JPH09221512A - Dried prepolymerized catalyst for olefin polymerization, its production, and process for polymerizing olefin in vapor phase - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepolymerizing catalyst which has excellent polymerization activity and can give an olefin polymer stably for a long time. SOLUTION: This catalyst is prepared by prepolymerizing an olefin on a solid catalyst component prepared by impregnating a microparticulate support comprising an oxide of at least one element selected from among groups II, III and IV elements in the periodic table with a compound of a group IVB transition metal in the periodic table and an organoaluminumoxy compound and has a content of volatiles of 2wt.% or below. The production process comprises drying this catalyst at 50 deg.C or below in a stream of an inert gas. The polymerization process comprises feeding this catalyst in the state of a solid powder.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a dry prepolymerization catalyst for olefin polymerization which is excellent in polymerization activity and fluidity, a method for producing the same, and a gas phase polymerization method for olefins using such a dry prepolymerization catalyst. Is.

[0002]

BACKGROUND OF THE INVENTION Olefin polymers represented by polyethylene or linear low-density polyethylene (LLDPE), which is a copolymer of ethylene and α-olefin, are widely used as materials for film molding. ing. An olefin polymer is conventionally produced by (co) polymerizing an olefin in the presence of a titanium-based solid catalyst component containing magnesium, titanium and halogen as essential components. In recent years, as a catalyst capable of (co) polymerizing an olefin with higher polymerization activity,
Metallocene catalysts comprising a solid catalyst component containing a metallocene compound of a Group IVB metal of the periodic table such as zirconium and an organoaluminum component have been developed.

[0003] The (co) polymerization of olefins using a catalyst as described above is carried out by a solution polymerization method, a suspension polymerization method or a gas phase polymerization method. In the gas phase polymerization method, a polymer can be obtained in the form of particles, and the liquid phase polymerization method does not require a polymer precipitation step after polymerization, a polymer separation step, and the like. As a result, the manufacturing process can be simplified, and the manufacturing cost can be reduced.

In the gas phase polymerization method, a solid catalyst and an olefin are continuously supplied to a polymerization reactor (fluidized bed reactor), and the olefin is polymerized or copolymerized in a fluidized bed to obtain a particulate polymer. Is a method of continuously performing (co) polymerization of an olefin by continuously extracting the olefin. However, when polymerizing an olefin by a gas phase polymerization method, polymer particles adhere to each other in the fluidized bed to form a polymer lump, thereby reducing the fluidity of the fluidized bed, or causing the polymer particles to be dispersed on the inner wall of the polymerization reactor or the gas dispersion plate. In some cases, the polymer adheres to the sheet to form a sheet-like polymer and the fluidity of the fluidized bed is reduced, so that the operation has to be stopped.

Under these circumstances, it has been desired to develop a polymerization method capable of stably performing gas phase polymerization of olefins for a long period of time. In particular, olefins can be produced over a long period of time using a metallocene catalyst having excellent polymerization activity. There is a demand for a polymerization method capable of performing stable gas phase polymerization.

As a result of intensive studies on the problems in the gas phase polymerization method of such olefins, the present inventors have introduced a solid catalyst into the polymerization system in order to supply it as a slurry of a hydrocarbon medium to the polymerization reactor. It was found that one of the causes is that hydrocarbons are liquefied depending on the temperature and deteriorate the fluidity of the fluidized bed. However, if it is attempted to supply the solid catalyst to the polymerization reactor without making it into a slurry, it is difficult to stably supply the solid catalyst to the polymerization reactor due to the low fluidity of the solid catalyst. When a fluidity improver was added to improve the properties, the polymerization activity was sometimes lowered. Further, when the solid catalyst is dried in order to improve the fluidity of the solid catalyst, the polymerization activity of the solid catalyst may decrease depending on the drying conditions.

As a result of further studies based on such findings, the present inventors have found that a prepolymerization catalyst which is dried under specific conditions and has a volatile component amount of not more than a specific amount has excellent polymerization activity and The inventors have found that they have excellent fluidity and completed the present invention.

[0008]

The present invention has excellent olefin polymerization activity,
And to provide a dry prepolymerization catalyst for olefin polymerization having excellent fluidity and a method for producing the same, and to provide a gas phase polymerization method of an olefin using such a dry prepolymerization catalyst. There is.

[0009]

SUMMARY OF THE INVENTION The dry prepolymerization catalyst for olefin polymerization according to the present invention comprises (A) a particulate carrier comprising an oxide of at least one element selected from Groups II, III and IV of the periodic table. A prepolymerized catalyst obtained by prepolymerizing an olefin onto a solid catalyst component comprising (B) a transition metal compound belonging to Group IVB of the periodic table and (C) an organoaluminum oxy compound, wherein the amount of volatile components is It is characterized by being at most 2.0% by weight.

[0010] The dry prepolymerization catalyst for olefin polymerization of the present invention has excellent fluidity and can be stably supplied to a polymerization reactor. Further, the dry prepolymerization catalyst for olefin polymerization of the present invention is excellent in olefin polymerization activity.

The process for producing a dry prepolymerized catalyst for olefin polymerization according to the present invention comprises: (A) a particulate carrier comprising an oxide of at least one element selected from Groups II, III and IV of the periodic table. Then, a pre-polymerized catalyst obtained by pre-polymerizing an olefin on a solid catalyst component comprising (B) a transition metal compound of Group IVB of the periodic table and (C) an organoaluminum oxy compound is passed under an inert gas flow. , And dried at a temperature of 50 ° C. or less to reduce the amount of volatile components to 2.0% by weight or less.

In the present invention, it is preferable to dry the prepolymerized catalyst using an inert gas having an oxygen concentration of 20 ppm or less and a water content of 20 ppm or less. In addition, the inert gas preferably used in the present invention is such that copper is 20 to 4 times.
Using a catalyst containing 0% by weight, the temperature is 0 to 100 ° C., the pressure is 1 to 30 kg / cm ² -G, and the GHSV is 100 to 200.
After treatment under the condition of ⁰ hr ^-1 , the temperature is 0 to 100 ° C. and the pressure is 1 to 30 kg / cm using a molecular sieve.
^2- G and GHSV can be obtained by processing under conditions of 100 to 2000 hr ^-1 .

In the present invention, the inert gas treated as described above has an oxygen concentration of 20 ppm or less and a water content of 2 ppm.
It is preferably 0 ppm or less.

When the prepolymerized catalyst is dried by such a method, a dried prepolymerized catalyst having excellent fluidity can be produced without lowering the olefin polymerization activity.
The gas-phase polymerization method for olefins according to the present invention comprises: (A) at least one selected from Group II, Group III and Group IV of the periodic table.
An olefin is prepolymerized on a solid catalyst component in which (B) a transition metal compound of Group IVB of the Periodic Table and (C) an organoaluminum oxy compound are supported on a fine-particle carrier made of an oxide of an element of the kind. When the olefin is polymerized in the gas phase while supplying the prepolymerized catalyst to the polymerization reactor, the prepolymerized catalyst having a volatile component amount of 2.0% by weight or less is supplied to the polymerization reactor in a solid powder state. Features.

The olefin polymerization method of the present invention can stably polymerize an olefin over a long period of time with excellent polymerization activity. In addition, since the catalyst is not supplied to the polymerization reactor in the form of slurry, the polymerization can be carried out even at a temperature equal to or lower than the boiling point of the hydrocarbon used for slurrying the catalyst, and the polymerization temperature range becomes wider than before.

[0016]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the dry prepolymerization catalyst for olefin polymerization according to the present invention, a method for producing the same, and a gas phase polymerization method for olefins will be specifically described.

In the present specification, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also homopolymer. , May also be used in a meaning including a copolymer.

The dry prepolymerization catalyst for olefin polymerization according to the present invention comprises (A) a finely divided carrier, (B)
A prepolymerized catalyst in which an olefin is prepolymerized on a solid catalyst component comprising a group B transition metal compound and (C) an organoaluminum oxy compound, wherein the solid component has a volatile content of 2.0% by weight or less. It is a catalyst.

First, each component forming the dry prepolymerization catalyst for olefin polymerization according to the present invention will be described. The fine particle carrier (A) used in the present invention may be any of the following:
It is a particulate inorganic compound composed of an oxide of at least one element selected from Group III and Group IV.

Porous oxides are preferred as the finely divided inorganic compound, specifically SiO ₂ , Al ₂ O ₃ and Mg.
O, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO,
BaO, ThO _2, etc., or a mixture thereof or a mixture containing them and another oxide, for example, SiO ₂ —Mg
O, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO _{2-
V 2 O 5, SiO 2 -Cr} 2 O 3, SiO 2 -TiO 2 -MgO
And the like. Among these, SiO ₂ ,
It is preferable that the main component is at least one component selected from the group consisting of Al ₂ O ₃ and MgO.
iO ₂ is preferred. These can be used in combination of two or more.

The fine-particle carrier (A) used in the present invention
Has a specific surface area in the range of 50 to 1000 m ² / g, a pore volume in the range of 0.3 to 2.5 cm ³ / g, and an average particle size in the range of 1 to 300 μm. Is desirable.

As the transition metal compound (B) belonging to Group IVB of the periodic table used in the present invention, a compound containing a ligand having a cyclopentadienyl skeleton represented by the following general formula (I) is exemplified. be able to.

ML _X (I) In the formula, M represents one kind of transition metal atom selected from the group IVB transition metal atoms of the periodic table, preferably zirconium, titanium or hafnium.

X is the valence of the transition metal atom M, and indicates the number of ligands L coordinated to the transition metal atom M. L is
Represents a ligand or a group which coordinates to the transition metal atom M, and at least one L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having the cyclopentadienyl skeleton Is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group,
SO ₃ R (provided that R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom or a hydrogen atom. Two or more L may be the same or different from each other.

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

Among these ligands having a cyclopentadienyl skeleton, an alkyl-substituted cyclopentadienyl group is particularly preferred. When the compound represented by the general formula (I) contains two or more ligands having a cyclopentadienyl skeleton, two of the ligands having a cyclopentadienyl skeleton are ethylene, propylene And a substituted alkylene group such as isopropylidene and diphenylmethylene; a silylene group; a dimethylsilylene group; and a bonding group such as a substituted silylene group such as a diphenylsilylene group and a methylphenylsilylene group.

Specific examples of the ligand other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and the like. Specifically, examples of the alkyl group include a methyl group, an ethyl group, A propyl group, an isopropyl group, a butyl group and the like are exemplified.The cycloalkyl group is exemplified by a cyclopentyl group and a cyclohexyl group.The aryl group is exemplified by a phenyl group and a tolyl group, and the aralkyl group is exemplified by benzyl group. And a neofil group.

The alkoxy group has 1 to 1 carbon atoms.
Ten examples, for example, methoxy group, ethoxy group, butoxy group and the like are exemplified. Examples of the aryloxy group include those having 6 to 20 carbon atoms, such as a phenoxy group.

Examples of the trialkylsilyl group include those having a total of 3 to 21 carbon atoms, such as a trimethylsilyl group and a triethylsilyl group. Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.

Halogen includes fluorine, chlorine, bromine,
Examples include iodine. When the valence of the transition metal atom is 4, for example, the transition metal compound (B) used in the present invention is more specifically represented by the following general formula (I ′).

R ¹ R ² R ³ R ⁴ M (I ') In the formula, M is a transition metal atom similar to the above, and R ^{1 to} R
⁴ represents a ligand or a group which coordinates to the transition metal atom M.

R ¹ is a ligand having a cyclopentadienyl skeleton similar to L.

R ² , R ³ and R ^{4, which} may be the same or different from each other, have a ligand having a cyclopentadienyl skeleton similar to the above L, a hydrocarbon group having 1 to 12 carbon atoms, It is one kind of group or atom selected from the group consisting of an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃ R, a halogen atom and a hydrogen atom.

In the present invention, a transition metal compound in which one of R ² , R ³ and R ^{4 in} the above general formula (I ′) is a ligand having a cyclopentadienyl skeleton, for example R ¹ and R ² is A transition metal compound which is a ligand having a cyclopentadienyl skeleton is preferably used. The ligands having these cyclopentadienyl skeletons are
It may be bonded via the above-mentioned bonding group. In this case, R ³ and R ⁴ are alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, SO ₃ R, halogen atoms or hydrogen atoms.

The following are specific examples of the transition metal compound in which M is zirconium among the compounds represented by the general liquid (I). Bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium bis (p-
Toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (indenyl) ) Dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulphonate), ethylenebis (indenyl) zirconium bis (p-toluenesulphonate), Ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonate), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropyl Den (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride, dimethylsilylene bis (methylcyclopentadienyl) ) Zirconium dichloride, dimethyl silylene bis (dimethylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (trimethylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium bis (trifluoromethane) Sulfonato), dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichlorine , Dimethyl silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenyl silylene bis (indenyl) zirconium dichloride, methylphenyl silylene bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) Zirconium dibromide, bis (cyclopentadienyl)
Methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopentadienyl) cyclohexylzirconium monochloride, bis (cyclopentadienyl) phenylzirconium monochloride, bis (cyclopentadienyl)
Benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, Bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl)
Zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclo Pentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl)
Zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadiene) (Enyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl)
Zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) ) Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride,
Bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl)
Zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples, compounds having a di-substituted cyclopentadienyl ring include compounds having 1,2- and 1,3-substituted cyclopentadienyl rings, and compounds having a tri-substituted cyclopentadienyl ring. Compounds include compounds having 1,2,3- and 1,2,4-substituted cyclopentadienyl rings. Alkyl groups such as propyl and butyl are n-,
It includes isomers such as i-, sec- and tert-.

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

These transition metal compounds (B) may be used alone or in combination of two or more.
It may be diluted with a hydrocarbon or a halogenated hydrocarbon before use.

In the present invention, as the transition metal compound (B), a zirconocene compound in which the central transition metal atom is zirconium and which has a ligand containing at least two cyclopentadienyl skeletons is preferably used.

Specific examples of the organoaluminum oxy compound (C) used in the present invention include conventionally known aluminoxanes and benzene-insoluble organoaluminum oxy compounds exemplified in JP-A-2-78687. .

The conventionally known aluminoxane can be produced from the organoaluminum compound (D) described later, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of the hydrocarbon medium in the above, and reacting the organoaluminum compound with adsorbed water or water of crystallization. (2) A method in which water, ice, or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent of aluminoxane.

The dry prepolymerization catalyst for olefin polymerization according to the present invention is prepared by adding (B)
A solid catalyst obtained by drying a prepolymerized catalyst obtained by prepolymerizing an olefin in the presence of a solid catalyst component carrying a transition metal compound and an organic aluminum oxy compound (C).

FIG. 1 shows a process for preparing a dry prepolymerization catalyst for olefin polymerization according to the present invention. The solid catalyst component can be prepared by bringing the (A) transition metal compound and the (C) organoaluminum oxy compound into contact with the (A) particulate carrier as described above.

The contact of each of the above components can be performed in an inert hydrocarbon medium. Specific examples of such an inert hydrocarbon medium include propane, butane, pentane, hexane, heptane, octane, decane, Aliphatic hydrocarbons such as dodecane and kerosene; cyclopentane, cyclohexane,
Alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

In preparing the solid catalyst component, (B)
The transition metal compound (in terms of transition metal atom) is used in an amount of usually 0.001 to 1.0 mmol, preferably 0.01 to 0.5 mmol, per 1 g of the fine particle carrier (A).
(C) The organic aluminum oxy compound is usually 0.1 to
It is used in an amount of 100 mmol, preferably 0.5-20 mmol.

The solid catalyst component thus obtained is
In addition to the above-mentioned catalyst components, other components useful for olefin polymerization, such as an electron donor and a reaction aid, may be contained as necessary.

As a method for prepolymerizing an olefin in the presence of the solid catalyst component, a conventionally known method is used.
For example, it can be carried out by introducing an olefin into an inert hydrocarbon medium in the presence of the solid catalyst component. As the inert hydrocarbon medium used for preparing the prepolymerized catalyst, the same as those described above can be mentioned.

In the prepolymerization, the following organoaluminum compound (D) can be used together with the solid catalyst component. Specific examples of the organoaluminum compound (D) used in the present invention as the organoaluminum compound and also used in preparing the aluminoxane described above include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum. Aluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, trialuminum Tricycloalkylaluminum such as cyclooctylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diethyl Rumi bromide, dialkyl aluminum halide such as diisobutyl aluminum chloride; diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide;
Examples include dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, trialkylaluminum is more preferred, and triethylaluminum and triisobutylaluminum are particularly preferred.

As the organic aluminum compound, isoprenyl aluminum represented by the following general formula can also be used. _{(I-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, and z ≧ 2x.) These are the combination of two or more It may be.

The (A) organoaluminum compound used as necessary in the present invention may contain a small amount of a metal component other than aluminum. In the thus prepared prepolymerized catalyst, it is desirable that 0.5 to 300 g, preferably 1 to 200 g, more preferably 2 to 100 g of the prepolymerized olefin polymer is present per 1 g of the solid catalyst component. .

The dry prepolymerization catalyst for olefin polymerization according to the present invention can be obtained by drying the above prepolymerization catalyst. The drying of the prepolymerized catalyst is usually performed after removing the dispersion medium hydrocarbon from the obtained suspension of the prepolymerized catalyst by filtration or the like.

Drying of the prepolymerized catalyst is carried out by flowing the prepolymerized catalyst under an inert gas stream at 50 ° C. or lower, preferably 20 to 40 ° C.
This is done by maintaining the temperature in the range of ° C. The volatile component amount of the obtained dried prepolymerized catalyst is 2.0% by weight or less,
Preferably, it is not more than 1.0% by weight. The amount of the volatile component of the dry prepolymerization catalyst is preferably as small as possible, and there is no particular lower limit, but practically it is 0.001% by weight. The drying time is usually 3 to 8 hours, depending on the drying temperature.

When the amount of the volatile component of the dried prepolymerized catalyst exceeds 2.0% by weight, the fluidity of the dried prepolymerized catalyst decreases,
In some cases, it may not be possible to stably supply the mixture to the polymerization reactor. The angle of repose of the dried prepolymerized catalyst is 50 ° or less, preferably 5 to 47 °, more preferably 10 to 45 °.
If the angle of repose of the dried pre-polymerization catalyst exceeds 50 °, the fluidity of the dried pre-polymerization catalyst may decrease, and it may not be possible to stably supply the catalyst to the polymerization reactor.

Here, the amount of volatile components of the dry prepolymerization catalyst is measured by, for example, a weight loss method, a method using gas chromatography, or the like.

In the weight loss method, the weight loss when the dried prepolymerized catalyst is heated at 110 ° C. for 1 hour in an inert gas atmosphere is determined and expressed as a percentage based on the weight of the dried prepolymerized catalyst before heating.

In the method using gas chromatography, volatile components such as hydrocarbons are extracted from the dried prepolymerized catalyst, and a calibration curve is prepared in accordance with the internal standard method, and then calculated as a percentage by weight from the GC area.

The method for measuring the amount of volatile components in the dry prepolymerized catalyst is a weight loss method when the amount of volatile components in the dry prepolymerized catalyst is about 1% by weight or more. Is less than about 1% by weight, a method using gas chromatography is employed.

Examples of the inert gas used for drying the prepolymerized catalyst include nitrogen gas, argon gas, and neon gas. Such an inert gas has an oxygen concentration of 2
0 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less, the water content is 20 ppm or less,
It is preferably at most 10 ppm, more preferably at most 5 ppm. If the oxygen concentration and the water content in the inert gas exceed the above ranges, the olefin polymerization activity of the dry prepolymerization catalyst may be significantly reduced.

An inert gas having an oxygen concentration of 20 ppm or less and a water content of 20 ppm or less can be obtained, for example, by contacting a commercially available inert gas with a catalyst containing 20 to 40% by weight of copper, It can be obtained by contact treatment with a sieve.

Used in treating the inert gas
As the copper-containing catalyst, water containing 20 to 40% by weight of copper is used.
More specifically, basic addition catalysts, deoxidation catalysts, etc.
Is a copper-chromium catalyst (for example, Cu; 35% by weight, C
r; 31% by weight, Ba; 2% by weight, Mn; 2.5% by weight
%), A copper-based catalyst in which copper is supported on silica (for example, Si
O _Two50 to 65% by weight, Cu; 16 to 30% by weight)
And so on.

Such a catalyst is R3-11 (BASF
G-99B, G-108A, G-108B (Ni
ssan-Girdler). Inactive
The gas is brought into contact with a catalyst containing 20 to 40% by weight of copper.
In this case, the temperature is 0 to 100 ° C, preferably 0 to 50 ° C.
Range, pressure is 1-30 kg / cm ^Two-G, preferably
Is 1-10kg / cm^Two-G and GHSV is 1
00-2000hr^-1, Preferably 200-2000h
r^-1, More preferably 200 to 400 hours^-1In the range of
Is desirable.

[0064] Here, "GHSV" is used to mean a gas space velocity per unit time, the reactor volume the volume rate of the feed gas (m ³ / hr) at a temperature and pressure during the reaction (m ³⁾ And the unit is hr ^-1 . The reactor volume at this time is an empty volume not filled with the catalyst.

The molecular sieve used for preparing the inert gas has a bulk density of 0.6 to 0.9.
g / cm ³ , and such molecular sieves are commercially available as Zeorum A-3, Zeorum A-4 (trade name, manufactured by Tosoh), Molecular Sieve 3A, Molecular Sieve 4A (trade name, manufactured by Nippon Unicar) Have been.

Contact the inert gas with the molecular sieve.
When touched, the temperature is 0 to 100 ° C., preferably 0 to
It is in the range of 50 ° C and the pressure is 1 to 30 kg / cm.^Two-G,
Preferably 1-10 kg / cm^Two-G range, GH
SV is 100 ~ 2000hr ^-1, Preferably 200-2
000hr^-1, More preferably 200 to 400 hours^-1of
It is desirable that it is in the range.

As described above, the inert gas used for drying the prepolymerized catalyst is a catalyst containing 20 to 40% by weight of copper, and has a temperature of 0 to 100 ° C. and a pressure of 1 to 30 kg / cm ^2-.
G, after treatment under the conditions of GHSV 100 to 2000 hr ^-1 , using a molecular sieve, at a temperature of 0 to 100 ° C.,
Pressure 1-30kg / cm ² -G, GHSV100-200
The treatment is preferably performed at ⁰ hr ^-1 to reduce the oxygen concentration to 20 ppm or less and the water content to 20 ppm or less.

Since the dry prepolymerization catalyst for olefin polymerization according to the present invention is excellent in fluidity, it can be stably supplied to the polymerization reactor. Further, the olefin can be (co) polymerized with excellent polymerization activity.

In the olefin gas phase polymerization method according to the present invention, when the olefin is polymerized in the gas phase while continuously supplying the solid catalyst and the olefin to the polymerization reactor (fluidized bed reactor), The dry prepolymerization catalyst for olefin polymerization is supplied to the polymerization reactor in a solid powder state to polymerize the olefin. In the polymerization, the above-mentioned (D) is used together with this dry prepolymerization catalyst for olefin polymerization.
Organoaluminum compounds can also be used. (D)
The organoaluminum compound is used in an amount of usually 1 to 1000 mol, preferably 2 to 300 mol, per 1 mol of the transition metal atom in the transition metal compound (B) contained in the dry prepolymerization catalyst for olefin polymerization. Is desirable.

The polymerization reaction can be carried out in any of a batch system, a semi-continuous system and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions. In the present invention, it is preferable to employ a continuous fluidized-bed gas-phase polymerization method.

The polymerization temperature in the gas phase polymerization method is usually 50
To 120 ° C, preferably 60 to 100 ° C.
The polymerization pressure is usually normal pressure to 100 kg / cm ^2, a range preferably from normal pressure to 50 kg / cm ^2. The gas line speed is
0.4 to 1.5 m / sec, preferably 0.6 to 1.2
m / sec.

The olefin gas phase polymerization method according to the present invention will now be described in detail with reference to FIG. The dry prepolymerization catalyst (solid catalyst) 1 for olefin polymerization as described above is continuously supplied to a fluidized bed reactor 3 in a solid powder state, for example, via a line 2.

The solid catalyst 1 is generally used in an amount of 0.00001 to 1.0 mmol / hour, preferably 0.0001 to 0.1 mmol / hr, as calculated as transition metal atoms in the transition metal compound (A) per liter of polymerization volume. Desirably, it is used in an amount of 1 mmol / hr.

The gaseous olefin is fed to the fluidized bed reactor 3
For example, its lower part is blown continuously by a gas blower 7 via a line 6. The olefin is supplied from the olefin supply line 9 to the gas blower 7. The olefin blown into the lower part of the fluidized bed reactor 3 disperses the solid catalyst 1 through a gas dispersion plate 4 such as a perforated plate to form a fluidized bed (reaction system) 5. In the fluidized bed 5, the olefin is (co) polymerized to form a particulate olefin (co) polymer. As described above, the olefin supplied to the reactor 3 also serves as a fluidizing gas that keeps the catalyst particles in the reaction system in a fluidized state. It is also possible to use a gas mixture of an olefin and an inert gas such as nitrogen as the fluidizing gas. The produced polymer particles are continuously withdrawn from the fluidized bed reactor 3 via the polymer recovery line 11.

On the other hand, the gaseous unreacted olefin that has passed through the fluidized bed 5 is decelerated in the deceleration zone 3 a provided in the upper part of the fluidized bed reactor 3 and then exits the fluidized bed reactor 3. . The unreacted olefin emerging from the fluidized bed reactor 3 can be circulated via the circulation line 10 together with fresh olefin from the olefin feed line 9. It is preferable that the unreacted olefin is removed by the heat exchanger 8 before the circulation. However, the heat of polymerization can also be used to heat fresh olefin before feeding it to reactor 3. Although the heat exchanger 8 is shown downstream of the blower 7 in FIG. 2, it may be arranged upstream of the blower 7.

As described above, the polymerization method of the present invention can be operated continuously.

The molecular weight of the obtained olefin polymer can be adjusted by adding a molecular weight modifier such as hydrogen to the polymerization system or by changing the polymerization temperature. Hydrogen can be supplied from any location in the gas phase fluidized bed reactor, for example, from line 10.

The olefin used in the present invention is preferably an α-olefin having 2 to 18 carbon atoms, for example, ethylene, propylene, 1-butene,
1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene , 1-hexadecene, 1-octadecene and the like.

Further, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
Monocyclic and polycyclic olefins such as a, 5,8,8a-octahydronaphthalene, and aromatic and alicyclic vinyl compounds such as styrene, vinyltoluene and vinylcyclohexane are also included.

In addition to the olefin, butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene,
Polyenes such as 5-ethylidene-2-norbornene can also be copolymerized.

In the present invention, among these, it is preferable to produce linear low density polyethylene (LLDPE) by copolymerizing ethylene and an α-olefin having 3 to 18 carbon atoms. In the present invention, among the olefin polymers, particularly, a constituent unit derived from ethylene is contained at a ratio of 75 to 98% by weight, preferably 80 to 97% by weight, and is derived from an α-olefin having 3 or more carbon atoms. Constituent units
Particularly preferred is a low-crystalline ethylene / α-olefin copolymer so-called linear low-density polyethylene (LLDPE) containing 3 to 25% by weight, preferably 3 to 20% by weight.

[0082]

EFFECTS OF THE INVENTION The dry prepolymerization catalyst for olefin polymerization according to the present invention comprises (A) a fine particle carrier and (B) a periodic table.
A prepolymerization catalyst in which an olefin is prepolymerized on a solid catalyst component carrying a group IVB transition metal compound and (C) an organoaluminum oxy compound, wherein the volatile component in the prepolymerization catalyst is 2% by weight. % Or less, the fluidity is excellent, and the supply to the polymerization reactor can be stably performed. Further, such a catalyst has excellent olefin polymerization activity.

The method for producing a dry prepolymerized catalyst for olefin polymerization according to the present invention can produce a dry prepolymerized catalyst having excellent fluidity without lowering the olefin polymerization activity.

Since the olefin polymerization method according to the present invention polymerizes olefins in the gas phase while supplying the dry prepolymerization catalyst for olefin polymerization in a solid powder state to the polymerization reactor, it has excellent polymerization activity. Olefin can be stably polymerized over a long period of time. Further, since the catalyst is not supplied to the polymerization reactor in the state of suspension of hydrocarbon, the polymerization temperature range is wider than before.

[0085]

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

In this specification, the amount of volatile components and the angle of repose were measured as follows. [Amount of Volatile Components] 0.5 g of pretreated sample was weighed and extracted with 30 ml of acetone while cooling with dry ice acetone, and then an acetone solution of methyl benzoate as an internal standard was 0.05 g / 5.
Add ml. 1 ml of 13% aqueous ammonia is added, and then acetone is added to make 50 ml. Filter the sample with a 0.2 μm filter. Analytical method Take 1 microliter of the pretreated sample,
Hydrocarbons having 6 to 10 carbon atoms are detected as volatile components by gas chromatography. The content of the volatile component is calculated from the GC area after preparing a calibration curve according to the internal standard method, and is expressed as% by weight. Measurement condition column; fused silica capillary column DB-WAX (J &
W-company, 122-7062) Column length; 0.25 mmφ × 60 m df = 0.25
μm Column temperature; 50 ° C. → 230 ° C. (retention time 2 minutes, temperature rise 1
5 ° C./min) Detector; FID carrier gas; helium split ratio; 1:65 split flow rate; 73 ml / min.

[Angle of repose] The angle of repose is determined by Seishin Enterprise Co., Ltd.
It was measured by the discharge method using a multi-tester MT-1000 ^™ . That is, the dry prepolymerized catalyst was dropped from the upper funnel onto the measurement table, and the angle (repose angle) of the slope of the conical mountain of the dry prepolymerized catalyst deposited on the table was measured. At this time, the angle was measured at three or more points, and the value obtained by arithmetically averaging those values was defined as the angle of repose. The smaller the angle of repose, the better the fluidity of the dried prepolymerized catalyst.

[0088]

Example 1 [Preparation of solid catalyst component] 10 kg of silica (SiO ₂ ) dried at 250 ° C. for 10 hours was suspended in 154 liters of toluene and then cooled to 0 ° C. To this suspension, 50.5 liters of a methylaminooxane toluene solution (Al = 1.52 mol / liter) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 5 ° C. Continue 0
React at ℃ for 30 minutes, then over 95 hours at 95 ℃
The temperature was raised to, and the reaction was carried out at that temperature for 4 hours. Then 60
The temperature was lowered to ℃, and the supernatant was removed by decantation. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene to make the total volume 160 liters.

To the obtained suspension, a solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride in toluene (Zr = 25.7 mmol / liter) was added.
2.0 liter was added dropwise at 80 ° C. over 30 minutes, and the reaction was further performed at 80 ° C. for 2 hours. Then, the supernatant was removed and the solid was washed twice with hexane to obtain a solid catalyst component containing 3.2 mg of zirconium per 1 g of silica.

[Preparation of Prepolymerized Catalyst] The solid catalyst component of 7.0 k was placed in a 350 liter reactor which was sufficiently replaced with nitrogen.
g and hexane were charged to bring the total volume to 285 liters. After cooling the system to 10 ° C, ethylene was added to 8 Nm ³
Bubbling into the hexane suspension of the solid catalyst component for 5 minutes at a flow rate of / hr. During this time, the temperature in the system was maintained at 10 to 15 ° C. Then, the supply of ethylene was stopped, and 2.4 mol of triisobutylaluminum and 1.2 kg of 1-hexene were charged. After making the system a closed system, 8Nm ³
The supply of ethylene was restarted at a flow rate of / hr. After 15 minutes, the flow rate of ethylene was reduced to 2 Nm ³ / hr, and the pressure in the system was set to 0.8 kg / cm ² -G. During this time, the temperature in the system rose to 35 ° C. After that, the temperature in the
While controlling at 35 ° C., ethylene was added to 4 Nm ³ /
It was supplied at a flow rate of hr for 3.5 hours. During this time, the pressure in the system was maintained at 0.7 to 0.8 kg / cm ² -G. Then
The inside of the system was replaced with nitrogen, the supernatant was removed, and the system was washed twice with hexane. In this way, a prepolymerized catalyst in which 3 g of the polymer was prepolymerized per 1 g of the solid catalyst component was obtained.
[Η] of this prepolymerized polymer was 2.1 dl / g, and the content of 1-hexene was 4.8% by weight.

Further, the supernatant liquid after the prepolymerization was colorless and transparent, the shape of the prepolymerization catalyst was good, and the bulk density was 0.4 g / cm ³ . [Drying of Prepolymerized Catalyst] 20 kg of the hexane suspension of the prepolymerized catalyst obtained above was charged into a jacketed filter dryer having a capacity of 130 liters as the amount of the prepolymerized catalyst.
Hexane was filtered. Thereafter, the temperature of the jacket was raised to 40 ° C., and the system was dried for 3 hours while passing nitrogen gas (oxygen concentration: 10 ppm, water content: 5 ppm) through the system at 6 Nm ³ / hr. During that time, the temperature in the system rose from 20 ° C to 35 ° C. By this operation, the volatile component is 0.1% by weight, the bulk density is 0.40 g / cm ³ , and the angle of repose is 3
A dry prepolymerization catalyst with a 8.1 ° was obtained.

[Gas Phase Polymerization] Using a continuous fluidized bed gas phase polymerization apparatus, ethylene and 1-hexene were reacted at a total pressure of 20 kg / cm ² -G, a polymerization temperature of 85 ° C., and a gas linear velocity of 0.7 m / sec. Copolymerization was performed. 60 g of the dry prepolymerized catalyst prepared above
It was continuously fed at a rate of hr and ethylene, 1-hexene, hydrogen and nitrogen were continuously fed in order to maintain a constant gas composition during the polymerization (gas composition; 1-hexene / ethylene = 0.025 , Hydrogen / ethylene = 1.5 × 10 ⁻⁴ , ethylene concentration = 71%).

The obtained ethylene / 1-hexene copolymer had a yield of 80 kg / hr and a density of 0.91 g / c.
m ³ and a melt flow rate (MFR) of 0.61
g / 10 minutes, the bulk density is 0.44 g / cm ³ ,
The average particle size of the polymer particles is 1050 μm,
The proportion of the finely divided polymer having a particle size of not more than 0.1 μm was not more than 0.1% by weight.

After 10 days of continuous polymerization, the inner wall of the polymerization apparatus and the dispersion plate were inspected, and no adhered polymer was observed.

[0095]

Example 2 Oxygen concentration was 25 pp for drying the prepolymerized catalyst.
A dry prepolymerized catalyst having a volatile content of 0.1% by weight was prepared in the same manner as in Example 1 except that nitrogen gas of m was used, and the dry prepolymerized catalyst was used in the same manner as in Example 1. As a result of copolymerizing ethylene and 1-hexene, the yield was 56 kg / hr.

[0096]

Example 3 As a nitrogen gas for drying the prepolymerization catalyst, a nitrogen gas having an oxygen concentration of 25 ppm was first prepared by BASF.
A reaction tube filled with 25 liters of R3-11 at 40 ° C, 1
At a pressure of GHSV 300 hr ^-1 , the adsorption tube filled with 25 liters of molecular sieve (Zeoram A-3, manufactured by Tosoh Corporation) was charged at 40 ° C., 1 atm, GHS
Example 1 except that nitrogen gas having an oxygen concentration of 5 ppm and a water content of 3 ppm was used under the condition of V 300 hr ^-1.
A dry prepolymerized catalyst was prepared in the same manner as above, and the copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1 except that this dry prepolymerized catalyst was used. As a result, the yield was 82 kg.
/ Hr.

[0097]

Example 4 [Drying of Preliminary Polymerization Catalyst] 20 kg of the hexane suspension of the prepolymerization catalyst obtained in Example 1 as a prepolymerization catalyst amount was put into a filtration dryer with a jacket having an inner volume of 130 liters, and hexane was added. Filtered. After that, the jacket is 40 ℃
The temperature was raised to 3, and nitrogen gas (oxygen concentration 10 ppm, water content 7 ppm) was aerated at 6 Nm ³ / hr to dry the system for 3 hours. During that time, the temperature in the system rose from 20 ° C to 35 ° C. By this operation, the volatile component is 0.1% by weight, the bulk density is 0.40 g / cm ³ , and the angle of repose is 3
A dry prepolymerized catalyst having a 9.3 ° was obtained.

[Gas Phase Polymerization] Ethylene and 1- were prepared in the same manner as in Example 1 except that the dry prepolymerized catalyst prepared above was used.
Polymerized with hexene.

The obtained ethylene / 1-hexene copolymer had a yield of 78 kg / hr and a density of 0.91 g / c.
m ³ , the MFR is 0.65 g / 10 min, the bulk density is 0.43 g / cm ³ , the average particle size of the polymer particles is 1000 μm, and the ratio of the fine powder polymer of 100 μm or less is 0.1. It was less than weight%.

After continuous polymerization for 10 days, the inner wall of the polymerization apparatus and the dispersion plate were inspected and no adhering polymer was found.

[0101]

Comparative Example 1 [Drying of Preliminary Polymerization Catalyst] 20 kg of the hexane suspension of the prepolymerization catalyst obtained in Example 1 as a prepolymerization catalyst amount was put into a filtration dryer with a jacket having an inner volume of 130 liters, and hexane was added. Filtered. After that, the jacket is 40 ℃
The temperature was raised to 1, and nitrogen gas (oxygen concentration 10 ppm, water content 5 ppm) was aerated at 6 Nm ³ / hr for 1 hour while being aerated. During that time, the temperature in the system rose from 20 ° C to 22 ° C. By this operation, the volatile component was 3% by weight, the bulk density was 0.33 g / cm ³ , and the angle of repose was 6
A dry prepolymerized catalyst having a 0.5 ° was obtained.

[Gas Phase Polymerization] Ethylene and 1- were prepared in the same manner as in Example 1 except that the dry prepolymerized catalyst prepared above was used.
An attempt was made to polymerize with hexene, but the fluidity of the dry prepolymerization catalyst was poor and it could not be continuously supplied to the polymerization reactor.

[0103]

Example 5 [Preparation of Prepolymerized Catalyst] 10 kg of silica (SiO ₂ ) dried at 250 ° C. for 10 hours was suspended in 154 liters of toluene and then cooled to 0 ° C. To this suspension, 44.1 liters of a methylaminooxane toluene solution (Al = 1.52 mol / liter) was added dropwise over 1 hour. At this time, the temperature in the system was kept at 0 to 5 ° C. Continue 0
React at ℃ for 30 minutes, then over 95 hours at 95 ℃
The temperature was raised to, and the reaction was carried out at that temperature for 4 hours. Then 60
The temperature was lowered to ℃, and the supernatant was removed by decantation. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene to make the total volume 160 liters.

62 liters of the resulting suspension was transferred to another reactor and another 75 liters of toluene were added. Then, rac-dimethylsilylenebis {1- (2-methyl
After adding 50 g of -4,5-benzoindenyl)} zirconium dichloride and stirring for 20 minutes, 270 liters of hexane and 4.35 mol of triisobutylaluminum were added. Subsequently, propylene was added at 8 kg / hr. Pre-polymerization was carried out at 20 ° C. for 2 hours while feeding at a rate of. After 2 hours, the supply of propylene was stopped and the reaction was continued for another 30 minutes. Then, the system was replaced with nitrogen, the supernatant was removed, and the system was washed with hexane three times. In this way, a prepolymerized catalyst in which about 3 g of the polymer was prepolymerized per 1 g of the solid catalyst component was obtained.

[Drying of Prepolymerized Catalyst] The prepolymerized catalyst was dried in the same manner as in Example 1 except that the above prepolymerized catalyst was used. As a result, the volatile component was 0.2% by weight, the bulk density was 0.40 g / cm ³ , and the angle of repose was 36.0 °.
To obtain a dry prepolymerized catalyst.

[0106]

Comparative Example 2 [Drying of Prepolymerized Catalyst] The prepolymerized catalyst obtained in Example 5 was dried in the same manner as in Comparative Example 1. As a result, the volatile component was 2.8% by weight and the bulk density was 0.34 g / c.
m ³ and a repose angle of 58.9 ° were obtained.

[Brief description of drawings]

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

FIG. 2 is a schematic diagram showing an example of a gas phase fluidized bed reactor capable of polymerizing olefins according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Solid catalyst 3 ... Fluid bed reactor 3a ... Deceleration zone 4 ... Gas dispersion plate 5 ... Fluidized bed 7 ... Blower 8 ... Heat exchanger 9 ... Olefin supply line 10 ... Circulation line 11 ... Polymer recovery line

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Kenji Doi Inventor Kenji Doi 6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. Waki-cho 6-1-2 Waki Mitsui Petrochemical Industry Co., Ltd.

Claims (5)

[Claims] 1. A fine particle carrier comprising (A) an oxide of at least one element selected from groups II, III and IV of the periodic table, and (B) a transition metal of group IVB of the periodic table. A prepolymerization catalyst in which an olefin is prepolymerized on a solid catalyst component in which a compound and (C) an organoaluminum oxy compound are supported, and the amount of volatile components is 2.0% by weight or less. Dry prepolymerization catalyst for olefin polymerization. 2. A fine particle carrier comprising (A) an oxide of at least one element selected from groups II, III and IV of the periodic table, and (B) a transition metal of group IVB of the periodic table. The compound and the (C) organoaluminum oxy compound are supported on the solid catalyst component, and the prepolymerized catalyst in which the olefin is prepolymerized is dried at a temperature of 50 ° C. or less under the flow of an inert gas, and the amount of the volatile component To 2.0 wt% or less, a method for producing a dry prepolymerized catalyst for olefin polymerization. 3. The inert gas has an oxygen concentration of 20 pp.
The method for producing a dry prepolymerization catalyst for olefin polymerization according to claim 2, wherein the water content is m or less and the water content is 20 ppm or less. 4. The inert gas uses a catalyst containing 20 to 40% by weight of copper and has a temperature of 0 to 100 ° C. and a pressure of 1 to 10.
30kg / cm ² -G, GHSV is 100 ~ 2000hr
After treatment under the condition of ^-1 , using a molecular sieve,
Temperature 0 to 100 ° C, pressure 1 to 30 kg / cm ² -G,
The method for producing a dry prepolymerized catalyst for olefin polymerization according to claim 3, wherein GHSV is obtained by treating under a condition of 100 to 2000 hr ^-1 . 5. A fine particle carrier comprising (A) an oxide of at least one element selected from Group II, Group III and Group IV of the periodic table, and (B) a transition metal of Group IVB of the periodic table. When a olefin is polymerized in a gas phase while supplying a prepolymerization catalyst obtained by prepolymerizing an olefin to a solid catalyst component carrying a compound and (C) an organoaluminum oxy compound, the amount of volatile components The method for vapor phase polymerization of olefins is characterized in that the prepolymerization catalyst having a content of 2.0% by weight or less is supplied to the polymerization reactor in a solid powder state.