and sufficiently dispersed, and 150 ml of 9,6 g of toluene of silica was mixed to obtain a suspension, and cooled to 0 ° C. To this suspension was added dropwise 40.4 ml of the toluene solution of the organoaluminum oxy compound (Al: 1.365 mmol / L) prepared in Example 1 over 50 minutes while maintaining the temperature of the reaction system at 0 ° C. Next, the reaction was carried out at 0 ° C. for 1 hour, at room temperature for 1 hour, and at 80 ° C. for 4,5 hours. After the reaction was completed, the suspension was cooled to 20 ° C, and 22.9 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr: 0/0380 mol / L) was added dropwise to the suspension over 45 minutes. After the end of the dropwise addition, the temperature of the suspension was raised to 30 ° C. and stirred at this temperature for 2 hours.

After the completion of the reaction, the solvent in the suspension was decanted and removed, and the residue was washed with 250 ml of toluene.

The above washing treatment was sufficiently performed three times to obtain a solid catalyst containing 8.0 mg of Zr and 150 mg of Al with respect to 1 g of silica. This solid catalyst was dissolved in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

Except having used the solid catalyst obtained above, copolymerization of ethylene / 1-butene was carried out similarly to Example 1, the MFR measured at 190 degreeC and the load of 2.16 kg was 3.98 g / 10min, and the density was 0.914 g / cm <^3> , 177 g of ethylene / 1-butene copolymer having a density of 0.37 g / cm ³ , a polymer average diameter of 610 μm, and fine particles of less than 100 μm of 2.5% by weight were obtained.

Example 8

[Production of Solid Catalyst (Zirconium Catalyst)]

5.5 g of the same silica as in Example 1 and 60 ml of toluene were mixed to obtain a suspension, which was cooled to 0 ° C. 28.5 ml of the toluene solution of the organoaluminum oxy compound (Al; 1.465 mol / L) prepared in Example 1 was added dropwise to this suspension over 30 minutes. After completion of the dropwise addition, the reaction was carried out in the same manner as in Example 1. After the completion of the reaction, the reaction mixture was cooled to 20 ° C, and 14.8 ml of toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr: 0.0313 mol / L) was added over 20 minutes to the mixture. Dropped. After the dropwise addition ended, the temperature of the reaction system was raised to 30 ° C. and stirred at this temperature for 100 minutes. Next, it carried out similarly to Example 1, and obtained the solid catalyst containing 7.5 mg of Zr and 200 mg of Al with respect to 1 g of silica.

To the suspension obtained by adding 100 ml of hexane to 50 ml of the hexane suspension (Zr: 0.0023 mol / L) of the solid catalyst obtained above, 10.4 mmol of triisobutyl aluminum was added and stirred for 10 minutes. Next, ethylene gas was introduced continuously, and prepolymerization was performed at 30 degreeC for 7 hours. In this prepolymerization, no prepolymerized catalyst attached to the prepolymerization reactor wall was observed. Then, the solvent of the reaction mixture was removed, and the residue was washed with 200 ml of toluene. The washing treatment was carried out four times to obtain a prepolymerized solid catalyst containing 7.0 g of Zr and 196 mg of Al with 28 g of polyethylene per 1 g of silica. This solid catalyst was dissolved in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

The 1-butene content of the mixed gas was 8.2 mol%, the amount of hydrogen introduced was 30N ml, except that the polymerization temperature was 75 ° C. 0% by weight of fine particles having an MFR of 3.04 g / 10 min, a density of 0.899 g / cm ³ , a density of 0.39 g / cm ³ , and an average diameter of polymer particles of 940 μm and less than 100 μm, measured at a load of 2.16 kg. 248 g of phosphorus ethylene / 1-butene copolymer was obtained.

Example 9

[Production of Solid Catalyst (Zirconium Catalyst)]

Except for using bis (indenyl) zirconium chloride as the Zr compound was carried out in the same manner as in Example 1 to obtain a solid catalyst containing 8.1mg of zirconium and 152mg of aluminum per 1g of silica.

[Ethylene / 1-butene Copolymerization]

Except using the solid catalyst obtained above, it carried out similarly to the ethylene / 1-butene copolymerization of Example 1, the MFR measured at 190 degreeC and the load of 2.16 kg was 6.10g / 10min, and the density was 0.913g / cm <^3> , 185 g of an ethylene / 1-butene copolymer having a density of 0.40 g / cm ³ and an average diameter of the polymer particles of 780 µm and 0.7% by weight of fine particles of less than 100 µm were obtained.

Example 10

[Ethylene / 1-butene Copolymerization]

Except not using triisobutyl aluminum, it was carried out in the same manner as in the ethylene / 1-butene copolymerization of Example 1, and the MFR measured at 190 ° C and a load of 2.16 kg was 6.63 g / 10 min, and the density was 0.916 g / cm ³ , 95 g of the ethylene / 1-butyl copolymer having a density of 0.39 g / cm ³ and an average particle diameter of the polymer particles of 610 µm and less than 100 µm of 0.8 wt% were obtained.

Example 11

[Production of Solid Catalyst (Zirconium Catalyst)]

Except for using bis (1,3-dimethylcyclopentadienyl) zirconium chloride instead of bis (n-butylcyclopentadienyl) zirconium chloride, the same procedure as in Example 1 was carried out to give 8.1 mg of zirconium for 1 g of silica, A solid catalyst containing 154 mg of aluminum was obtained.

[Ethylene / 1-butene Copolymerization]

The solid catalyst obtained above was used in the same manner as in the ethylene / 1-butene copolymerization of Example 1 except that 0.005 mg of the atom in terms of Zr atoms was used. The MFR was 0.032 g / 10 min, the density was 0.40 g / cm ³ , and the polymer particles were used. 245 g of ethylene / 1-butene copolymers having an average diameter of 690 µ and less than 100 µ of 0.6 wt% were obtained.

Table 1 and 2 show the results of the above catalyst preparation and polymerization.

TABLE 1

* The amount loaded on 1g of silica

TABLE 2

Zr was used without silica.

Example 12

[Production of Solid Catalyst (Zirconium Catalyst)]

A nitrogen-substituted 400 ml glass flask was charged with 18.8 g of silica (TG 40209 manufactured by Fuji Devison Co., Ltd., adsorbed water: 2.7 wt% of 0.3 wt% hydroxyl group) and 300 ml of toluene to obtain a suspension, and cooled to 0 ° C. To this suspension was added dropwise 34.7 ml of a toluene solution of an organoaluminum oxy compound (manufactured by Selling, Al: 4.16 mol / l) over 1 hour while maintaining the temperature of the reaction system at 0 ° C. Next, reaction was performed at 0 degreeC for 30 minutes and 95 degreeC for 16 hours. After the reaction was completed, the suspension was cooled to 20 ° C. and the solvent of the suspension was tilted to remove. The residue was washed three times with 300 ml of toluene.

The obtained solid component 3.89g and 70 ml of toluene were mixed, the suspension was obtained, and the temperature of this suspension was heated up at 80 degreeC. To this suspension, 1.5 ml of a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr: 9.33 mmol / L) was added dropwise over 20 minutes. After the dropwise addition was stirred at 80 ° C. for 2 hours. Next, the solvent was removed, and the residue was washed with 150 ml of hexane.

The washing process was sufficiently performed three times to obtain a solid catalyst containing 4.5 mg of Zr and 176 mg of Al with respect to 1 g of silica. This solid catalyst was dissolved in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

150 g of sodium chloride (made by Wako Pure Chemical Industries, Ltd.) was put into the 2 L stainless steel autoclave sufficiently nitrogen-substituted, and it vacuum-dried at 90 degreeC for 1 hour. Next, a mixed gas containing ethylene and 1-butene (1-butene content was 5.1 mol%) was introduced into the autoclave to reduce the pressure in the reaction system to atmospheric pressure, and the temperature in the reaction system was lowered to 75 ° C.

Next, 1 mmol of triisobutyl aluminum and 0.004 mmol of the solid catalyst obtained in the above was added to the autoclave.

50 Nml of hydrogen was introduced into the autoclave, and then the mixed gas was introduced to initiate polymerization under a voltage of 8 kg / cm ² -G. The temperature of the polymer immediately rose to 85 ° C.

Next, only the mixed gas was charged and maintained at a voltage of 8 kg / cm ² -G and a reaction system temperature of 85 ° C., and polymerization was performed for 1.5 hours.

After the completion of the polymerization, the unreacted sodium chloride was washed with water, the remaining polymer was washed with methanol, and vacuum dried overnight at 80 ° C. Ethylene / 1-butene copolymer having an MFR of 190 g / 10 min, a density of 0.42 g / cm ³ , a polymer particle average particle diameter of 870 μm and less than 100 μm at 0.3 wt% measured at 190 ° C. and a load of 2.16 kg. 415 g was obtained.

Example 13

[Production of Solid Catalyst (Zirconium Catalyst)]

The solid catalyst obtained in Example 12 and 130 ml of hexane were mixed to obtain a suspension.

13.0 mmol of triisobutyl aluminum was added to the suspension, ethylene gas was continuously introduced, and prepolymerization was carried out at 35 ° C. for 130 minutes. As a result, a solid catalyst containing 4 g of polyethylene with respect to 1 g of silica was obtained. In this prepolymerization, no prepolymerized catalyst attached to the prepolymerization reactor wall was observed.

[Ethylene / 1-butene Copolymerization]

Except for using the prepolymerized solid catalyst obtained above, MFR was 0.01 g / 10 min, density was 0.46 g / cm ³ , and the average diameter of the polymer particles was 90 μm, in the same manner as in the ethylene / 1-butene copolymerization of Example 12. 465 g of ethylene / 1-butene copolymers having 0% by weight of fine particles of less than 100 µm were obtained.

Example 14

[Production of Solid Catalyst (Zirconium Catalyst)]

15.3 g of silica (adsorbed water: 0.1% by weight or less, 2.7% by weight of hydroxyl group) and 153 ml of toluene were obtained by drying silica (TG-20643, manufactured by Fuji-Davison) for 6 hours in a nitrogen-substituted 400 ml glass flask under 200 ° C nitrogen flow. Filled to obtain a suspension and cooled to 0 ° C.

65.2 ml of a toluene solution of an organoaluminum oxy compound (manufactured by Selling, Al: 1.344 mol / l) was added dropwise to the suspension over 1 hour, and the temperature of the reaction system was maintained at 0 ° C. Next, reaction was performed at 0 degreeC for 1 hour, room temperature for 1 hour, and 80 degreeC for 4 hours. Al was not detected in the obtained slurry supernatant.

The slurry was then made 300 ml of toluene and 100 ml thereof separated and introduced into another 200 ml glass flask. To this flask, 10 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride and 0.20 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride were added dropwise over 10 minutes. . After completion of the dropwise addition, the mixture was reacted at 30 ° C. for 1.5 hours. Next, the solvent of the reaction mixture was removed to remove the residue, and the residue was washed three times with hexane to obtain a solid catalyst containing 5.3 mg of Zr and 155 mg of Al with respect to 1 g of silica.

[Ethylene / 1-butene Copolymerization]

150 g of sodium chloride (made by Wako Pure Chemical Industries, Ltd., etc.) was put into the 2 L stainless steel autoclave sufficiently nitrogen-substituted, and it vacuum-dried at 90 degreeC for 1 hour. Next, a mixed gas containing ethylene and 1-butene (1-butene content was 4.5 mol%) was introduced into the autoclave to reduce the pressure in the reaction system to normal pressure, and the temperature in the reaction system was lowered to 70 ° C. Next, 0.5 mmol of chrysobutyl aluminum and 0.003 mmol of the solid catalyst obtained above were added to the autoclave in terms of Zr atoms. 50 Nml of hydrogen was introduced into the autoclave, and then the mixed gas was introduced to initiate polymerization under a voltage of 8 kg / cm ² -G). The temperature of the polymerization system immediately increased to 80 ° C. Next, only the mixed gas was charged and maintained at a voltage of 8 kg / cm ² -G and a reaction system temperature of 80 ° C. for polymerization for 1 hour.

After the completion of the polymerization, the unreacted sodium chloride was washed with water, the remaining polymer was washed with methanol, and dried in vacuo at 80 ° C overnight.

As a result, MFR measured at 190 ° C and 2.16kg load was 0.17g / 10min, density was 0.925g / cm ³ , 23 ° C n-decane soluble loading was 0.2% by weight, density was 0.38g / cm ³ , polymer 105.1 g of ethylene / 1-butene copolymers having 0.3 wt% of the fine particles having an average particle diameter of 600 µm and less than 100 µm, having a melt tension of 14 g and Mw / Mn of 4.0 were obtained.

Example 15

[Production of Solid Catalyst (Zirconium Catalyst)]

Except for using 0.15 mmol of bis (n-butylcyclopentadienyl) zirconium chloride and 0.15 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium chloride, the same procedure as in Example 14 was carried out to give 1 g of silica. A solid catalyst containing 5.3 mg of zirconium and 153 mg of aluminum was obtained.

[Ethylene / 1-butene Copolymerization]

Except using the solid catalyst obtained above, it carried out similarly to the ethylene / 1-butene copolymerization of Example 14, the MFR measured at 190 degreeC and the load of 2.13 kg was 0.56g / 10min, and the density was 0.919g / cm <^3> , 98.5 g of ethylene / 1-butene copolymers having a soluble content of 23 ° C n-decane, 0.3% by weight, a density of 0.38 g / cm ³ , and an average diameter of polymer particles of 530 μm and less than 100 μm of 0.5% by weight of fine particles were obtained.

Example 16

[Production of Solid Catalyst (Zirconium Catalyst)]

In a fully nitrogen-substituted 400 ml glass flask, 0.07 mg atom was introduced in terms of zirconium atoms into 120 ml of hexane, 1.5 mmol of triisobutyl aluminum, and the solid catalyst obtained in Example 14. Next, ethylene gas was continuously introduced, and prepolymerization was performed at 35 ° C. for 6 hours. In this prepolymerization, no prepolymerized catalyst attached to the prepolymerization reactor wall was observed. As a result, a solid catalyst containing 39 g of Zr 5.1 mg and Al 137 mg polyethylene was obtained for 1 g of silica.

[Ethylene / 1-butene Copolymerization]

Except using the solid catalyst obtained above, it carried out similarly to the ethylene / 1-butene copolymerization of Example 14, and the MFR measured at 190 degreeC and the load of 2.13 kg is 0.15g / 10min, and the density is 0.926g / cm <^3>. Ethylene having 0.2% by weight of 23-degree n-decane soluble content, density of 0.40 g / cm ³ , average particle diameter of polymer particles of 640 μm, fine particles of less than 100 μm of 0.1 weight% melt tension of 15 g, 4.2 of Mw / Mn 100 g of / 1-butene copolymer was obtained.

Example 17

[Production of Solid Catalyst (Zirconium Catalyst)]

It carried out similarly to Example 16 except having used the solid catalyst obtained in Example 15 instead of the solid catalyst obtained in Example 14. As a result, a solid catalyst containing 5.1 mg of Zr, 142 mg of Al, and 13 g of polyethylene was obtained for 1 g of silica. In this prepolymerization, no prepolymerized catalyst attached to the prepolymerization reactor wall was observed.

[Ethylene / 1-butene Copolymerization]

MFR measured at 190 ° C and a load of 2.13 kg in the same manner as in the ethylene / 1-butene copolymerization of Example 14 was 0.54 g / 10 minutes, and the soluble content of 23 ° C n-decane was 0.4% by weight and the density was 0.40g. 95 g of an ethylene / 1-butene copolymer having an average diameter of 580 μm, polymer particles of less than 100 μm in 0.1 cm, melt tension of 7.5 g, and Mw / Mn of 3.5 in / cm ³ .

[Comparative Example 4]

[Production of Solid Catalyst (Zirconium Catalyst)]

Except for using only 0.3 mmol of bis (n-butylcyclopentadienyl) zirconium chloride, the same procedure as in Example 14 was carried out to obtain a solid catalyst containing 5.2 mg of zirconium and 150 mg of aluminum based on 1 g of silica.

[Ethylene / 1-butene Copolymerization]

Except having made the amount of hydrogen introduced into 10 Nml, it carried out similarly to the ethylene / 1-butene copolymerization of Example 14, and the MFR measured at the load of 2.13 kg of 190 degreeC is 3.02g / 10min, and the density is 0.921g / cm. ³ , 23 ° C n-decane soluble content of 0.52% by weight, density 0.37g / cm ³ , average particle diameter of polymer particles is 750μm, 0.5% by weight of fine particles less than 100μm, melt tension 0.5, Mw / Mn is 2.4 192.4 g of ethylene / 1-butene copolymer were obtained.

Example 18

[Preparation of Solid Catalyst [Zirconium Catalyst]]

18.0 g of silica (adsorbed water: 0.1 wt% or less, 2.7 wt% hydroxyl) and 200 ml of toluene were obtained by drying silica (TG-20643, manufactured by Fuji-Davison) for 6 hours in a nitrogen-substituted 400 ml glass flask under a nitrogen stream of 200 ° C. Was charged to obtain a suspension and cooled to 0 ° C.

To this suspension was added dropwise over 7 minutes, 70.3 ml of a toluene solution (Al: 1.465 mol / l) of an organoaluminum oxy compound prepared by dissolving dry aluminoxane manufactured by Selling Company in toluene was maintained at 0 ° C. Next, reaction was performed at 0 degreeC for 1.5 hours, room temperature for 2 hours, and 80 degreeC for 4 hours.

Next, 30 ml of the slurry obtained above, 100 ml of decane, and 3.0 ml of decane solution of triisobutyl aluminum (Al; 1 mol / L) were introduced into another 400 ml glass flask, followed by stirring for 10 minutes.

To the flask was added 2.2 ml of a toluene solution (Zr: 0.045 mol / l) of bis (n-butylcyclopentadienyl) zirconium dichloride. Next, 100 ml of decane was added, and then ethylene gas was continuously introduced, followed by prepolymerization at atmospheric pressure at 30 ° C. for 9 hours. No prepolymerized catalyst attached to the wall of the prepolymerization reactor was observed in this prepolymerization.

After the completion of the prepolymerization, the solvent of the reaction mixture was removed, and the residue was washed with 150 ml of hexane. The washing process was sufficiently performed six times to obtain a solid catalyst containing 4.4 mg of Zr, 164 mg of Al, and 40 g of polyethylene with respect to 1 g of silica. This solid catalyst was resuspended in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

150 g of sodium chloride (made by Wako Pure Chemical Industries, Ltd., etc.) was put into the 2 L stainless steel autoclave sufficiently nitrogen-substituted, and it vacuum-dried at 90 degreeC for 1 hour. Next, a mixed gas containing ethylene and 1-butene (1 -butene content was 7.2 mol%) was introduced into the autoclave to reduce the pressure in the reaction system to atmospheric pressure, and the temperature in the reaction system was lowered to 70 ° C.

Next, 0.5 mmol of triisobutyl aluminum and 0.003 mmol of the solid catalyst obtained above were added to the autoclave in terms of Zr atoms.

30 Nml of hydrogen was introduced into the autoclave, and then the mixed gas was introduced to initiate polymerization under a voltage of 8 kg / cm ² -G. The temperature of the polymerization system immediately increased to 75 ° C.

Next, only the mixed gas was charged and maintained at a voltage of 8 kg / cm ² -G and a reaction system temperature of 75 ° C. for polymerization for 1 hour.

After the completion of the polymerization, the unreacted sodium chloride was washed with water, the remaining polymer was washed with methanol, and vacuum dried overnight at 80 ° C. As a result, the MFR measured under a load of 190 ℃, 2.16kg 1.79g / 10 min and a density of 0.903g / cm ^3, n- decane-soluble fraction is 3.4% by weight, a density of 0.40g / cm ^3, the polymer particles 192 g of ethylene / 1-butene copolymers having 0% by weight of fine particles having an average particle diameter of 700 µm and less than 100 µm were obtained.

Example 19

[Production of Solid Catalyst (Zirconium Catalyst)]

17.8 g of silica prepared in Example 18 and 225 ml of toluene were mixed to obtain a suspension, which was cooled to 0 ° C. To this suspension, 2.77 ml of a toluene solution (Al: 1.157 mol / L) of an organoaluminum oxy compound prepared by dissolving dry methyl aluminoxane manufactured by Selling Company in toluene was introduced and stirred for 15 minutes.

To the flask was added 3.54 ml of a toluene solution (Zr: 0.0348 mol / L) of bis (n-butylcyclopentadienyl) zylconium dichloride.

Next, 100 ml of decane was added, and then ethylene gas was continuously introduced, followed by prepolymerization at atmospheric pressure at 30 ° C. for 9 hours. No prepolymerized catalyst attached to the wall of the prepolymerization reactor was observed in this prepolymerization.

After the completion of the prepolymerization, the solvent of the reaction mixture was removed, and the residue was washed with 150 ml of hexane. The washing was carried out six times to obtain a solid catalyst containing 6.9 mg of Zr, 200 gm of Al, and 33 g of polyethylene with respect to 1 g of silica. This solid catalyst was resuspended in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

Ethylene / 1 of Example 18 was used except that the 1-butene content of the mixed gas was 9.0 mol%, the amount of hydrogen introduced was 20 Nml, and the polymerization temperature was 65 ° C. -MFR measured at 190 ° C and 2.16 kg load in the same manner as the butene copolymerization, 1.46 / 10 minutes, density 0.890 g / cm ³ , density 0.42 g / cm ³ , average particle diameter of polymer particles 870 μm, 236 g of ethylene / 1-butene copolymer having 0% by weight of fine particles of less than 100 µm was obtained.

Example 20

[Ethylene / 1-butene Copolymerization]

1-butene content of the mixed gas was 5.5 mol%, the amount of hydrogen introduced was 30Nml, and the polymerization temperature was carried out in the same manner as in the ethylene / 1-butene copolymerization of Example 19 to 190 ° C. , the average diameter of the one having a MFR of 2.68g / 10 bun density measured under a load of 2.16kg of 0.906m / cm ^3, decane-soluble fraction 23 ℃ n- is 1.4% by weight, a density of 0.42g / cm ^3, the polymer particles 201 g of ethylene / 1-butene copolymers having 0% by weight of fine particles of 800 µm and less than 100 µm were obtained.

Example 21

[Ethylene / 1-butene Copolymerization]

The polymerization was carried out in the same manner as in the ethylene / 1-butene copolymerization of Example 19, except that the polymerization temperature was 85 ° C. The MFR measured at 190 ° C and a load of 2.16 kg was 3.95 g / 10 min and the density was 0.906 g / cm ³ , 158 g of an ethylene / 1-butene copolymer having an soluble content of 23 ° C n-decane, 3.2% by weight, a density of 0.42 g / cm ³ , and an average diameter of polymer particles of 800 μm and less than 100 μm of 0% by weight of fine particles were obtained.

Example 22

[Ethylene / 1-pentene copolymerization]

Ethylene was introduced into the autoclave of Example 18 to reduce the reaction system internal pressure to atmospheric pressure, and the reaction system temperature was lowered to 70 ° C. Next, 0.5 mmol of triisobutyl aluminum and 0.005 mmol of the solid catalyst obtained in Example 19 were added to the autoclave in terms of Zr atoms. 3 ml of 1-pentene and 30 Nml of hydrogen were introduced into the autoclave, and then ethylene was introduced to initiate polymerization under a voltage of 8 kg / cm ² -G. Next, ethylene and 1-pentene were fed continuously, and polymerization was carried out at a voltage of 8 kg / cm ² -G at 80 ° C. for 1 hour. The conductivity of 1-pentene was 29 ml.

Next, it carried out similarly to Example 18, MFR measured at 190 degreeC and 2.16 kg load is 2.38g / 10min, density is 0.922g / cm <^3> , 23 degreeC n-decane soluble loading is 0.1 weight%, density 182 g of ethylene / 1-pentene copolymer having 0.39 g / cm <^3> and the average particle diameter of a polymer particle of 650 micrometers and 0.1 micrometer of less than 100 micrometers was obtained.

Example 24

[Production of Solid Catalyst (Zirconium Catalyst)]

6.8 g of silica (absorbed water: 0.1 wt% or less, 2.1 wt% hydroxyl) and 150 ml of toluene were charged to dry the mixture for 6 hours under nitrogen stream at 300 캜 to obtain a suspension, and cooled to 0 캜. 21.8 ml of toluene solution (Al: 1.465 mol / l) of the organoaluminum oxy compound prepared in Example 18 was added dropwise to this suspension over 20 minutes, and the temperature of the reaction system was maintained at 0 ° C. Next, reaction was performed at 0 degreeC for 1 hour, room temperature for 1 hour, and 80 degreeC for 4 hours.

Next, 40 ml of the suspension obtained above, decane, 100 ml, and 2.23 ml of a decane solution of triisobutyl aluminum (Al; 1 mol / L) were introduced into another 400 ml glass flask, followed by stirring for 10 minutes. 1.65 ml of toluene solution (Zr: 0.0451 mol / l) of bis (n-butylcyclopentadienyl) zirconium dichloride was added to this suspension, and it stirred for 10 minutes.

Next, 100 ml of decane was added, followed by introduction of ethylene gas continuously, followed by prepolymerization at atmospheric pressure at 30 ° C. for 6 hours. No prepolymerized catalyst attached to the wall of the prepolymerization reactor was observed in this prepolymerization. In the same manner as in Example 18, a solid catalyst containing 3.9 mg of Zr, 137 mg of Al, and 29 g of polyethylene was obtained with respect to 1 g of silica. This solid catalyst was resuspended in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

Except using the solid catalyst obtained above, it carried out similarly to the ethylene / 1-butene copolymerization of Example 18, the MFR measured at 190 degreeC and the load of 2.16 kg was 1.60g / 10min, and the density was 0.904g / cm <^3> , 203 g of ethylene / 1-butene copolymer having a soluble portion of 23 ° C n-decane, 3.1% by weight, density of 0.41 g / cm ³ , and polymer particles having an average diameter of 660 μm and less than 100 μm of 0.1% by weight of fine particles were obtained.

[Comparative Example 5]

[Production of Solid Catalyst (Zirconium Catalyst)]

3.9 g of silica (adsorbed water: 0.1% by weight or less, 0.5% by weight of hydroxyl group) obtained by sintering for 6 hours under a nitrogen stream at 700 ° C and 100 ml of toluene were mixed to obtain a suspension, and cooled to 0 ° C. 16.4 ml of toluene solution (Al: 1.365 mol / l) of the organoaluminum oxy compound prepared in Example 18 was added dropwise to this suspension over 30 minutes, and the temperature of the reaction system was maintained at 0 ° C. The autoclave was then reacted at 0 ° C for 1 hour, at room temperature for 1 hour, and at 80 ° C for 4 hours.

Next, 50 ml of the suspension obtained above, decane, 100 ml, and 2.88 ml of a decane solution of triisobutyl aluminum (Al: 1 mol / L) were introduced into another 400 ml glass flask, followed by stirring for 10 minutes. 4.00 ml of toluene solution (Zr: 0.0320 mol / l) of bis (n-butylcyclopentadienyl) zirconium dichloride was added to this suspension.

Next, ethylene gas was continuously introduced, followed by prepolymerization at atmospheric pressure at 30 ° C. for 2 hours. In this prepolymerization, white matter was attached to the walls of the prepolymerization reactor.

After the completion of the prepolymerization, the solvent of the reaction mixture was removed, and the residue was washed with 150 ml of hexane. The washing was carried out four times to give a solid catalyst containing 6.2 mg of Zr, 147 mg of Al, and 4 g of polyethylene with respect to 1 g of silica. This solid catalyst was resuspended in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

Except that the 1-butene content of the mixed gas was 4.6 mol% and the amount of hydrogen introduced was 10 Nml, the same procedure as in Example 20 of ethylene / 1-butene copolymerization was carried out, and the measurement was carried out at a load of 2.16 kg at 190 ° C. a MFR of 2.60g / 10 minutes, density of 0.912g / cm ^3, a density of 0.40g / cm ^3, the average diameter of the polymer particles are fine particles of 650μm, less than 100μm 0.4% by weight of ethylene / 1-butene copolymer 150 g was obtained.

Comparative Example 6

[Ethylene / 1-butene Copolymerization]

Instead of the solid catalyst, in the autoclave, an organoaluminum compound supported on silica prepared in Example 19 of 0.30 mg atom in terms of Al atoms and bis (n-butylcyclopentadienyl) zirconium dichloride 1 ml of toluene solution (Zr: 0.0030 mol / l) was added, and the same procedure as in Example 20 was carried out except that 1-butene content of the mixed gas was 4.6 mol% and hydrogen introduction amount was 10 Nml. As a result, 190 ℃, a MFR of 5.10g / 10 min Measuring from 2.16kg load, a density of 0.916g / cm ^3, the density to give the 0.21g / cm ³ of ethylene / 47g.

The polymer attached to the autoclave was observed in the polymerization, and many polymer particles were in a coarse form.

Comparative Example 7

[Production of Solid Catalyst (Zirconium Catalyst)]

In Example 18, the dried silica and 3.6% by weight of water were mixed and sufficiently dispersed. 150 ml of toluene was added to 9.6 g of this silica to obtain a suspension, and the mixture was cooled to 0 ° C. 65.4 ml of toluene solution (Al: 1.464 mol / l) of the organoaluminum oxy compound prepared in Example 18 was added dropwise to the suspension over 45 minutes, and the temperature of the reaction system was maintained at 0 to 1 ° C. Next, reaction was performed at 0 degreeC for 1 hour, room temperature for 1 hour, and 80 degreeC for 4 hours.

Next, 30 ml of the suspension obtained above, decane, 100 ml, and 4.03 ml of decane solution of triisobutyl aluminum (Al: 1 mol / L) were introduced into another glass flask, followed by stirring for 10 minutes.

4.29 ml of toluene solution (Zr: 0.0313 mol / l) of bis (n-butylcyclopentadienyl) zirconium dichloride was added to the suspension, followed by stirring for 5 minutes.

Next, ethylene gas was continuously introduced, followed by prepolymerization at 30 캜 for 2 hours at atmospheric pressure. In this prepolymerization, some white matter was attached to the wall of the prepolymerization reactor.

After the completion of the prepolymerization, the solvent of the reaction mixture was removed, and the residue was washed with 150 ml of hexane. The washing was carried out six times to obtain a solid catalyst containing 9.0 mg of Zr, 281 mg of Al, and 5 g of polyethylene with respect to 1 g of silica. This solid catalyst was resuspended in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

Except that the 1-butene content of the mixed gas was 6.0% by weight and the polymerization temperature was 85 ° C, the same process as in the ethylene / 1-butene copolymerization of Example 20 was carried out, and the temperature was measured at 190 ° C and 2.16 kg. MFR is 3.07g / 10min, density is 0.909g / cm ³ , 23 ° C n-decane soluble content is 2.9% by weight, density is 0.41g / cm ³ , polymer particles have an average diameter of 400μm and less than 100μm 82 g of ethylene / 1-butene copolymer was obtained which was 1.1 weight%.

Example 25

[Production of Solid Catalyst (Zirconium Catalyst)]

1.4 g of the same silica as in Example 18 and 20 ml of toluene were charged to obtain a suspension, which was cooled to 0 ° C. 7.3 ml of toluene solution (Al: 1.465 mol / l) of the organoaluminum oxy compound prepared in Example 18 was added dropwise to this suspension over 10 minutes. Next, reaction was performed similarly to Example 18.

To the suspension was added 100 ml of hexane and 4.56 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (Zr: 0.0313 mol / L), followed by stirring for 10 minutes. Next, 3.13 ml of a decane solution of triisobutyl aluminum (Al: 1 mol / L) was introduced, followed by introduction of ethylene gas (normal pressure) to initiate prepolymerization. Ethylene gas was continuously introduced and prepolymerization was carried out at 30 ° C. for 9 hours. No prepolymerized catalyst attached to the wall of the prepolymerization reactor was observed in this prepolymerization.

After the completion of the prepolymerization, a solid catalyst containing 9.0 g of Zr, 206 mg of Al and 43 g of polyethylene was obtained for 1 g of silica in the same manner as in Example 18. This solid catalyst was resuspended in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

The 1-butene content of the mixed gas was 5.8 mol%, the amount of hydrogen introduced was 20 Nml, and the polymerization was carried out in the same manner as in the ethylene / 1-butene copolymerization of Example 18, except that the polymerization temperature was 80 ° C. , MFR measured at a load of 2.16 kg, 3.34 g / 10 min, density 0.903 g / cm ³ , 23 ° C n-decane soluble content of 4.3 wt%, density 0.44 g / cm ³ , average diameter of polymer particles 247g of ethylene / 1-butene copolymers which are the weight% of these 900 micrometers and less than 100 micrometers were obtained.

Example 26

[Production of Solid Catalyst (Zirconium Catalyst)]

As the Zr compound, except for using bisindenyl zirconium chloride, it was carried out in the same manner as in Example 18, to obtain a solid catalyst containing 4.2 mg of Zr, 160 mg of Al, and 36 g of polyethylene with respect to 1 g of silica. No polymer attached to the reactor wall was observed in this prepolymerization.

[Ethylene / 1-butene Copolymerization]

Example 18 in the same manner as in 190 ℃, a MFR of 3.50g / 10 min Measuring at a load of 2.16kg, a density of 0.905g / cm ^3, a density of 0.39g / cm ^3, an average hit of the polymer particles 660μm , 178 g of an ethylene / 1-butene copolymer having 0.1% by weight of fine particles of less than 100 µm was obtained.

Example 27

[Ethylene / 1-butene Copolymerization]

Triisobutyl and aluminum except that the embodiment in use in the same manner as in Example 18 190 ℃, the MFR is measured under a load of 2.16kg 2.91g / 10 minutes and a density of 0.906g / cm ^3, a density of 0.39g / cm ³ , 77 g of ethylene / 1-butene copolymers having an average diameter of the polymer particles of 470 µm and less than 100 µm of 0.2 wt% were obtained.

Example 28

[Production of Solid Catalyst (Zirconium Catalyst)]

Except having performed the said prepolymerization for 2 hours, it carried out similarly to Example 18, and obtained the solid catalyst which contains 4.3 mg of zirconium, 159 mg of aluminum, and 5 g of polyethylene with respect to 1 g of silicas. No polymer attached to the reactor wall was observed in this prepolymerization.

[Ethylene / 1-butene Copolymerization]

Except using the solid catalyst obtained above, it carried out similarly to the ethylene / 1-butene copolymerization of Example 18, and the MFR measured at 190 degreeC and the load of 2.16 kg is 2.01g / 10min, and the density is 0.902g / cm <^3> , 189 g of ethylene / 1-butene copolymers having a density of 0.39 g / cm ³ and an average diameter of the polymer particles of 680 µm and less than 100 µm of 0.1 wt% were obtained.

Example 29

[Production of Solid Catalyst (Zirconium Catalyst)]

0.102 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium chloride was used instead of bis (n-butylcyclopentadienyl) zirconium chloride and the amount of silica and the amount of the organoaluminum compound were 1.4 g and 8.24, respectively. A solid catalyst containing 6.1 mg of zirconium, 157 mg of aluminum, and 4 g of polyethylene was obtained for 1 g of silica, except that the prepolymerization time was set to 1 mmol. No polymer attached to the reactor wall was observed in this prepolymerization.

[Ethylene / 1-butene Copolymerization]

The solid catalyst obtained above was 0.005 mg in terms of Zr atoms, 0.63 mmol of triisobutyl aluminum, 1-butene content of the mixed gas was 5.9 mol%, the amount of hydrogen introduced was 50 Nml, and the polymerization temperature was Except at 80 ° C, the MFR measured at 190 ° C and a load of 2.16 kg was carried out in the same manner as in the ethylene / 1-butene copolymerization of Example 18, and the MFR was 0.018 / 10 min, the density was 0.44 g / cm ³ , 187 g of ethylene / 1-butene copolymers having an average diameter of 660 µm and less than 100 µm of 0.1 wt% were obtained.

The catalyst preparation and polymerization results are shown in Tables 3 and 4.

TABLE 3

* Amount loaded on 1g of silica.

TABLE 4

Example 30

[Production of Solid Catalyst (Zirconium Catalyst)]

A nitrogen-substituted 400 ml glass flask was charged with 18.2 g of silica (TG-20643, manufactured by Fuji-Davison, adsorbed water: 0.3 wt%, 2.7 wt% hydroxyl) and 300 ml of toluene to obtain a suspension, and cooled to 0 ° C. The temperature of the reaction system was kept at 0 degreeC, dropping 33.6 ml of toluene solution (Al; 4.16 mol / L) of the organoaluminum oxy compound made by Selling Company to this suspension over 1 hour. Next, reaction was performed at 0 degreeC for 30 minutes and 95 degreeC for 24 hours. After the reaction was completed, the suspension was cooled to 60 ° C, the solvent was removed, and the residue was washed with 300 ml of hexane.

Next, 4.05 g of the solid catalyst component obtained above was mixed with hexane to obtain a suspension, in which a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (Zr: 0.0291 mol / L) was obtained. 5.2 ml were added. Next, ethylene gas was continuously introduced and prepolymerization was performed at 35 ° C. for 2 hours. In this prepolymerization no prepolymerized catalyst attached to the prepolymerization reactor wall was observed.

After the completion of the preliminary polymerization, the solvent of the reaction mixture was removed, and the residue was washed with 150 ml of hexane.

The washing was carried out four times to obtain a solid catalyst containing 4.6 mg of Zr, 195 mg of Al, and 4.2 g of polyethylene with respect to 1 g of silica.

[Ethylene / 1-butene Copolymerization]

150 g of sodium chloride (made by Wako Pure Chemical Industries, Ltd.) was put into the 2 L stainless steel autoclave sufficiently nitrogen-substituted, and it vacuum-dried at 90 degreeC for 1 hour. Next, a mixed gas containing ethylene and 1-butene (1-butene content was 5.1 mol%) was introduced into the autoclave to reduce the pressure in the reaction system to normal pressure, and the temperature in the reaction system was lowered to 75 ° C.

Next, 1 mmol of triisobutyl aluminum and the solid catalyst obtained above were added to 0.004 mmol in terms of Zr atoms in the autoclave.

50 Nml of hydrogen was introduced into the autoclave, and then the mixed gas was introduced to initiate polymerization under a voltage of 8 kg / cm ² -G. The temperature of the polymerization system immediately increased to 85 ° C. Next, only the mixed gas was charged and maintained at a voltage of 8 kg / cm ² -G and a reaction system temperature of 85 ° C., and polymerization was performed for 1.5 hours.

After the completion of the polymerization, the sodium chloride was washed with water, and the remaining polymer was washed with methanol and vacuum dried overnight at 80 deg. Ethylene / 1-butene air with an MFR of 0.01 g / 10 min, measured at 190 ° C and a load of 2.16 kg, density of 0.45 g / cm ³ , average particle diameter of polymer particles of 860 μm and 0% by weight of fine particles of less than 100 μm 422 g of coal were obtained.

Example 31

[Production of Solid Catalyst (Zirconium Catalyst)]

15.3 g of silica (adsorbed water: 0.1 wt% or less, 2.7 wt% hydroxyl) and 153 ml of toluene obtained by drying silica (TG-20643, manufactured by Fuji-Davison) for 6 hours at 200 ° C. under a nitrogen stream in a nitrogen-substituted 400 ml glass flask. Was charged to obtain a suspension and cooled to 0 ° C.

To this suspension was added dropwise 65.2 ml of a toluene solution (Al; 1.344 mmol / L) of an organic aluminum oxy compound prepared by dissolving dry aluminoxane manufactured by Selling Company in toluene over 1 hour, and the temperature of the reaction system was maintained at 0 ° C. Next, reaction was performed at 0 degreeC for 1 hour, room temperature for 1 hour, and 80 degreeC for 4 hours. Al was not detected in the supernatant of the reaction mixture.

Toluene was then added to the slurry to make 300 ml, and 40 ml of this diluted slurry was separated into another 400 ml glass flask. Next, 100 ml of decane and 3.5 ml of decane solution of triisobutyl aluminum (Al; 1 mol / L) were introduced into the flask, followed by stirring for 10 minutes.

Next, 6 ml of toluene solution containing 0.04 mmol of bis (n-butylcyclopentadienyl) zirconium dichloride and 0.08 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride were added to the suspension. It stirred for 10 minutes. Next, 100 ml of decane was added, ethylene gas was continuously introduced, and prepolymerization was carried out at normal pressure at 35 캜 for 7 hours. In this prepolymerization no prepolymerized catalyst attached to the prepolymerization reactor wall was observed.

After the completion of the prepolymerization, the solvent of the reaction mixture was removed, and the residue was washed with 150 ml of hexane.

The washing treatment was performed three times to obtain a solid catalyst containing 5.1 mg of Zr, 148 mg of Al, and 37 g of polyethylene with respect to 1 g of silica. This solid catalyst was resuspended in hexane and used for polymerization.

[Ethylene / 1-butene Copolymerization]

150 g of sodium chloride (made by Wako Pure Chemical Industries, Ltd., etc.) was put into the 2 L stainless steel autoclave sufficiently nitrogen-substituted, and it vacuum-dried at 90 degreeC for 1 hour. Next, a mixed gas containing ethylene and 1-butene (1-butene content: 4.7 mol%) was introduced into the autoclave to reduce the pressure inside the reaction system to normal pressure, and the temperature in the reaction system was lowered to 70 ° C. Next, 0.5 mmol of triisobutyl aluminum and 0.003 mmol of the solid catalyst obtained above were added to the autoclave in terms of Zr atoms.

50 Nml of hydrogen was introduced into the autoclave, and then the mixed gas was introduced to initiate polymerization under a voltage of 8 kg / cm ² -G. The temperature of the polymerization system immediately increased to 80 ° C. Next, only the mixed gas was charged and maintained at a voltage of 8 kg / cm ² -G and a reaction system temperature of 80 ° C. for polymerization for 1 hour.

After the completion of the polymerization, the sodium chloride was washed with water, the remaining polymer was washed with methanol, and vacuum dried overnight at 80 deg.

As a result, the MFR measured at a load of 190 ° C. and 2.16 kg was 0.21 g / 10 min, the density was 0.924 g / cm ³ , the available amount of 23 ° C. n-decane was 0.2% by weight, and the density was 0.410 g / cm ³ , 110.1 g of ethylene / 1-butene copolymers having an average particle diameter of 610 µm and particles having a mean particle size of less than 100 µm in 0.1 wt%, a melt tension of 13 g, and a Mw / Mn of 3.9 were obtained.

Example 32

[Production of Solid Catalyst (Zirconium Catalyst)]

Except for using 0.06 mmol of bis (n-butylcyclopentadienyl) zirconium dichloride and 0.06 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, the same procedure as in Example 31 was carried out to give 1 g of silica. On the other hand, a solid catalyst containing 5.0 mg of Zr, 150 mg of Al, and 40 g of polyethylene was obtained. No polymer attached to the reactor wall was observed in this prepolymerization.

[Ethylene / 1-butene Copolymerization]

Except for using the catalyst obtained above, it carried out similarly to Example 31, The MFR measured at 190 degreeC and the load of 2.16 kg is 0.48g / 10min, the density is 0.921g / cm <^3> , n-decane soluble loading is 0.4 10% by weight of ethylene / 1-butene copolymer having a density of 0.40 g / cm ³ , an average diameter of polymer particles of 590 μm, particles of less than 100 μm of 0.1 wt%, melt tension of 7.8 g, and Mw / Mn of 3.5 Got.

Example 33

[Production of Solid Catalyst (Zirconium Catalyst)]

Except for using 0.08 mmol of bis (n-butylcyclopentadienyl) zirconium dichloride and 0.04 mmol of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, the same procedure as in Example 31 was carried out to give 1 g of silica. On the contrary, a solid catalyst containing 5.0 mg of Zr, 145 mg of Al, and 43 g of polyethylene was obtained. No polymer attached to the reactor wall was observed in this prepolymerization.

[Ethylene / 1-butene Copolymerization]

Except using the catalyst obtained above, it carried out similarly to Example 31, MV measured at 190 degreeC and 2.16 kg load is 0.95g / 10min, density is 0.918g / cm <^3> , 23 degreeC n-decane soluble quantity Ethylene / 1-butene copolymer 91.0 with 0.6 weight%, density 0.40 g / cm 3, average particle diameter of polymer particles of 650 μm, 0.1 weight% of fine particles less than 100 μm, melt tension of 5.2 g, and Mw / Mn of 2.9 g was obtained.

Comparative Example 8

[Production of Solid Catalyst (Zirconium Catalyst)]

A solid catalyst containing 5.0 mg of Zr, 146 mg of Al, and 41 g of polyethylene was obtained in the same manner as in Example 31 except that only bis (n-butylcyclopentadienyl) zylconium dichloride 0.12 mmol was used. No polymer attached to the reactor wall was observed in this prepolymerization.

[Ethylene / 1-butene Copolymerization]

Aside from the amount of hydrogen introduced, 10 Nml was carried out in the same manner as in the ethylene / 1-butene copolymerization of Example 31, and the MFR measured at 190 ° C and a load of 2.16 kg was 2.88 g / 10 min, and the density was 0.919 g /. cm3, 23 ° C n-decane soluble content 0.6% by weight, density 0.41 g / cm ³ , average particle diameter of polymer particles is 770μm, less than 100μm 0% by weight, melt tension 0.6g, Mw / Mn 198.1 g of an ethylene / 1-butene copolymer of 2.5 was obtained.

Claims (28)

(a-1) (iii) consisting of oxides of at least one element selected from those belonging to groups II, III and IV of the periodic table, (ii) containing less than 1.0% by weight of water and (iii) 1.0% by weight of surface hydroxyl groups Composed of a transition metal compound of a metal belonging to group IVB of the periodic table containing a granular carrier comprising (a-2) an organoaluminum oxy compound and (a-3) a ligand having a cyclopentadienyl skeleton, wherein the organoaluminum oxy A solid catalyst for olefin polymerization comprising the solid catalyst component [A-1], wherein the compound (a-2) and the transition metal compound (a-3) are supported on the particulate carrier (a-1). The solid catalyst for olefin polymerization according to claim 1, wherein the transition metal compound (a-3) comprises two or more transition metal compounds. The transition metal compound (a-3) according to claim 1 or 2, wherein the transition metal compound (a-3) is a transition metal compound of a metal belonging to group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton substituted with a hydrocarbon group. Solid catalyst for olefin polymerization. The olefin polymerization solid catalyst according to claim 1 or 2, wherein the solid catalyst component for olefin polymerization is prepared by prepolymerizing olefin in suspension or gas phase. (a-1) (i) consisting of oxides of at least one element selected from those belonging to groups II, III and IV of the periodic table, (ii) less than 1.0% by weight of water and (i) 1.0% by weight of surface hydroxyl group A transition metal compound of a metal belonging to group IVB of the periodic table containing a granular carrier containing; and (a-2) an organoaluminum oxy compound and (a-3) a ligand having a cyclopentadienyl skeleton. A catalyst in which the aluminum oxy compound (a-2) and the transition metal compound (a-3) are supported on the particulate carrier (a-1) and the solid catalyst component [A-1] and the [C-2] organoaluminum compound Solid catalyst for olefin polymerization, characterized in that the component is configured. 6. The solid catalyst for olefin polymerization according to claim 5, wherein the transition metal compound (a-3) contains two or more transition metal compounds. The transition metal compound (a-3) according to claim 5 or 6, wherein the transition metal compound (a-3) is a transition metal compound of a metal belonging to group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton substituted with a hydrocarbon group. Solid catalyst for olefin polymerization. The solid catalyst for olefin polymerization according to claim 5 or 6, wherein the solid catalyst component for olefin polymerization is prepared by prepolymerizing olefin in suspension or gas phase. (a-1) (i) oxides of at least one element selected from those belonging to groups II, III and IV of the periodic table, (ii) less than 1.0% by weight of water, and (iii) 1.0% by weight or more of surface hydroxyl groups. It is composed of a transition metal compound of a metal belonging to group IVB of the periodic table containing a granular carrier containing and (a-2) an organoaluminum oxy compound and (a-3) a ligand having a cyclopentadienyl skeleton. Polymerizing or copolymerizing olefins in the presence of a catalyst component for olefin polymerization in which an oxy compound (a-2) and a transition metal compound (a-3) are a solid catalyst [A-1] supported on the particulate carrier (a-1). Solid catalyst for olefin polymerization, characterized in that. The olefin polymerization method according to claim 9, wherein the transition metal compound (a-3) contains two or more transition metal compounds. The transition metal compound (a-3) according to claim 9 or 10, wherein the transition metal compound (a-3) is a transition metal compound of a metal belonging to group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton substituted with a hydrocarbon group. Olefin polymerization method. The olefin polymerization method according to claim 9 or 10, wherein the solid catalyst component for olefin polymerization is prepared by prepolymerizing olefin in suspension or gas phase. (a-1) (i) consisting of oxides of at least one element selected from those belonging to groups II, III and IV of the periodic table, (ii) less than 1.0% by weight of water and (i) 1.0% by weight of surface hydroxyl group It is composed of a transition metal compound of a metal belonging to group IVB of the periodic table containing a granular carrier containing and (a-2) an organoaluminum oxy compound and (a-3) a ligand having a cyclopentadienyl skeleton. A catalyst for olefin polymerization in which the oxy compound (a-2) and the transition metal compound (a-3) are the solid catalyst component [A-1] supported on the particulate carrier (a-1), and [C-2] organoaluminum An olefin polymerization method characterized by polymerizing or copolymerizing with olefin in the presence of a catalyst for olefin polymerization composed of a catalyst component which is a compound. The olefin polymerization method according to claim 13, wherein the transition metal compound (a-3) comprises two or more transition metal compounds. The transition metal compound (a-3) according to claim 13 or 14, wherein the transition metal compound (a-3) is a transition metal compound of a metal belonging to group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton substituted with a hydrocarbon group. Olefin polymerization method. The olefin polymerization method according to claim 13 or 14, wherein the solid catalyst component for olefin polymerization is prepared by prepolymerizing olefin in suspension or gas phase. (a-1) (i) consisting of oxides of at least one element selected from those belonging to groups II, III and IV of the periodic table, (ii) less than 1.0% by weight of water and (iii) 1.0% by weight or more of surface hydroxyl groups A solid catalyst component comprising: a granular carrier comprising; and (a-2) an organoaluminum oxy compound, wherein the organoaluminum oxy compound (a-2) is supported on the granular carrier (a-1). And a pre-polymerization of olefins in the presence of a catalyst component which is a transition metal compound of a metal belonging to group IVB of the periodic table containing a ligand having a [B] cyclopentadienyl skeleton and a solid catalyst which is optionally [C] an organoaluminum compound. Solid catalyst for olefin polymerization, characterized in that produced by. 18. The solid catalyst for olefin polymerization according to claim 17, wherein the transition metal compound [B] contains two or more transition metal compounds. The solid catalyst for olefin polymerization according to claim 17 or 18, wherein the transition metal compound [B] is a transition metal compound of a metal belonging to group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton. (a-1) (i) oxides of at least one element selected from those belonging to groups II, III and IV of the periodic table, (ii) less than 1.0% by weight of water, and (iii) 1.0% by weight or more of surface hydroxyl groups. A solid catalyst component comprising a particulate carrier and (a-2) an organoaluminum oxy compound, wherein the organoaluminum oxy compound (a-2) is supported on the granular carrier (a-1) [A-2] And a catalyst component which is a transition metal compound of a metal belonging to group IVB of the Periodic Table containing a ligand having a [B] cyclopentadienyl skeleton, optionally a [C-1] organoaluminum compound, and a [C-2 A catalyst for olefin polymerization, characterized by consisting of a solid catalyst for olefin polymerization prepared by prepolymerization of olefins in the presence of a catalyst component which is an organoaluminum compound. 21. The catalyst for olefin polymerization according to claim 20, wherein the transition metal compound [B] contains two or more transition metal compounds. The olefin according to claim 20 or 21, wherein the transition metal compound (a-1) is a transition metal compound of a metal belonging to group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton substituted with a hydrocarbon group. Catalyst for polymerization. (a-1) (i) oxides of at least one element selected from those belonging to groups II, III and IV of the periodic table, (ii) less than 1.0% by weight of water, and (iii) 1.0% by weight or more of surface hydroxyl groups. A solid catalyst component comprising a particulate carrier and (a-2) an organoaluminum oxy compound, wherein the organoaluminum oxy compound (a-2) is supported on the granular carrier (a-1) [A-2] Olefins in the presence of a catalyst component which is a transition metal compound of a metal belonging to group IVB of the periodic table containing a ligand having a [B] cyclopentadienyl skeleton and a catalyst component which is optionally an [C-1] organoaluminum compound oxy. An olefin polymerization method characterized by polymerizing or copolymerizing olefins in the presence of a solid catalyst for olefin polymerization prepared by prepolymerization. The olefin polymerization method according to claim 23, wherein the transition metal compound [B] contains two or more transition metal compounds. The olefin polymerization method according to claim 23 or 24, wherein the transition metal compound [B] is a transition metal compound of a metal belonging to group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton substituted with a hydrocarbon group. . (a-1) (iii) consisting of oxides of at least one element selected from those belonging to groups II, III and IV of the periodic table, (ii) less than 1.0 wt% of water, and (iii) 1.0 wt% or more of surface hydroxyl groups A solid catalyst component comprising a granular carrier containing (a-2) and an organoaluminum oxy compound, wherein the organoaluminum oxy compound (a-2) is supported on the granular carrier (a-1). ], A catalyst component which is a transition metal compound of a metal belonging to group IVB of the Periodic Table containing a ligand having a [B] cyclopentadienyl skeleton, and optionally a catalyst component which is a [C-1] organoaluminum compound, and a [C- 2] An olefin polymerization method characterized by polymerizing or copolymerizing olefins in the presence of a catalyst for olefin polymerization prepared from a solid catalyst for olefin polymerization prepared by prepolymerization of olefins in the presence of a catalyst component which is an organoaluminum compound. 27. The olefin polymerization method according to claim 26, wherein the transition metal compound [B] contains two or more kinds of transition metal compounds. 28. The method of olefin polymerization according to claim 26 or 27, wherein the transition metal compound [B] is a transition metal compound of a metal belonging to group IVB of the periodic table containing a ligand having a cyclopentadienyl skeleton substituted with a hydrocarbon group. .