JPH08157515A - Olefin polymerization catalyst and method of polymerizing - Google Patents

Abstract

PURPOSE: To obtain an olefin polymer excellent in particle properties in high polymerization activity. CONSTITUTION: This catalyst is prepared by infiltrating a transition metal compound having ligands having cyclopentadienyl skeletons and an organoaluminumoxy compound into a carrier comprising an oxide of at least one element selected from among the elements of groups II, III and IV in the periodic table and having a specific surface area of 50-1000m<2> /g, a pore volume of 0.3-2.5m<3> /g, a specific strength of 0.8 or above, and a bulk density of 0.25g/cm<3> or above. This method comprises polymerizing an olefin in the presence of this catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and an olefin polymerization method, and more particularly to an olefin polymerization catalyst capable of producing an olefin polymer having high activity and excellent particle properties, and an olefin using this catalyst. The present invention relates to a polymerization method of.

[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 various molding materials. ing.

Such an olefin polymer has hitherto been obtained by a solution polymerization method, a suspension polymerization method or a gas phase polymerization method in the presence of a titanium-based solid catalyst component containing magnesium, titanium and halogen as essential components. Is produced by (co) polymerizing.

When the olefin polymerization is carried out by a gas phase polymerization method, the polymer can be obtained in the form of particles, and the step of precipitating particles or the step of separating particles after the polymerization becomes unnecessary. Therefore, it is known that the manufacturing process can be simplified and the manufacturing cost can be reduced.

In such a gas phase polymerization method, a solid catalyst and an olefin are continuously supplied to a fluidized bed reactor,
In this method, olefin is polymerized or copolymerized in a fluidized bed, and the resulting particulate polymer is continuously extracted to continuously (co) polymerize the olefin.

However, conventionally, in the gas phase polymerization method, the produced polymer locally aggregates into a polymer mass, or adheres to the wall surface of the gas phase polymerizer to form a sheet-like mass. There was something to do. When such a sheet-shaped polymer mass is formed, it accumulates on the gas dispersion plate under the fluidized bed, disturbs normal flow, or clogs the holes of the gas dispersion plate, and reacts. The operation of the system was significantly hindered, and eventually the polymerization operation was stopped.

Conventionally, the solid titanium-based catalyst components as described above have been known as catalysts capable of highly active gas phase polymerization of olefins, but in recent years, olefins (co) polymerization with higher polymerization activity have been known. As a catalyst that can be
A catalyst comprising a solid catalyst component containing a metallocene compound of Group IVB metal such as zirconium and an organoaluminum component has been developed. In order to stably carry out gas phase polymerization of olefins for a long period using such a highly active solid metallocene catalyst, it is desired that the fluidity of the fluidized bed (reaction system) is stable.

Therefore, in the presence of the metallocene catalyst,
To stably produce olefin (co) polymers with excellent particle properties such as excellent fluidity in a fluidized bed without generating polymer lumps during continuous olefin gas phase polymerization. The advent of olefin polymerization catalysts and olefin polymerization methods capable of producing olefins is desired.

Also in the suspension polymerization method, the appearance of an olefin polymerization catalyst and an olefin polymerization method capable of producing an olefin (co) polymer having excellent particle properties is desired.

As a result of intensive studies conducted by the present inventors in view of the above-mentioned prior art, a catalyst in which a transition metal compound and an organoaluminum oxy compound are supported on a specific carrier is a particle in the gas phase polymerization method. It has been found that an olefin polymer having excellent properties can be produced and that the operation stability is excellent. Further, they have found that when such a catalyst is used in suspension polymerization, it is possible to produce an olefin polymer having excellent particle properties, and have completed the present invention.

[0011]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and an olefin polymerization catalyst and a catalyst for obtaining an olefin polymer having high polymerization activity and excellent particle properties. An object of the present invention is to provide a method for polymerizing an olefin using a different catalyst.

Further, the present invention provides a catalyst for olefin polymerization which, when used in a gas phase polymerization method, gives an olefin polymer having excellent particle properties and can be stably produced for a long period of time. It is an object of the present invention to provide a method for polymerizing olefins using such a catalyst.

[0013]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention comprises (A-1) an oxide of at least one element selected from Groups II, III and IV of the Periodic Table, and (i) has a specific surface area 5
0 to 1000 m ² / g, (ii) pore volume of 0.3 to 2.5 cm ³ / g, (iii) specific strength of 0.8 or more, (iv) bulk Density is 0.25g / c
It is characterized in that (B) a transition metal compound having a coordination having a cyclopentadienyl skeleton and (C) an organoaluminum oxy compound are supported on a carrier having a size of m ³ or more.

In the present invention, the carrier (A-1) is used as a carrier.
Instead of (A-2) an oxide of at least one element selected from Groups II, III, and IV of the periodic table, (i) having an average particle size of 1
It is in the range of 0.00 to 1000 μm, and (ii) the specific strength is 0.
A carrier of 8 or more may be used, and (A-3) at least one element selected from Groups II, III and IV of the periodic table in place of the carrier (A-1). Consists of an oxide and (i) has a specific surface area of 5
0 to 1000 m ² / g, (ii) pore volume of 0.3 to 2.5 cm ³ / g, (iii) specific strength of 0.8 or more, (iv) bulk Density is 0.25g / c
m ³ or more, and (v) average particle size is 100 to 1000 μ
A carrier in the range of m may be used.

Since the catalyst for olefin polymerization according to the present invention has a specific transition metal compound and an organoaluminum oxy compound supported on a specific carrier, an olefin polymer having high polymerization activity and excellent particle properties can be obtained. It can be manufactured.

When used in suspension polymerization, the olefin polymerization catalyst according to the present invention can produce an olefin polymer having excellent particle properties. The olefin polymerization method according to the present invention is characterized by polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst.

In the present invention, it is preferable to polymerize an olefin by a continuous fluidized bed gas phase polymerization method using the above-mentioned olefin polymerization catalyst.

[0018]

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

In the present specification, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymers but also homopolymers. In some cases, it is used in the sense of including a copolymer.

The catalyst for olefin polymerization according to the present invention is a catalyst having (B) a cyclopentadienyl skeleton on a carrier made of an oxide of at least one element selected from Groups II, III and IV of the Periodic Table. And a (C) organoaluminum oxy compound is supported.

The carrier forming the olefin polymerization catalyst according to the present invention is a fine-particle inorganic compound composed of an oxide of at least one element selected from the groups II, III and IV of the periodic table.

Porous oxide as the finely divided inorganic compound
Is preferred, specifically SiO₂, Al₂O₃, Mg
O, ZrO₂, TiO₂, B₂O₃, CaO, ZnO,
BaO, ThO₂Or a mixture containing these,
For example SiO₂-MgO, SiO₂-Al₂O₃, SiO₂-
TiO₂, SiO₂-V₂O_Five, SiO₂-Cr₂O₃, Si
O₂-TiO₂-MgO etc. can be illustrated. this
Among the SiO₂, Al₂O ₃And a group consisting of Mg
The one that has at least one component selected from
preferable.

In the present invention, the carrier has a specific surface area of 5
0-1000m²/ G, preferably 100-700m²/
g, more preferably 100 to 500 m²In the range of / g
And the pore volume is 0.3-2.5 cm³/ G, preferably
Is 0.5 to 2.5 cm³/ G, more preferably 0.5 to
2.0 cm³/ G and the specific strength is 0.8 or less.
Above, preferably in the range of 0.9 to 1.0, the bulk density
But 0.25 g / cm³Or more, preferably 0.30
0.50 g / cm ³Use a carrier (A-1) in the range of
Is desirable.

In the present invention, the carrier has an average particle size of 1
It is in the range of 0 to 1000 μm, preferably 100 to 500 μm, and has a specific strength of 0.8 or more, preferably 0.9.
It is also possible to use the carrier (A-2) in the range of from 1.0 to 1.0.

In the present invention, the specific surface area is particularly used as a carrier.
But 50-1000m²/ G, preferably 100-70
0m²/ G, more preferably 100 to 500 m²/ G range
Enclosed with a pore volume of 0.3-2.5 cm³/ G, good
0.5-2.5 cm³/ G, more preferably
0.5-2.0 cm³/ G, the specific strength is
0.8 or more, preferably in the range of 0.9 to 1.0,
Bulk density is 0.25g / cm³Or more, preferably 0.3
0 to 0.50 g / cm ³And the average particle size is 1
00-1000 μm, preferably 100-500 μm
It is desirable to use a carrier (A-3) within the range.

The carrier used in the present invention satisfies the above-mentioned conditions, and the amount of adsorbed water is desirably 1.0 wt% or less, preferably 0.5 wt% or less. The amount is 1.0% by weight or more, preferably 1.5 to 4.0% by weight, more preferably 2.0 to 3.5.
It is desirable to be in the range of% by weight, and the angle of repose is 60
It is desirable that the angle is less than or equal to °, preferably in the range of 10 to 50.

Here, the amount of adsorbed water (% by weight) and the amount of surface hydroxyl groups (% by weight) are determined as follows. [Amount of adsorbed water] 4 at normal temperature and nitrogen flow at a temperature of 200 ° C
The amount of adsorbed water is defined as a percentage of the weight loss of the carrier after drying for a period of time relative to the weight of the carrier before drying. [Amount of surface hydroxyl groups] X (g) is the weight of the carrier obtained by drying at a temperature of 200 ° C under normal pressure and nitrogen flow for 4 hours.
Furthermore, the weight of the calcined product obtained by calcining the carrier at 1000 ° C. for 20 hours in which the surface hydroxyl groups have disappeared is Y (g),
Calculate by the following formula.

Amount of surface hydroxyl group (% by weight) = {(X−Y) / X} × 100 Group IVB transition metal containing a ligand having a cyclopentadienyl skeleton forming the olefin polymerization catalyst according to the present invention. Examples of the compound (B) include compounds represented by the following general formula (I).

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

X is the valence of the transition metal and represents the number of L. L represents a ligand or a group which coordinates to a transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and other than the ligand having the cyclopentadienyl skeleton. L is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO ₃ R (wherein R is a carbon atom which may have a substituent such as halogen is 1 ~ 8 hydrocarbon groups), a halogen atom, and a hydrogen atom.

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

Of these ligands having a cyclopentadienyl skeleton, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula (I) includes two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons are ethylene and propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group, and the like.

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, the alkyl group includes a methyl group, an ethyl group, Examples include propyl group, isopropyl group, butyl group, etc., examples of cycloalkyl group include cyclopentyl group, cyclohexyl group, etc., examples of aryl group include phenyl group, tolyl group, etc., and examples of aralkyl group include benzyl group. Examples thereof include a group and a neophyll group.

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

Examples of the trialkylsilyl group include a trimethylsilyl group and a triethylsilyl group. S
Examples of the ligand represented by O ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group.

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

R ¹ _k R ² _l R ³ _m R ⁴ _n M (I ') In the formula, M is a transition metal compound similar to the above. 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.

K is an integer of 1 or more, and l is 0 or 1.
, M is 0 or 1, n is 0 or 1, and k + l + m + n = 4. In the present invention, in the general formula (I ′), one of R ² , R ³ and R ⁴ is a transition metal compound which is a ligand having a cyclopentadienyl skeleton, for example, R ¹ and R ² are cyclopentadiene. A transition metal compound which is a ligand having an enyl skeleton is preferably used. Ligands having these cyclopentadienyl skeletons are alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or substituted such as dimethylsilylene, diphenylsilylene and methylphenylsilylene groups. It may be bound via a linking group such as a silylene group. In this case, R ³ and R ⁴ are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a trialkylsilyl group, SO
₃ One kind of group or atom selected from the group consisting of R, halogen atom and hydrogen atom.

Specific examples of transition metal compounds in which M is zirconium will be shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene Bis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis ( Indenyl) zirconium bis (p-toluene sulfonate), ethylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), ethylene bis (4,5,6, 7-Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride , Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethyl Silylene bis (indenyl)
Zirconium bis (trifluoromethane sulfonate),
Dimethyl silylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethyl silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenyl silylene bis (indenyl) zirconium dichloride, methylphenyl silylene bis (indenyl) zirconium dichloride , Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopenta Dienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl Benzalkonium monochloride,
Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) (Enyl) dibenzyl zirconium, bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl)
Zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis ( Dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, Bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadiene) Le) zirconium dichloride, bis (methyl-butylcyclopentadienyl) zirconium dichloride, bis (methyl-butylcyclopentadienyl)
Zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride,
Bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride and the like.

In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

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

The organoaluminum oxy compound (C) forming the olefin polymerization catalyst according to the present invention may be a conventionally known aluminoxane, and is also disclosed in JP-A-2-78.
It may be a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent No. 687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method of adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension described above and reacting the organoaluminum compound with adsorbed water or crystal water. (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 organic metal component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent or suspended in the poor solvent of the aluminoxane.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum and trisec-butyl. Aluminum, tri-tert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum and other trialkylaluminums; tricyclohexylaluminum, tricyclooctylaluminum and other tricycloalkylaluminums; dimethylaluminum chloride, diethylaluminum Chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, etc. Alkylaluminum halides; diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide; and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, trialkylaluminum is more preferable, and trimethylaluminum is particularly preferable.

Further, as the organoaluminum compound used when preparing the aluminoxane, the following general formula (I
It is also possible to use the isoprenylaluminum represented by I).

[0049] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ... (II) ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Above Such organoaluminum compounds may be used alone or in combination.

The olefin polymerization catalyst according to the present invention is a solid catalyst in which the transition metal compound (B) and the organoaluminum oxy compound (C) are supported on the carrier as described above. It may contain an aluminum compound (D).

Such an organoaluminum compound (D)
For example, an organoaluminum compound represented by the following formula (III) can be exemplified. During ^{_{R a n AlX 3-n ...}} (III) ( wherein, R ^a represents a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n represents 1
It is 3. ) In the formula (III), R ^a has 1 to 12 carbon atoms.
A hydrocarbon group of, for example, an alkyl group, a cycloalkyl group or an aryl group, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, Examples include a cyclopentyl group, a cyclohexyl group, a phenyl group and a tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-ethylhexylaluminum and tridecylaluminum; alkenylaluminums such as isoprenylaluminum; dimethylaluminum chloride, diethylaluminum chloride, diisopropyl. Dialkylaluminum halides such as aluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide; alkylaluminiums such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide. Arm sesquihalide; methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide; diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound (D), a compound represented by the following general formula (IV) can also be used. R ^a _n AlY _{3 −n} (IV) (In the formula, R ^a is the same as above, Y is a —OR ^b group,
OSiR ^c ₃ group, -OAlR ^d ₂ group, -NR ^e ₂ group, -SiR
^f ₃ group or —N (R ^g ) AlR ^h ₂ group, and n is 1 to 2
And R ^b , R ^c , R ^d and R ^h are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and a ^Re is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group. , Phenyl group, trimethylsilyl group and the like, and R ^f and R ^g are methyl group, ethyl group and the like. ) As such an organoaluminum compound, the following compounds are specifically used. (I) compounds represented by R ^a _n Al (OR ^b ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (ii) R ^a _n Al (OSiR ^c ₃ ) ₃ a compound represented by _-n , for example, Et ₂ Al (OSiMe ₃ ), (iso-B
u) ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (O
SiEt ₃ ), etc., (iii) R ^a _n Al (OAlR ^d ₂ ) _3-n
A compound represented by, for example, Et ₂ AlOAlEt ₂ ,
(Iso-Bu) ₂ AlOAl (iso-Bu) ₂ etc., (iv)
_{^{R a n Al (NR e 2}} ) a compound represented by _3-n, e.g., M
e ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNH
Et, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ Al
(V) R ^a _n Al (SiR ^f ₃ ) such as N (SiMe ₃ ) ₂
A compound represented by _3-n , for example, (iso-Bu) ₂ AlS
iMe _3, etc., such as (vi) R ^a _n Al [N (R ^g ) AlR ^h ₂ ].
A compound represented by _3-n , for example, Et ₂ AlN (Me)
AlEt ₂ , (iso-Bu) ₂ AlN (Et) Al (is
o-Bu) ₂ etc.

Among the organoaluminum compounds represented by the above general formulas (III) and (IV), the general formula R ^a ₃ Al,
Organoaluminum compounds represented by R ^a _n Al (OR ^b ) _3-n and R ^a _n Al (OAlR ^d ₂ ) _3-n can be mentioned as preferable examples, and R ^a is an isoalkyl group, and n = Two
Are particularly preferred.

The olefin polymerization catalyst according to the present invention comprises the above-mentioned carrier, transition metal compound (B) [component (B)].
And an organoaluminum oxy compound (C) [component (C)], if necessary an organoaluminum compound (D)
It can be prepared by contacting [Component (D)].

The order in which the carrier, the component (B), the component (C) and the component (D) are brought into contact with each other is arbitrarily selected, but preferably the carrier and the component (C) are mixed and brought into contact with each other, and then the component (B). ) Are mixed and contacted with each other, and if necessary, the component (D)
Are mixed and contacted.

The contact of the carrier, the component (B), the component (C) and the component (D) can be carried out in an inert hydrocarbon medium, which is a specific inert hydrocarbon medium used for preparing the catalyst. Includes aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane,
Examples thereof include alicyclic hydrocarbons such as methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

Carrier, component (B) and component (C), required
When mixing and contacting the component (D) according to
(B) is usually 5 × 10 per 1 g of the carrier.^-6~ 5 × 10^-FourMo
Le, preferably 10^-Five~ 2 x 10^-FourUsed in molar amounts
And the concentration of component (B) is about 10^-Four~ 2 x 10^-2Mol /
Liter (medium), preferably 2 × 10^-Four-10^-2Mole
/ Liter (medium). Al in ingredient (C)
Atomic ratio of aluminum and transition metal in component (B) (Al /
(Transition metal) is usually 10 to 500, preferably 20 to 2
00. A in the component (D) that is used as necessary
Luminium atom (Al _d) And aluminium in ingredient (C)
Mu atom (Al_c) Atomic ratio (Al_d/ Al_c) Is usually
0.02 to 3, preferably 0.05 to 1.5
It

The mixing temperature at the time of mixing and contacting the above components is usually -50 to 150 ° C, preferably -20 to 120.
And the contact time is 1 minute to 50 hours, preferably 10
Minutes to 25 hours.

The olefin polymerization catalyst (solid catalyst) obtained as described above contains the component (B) per 1 g of the carrier,
5 × 10 ⁻⁶ in terms of the transition metal atom in the component (B)
5 × 10 ^-4 gram atom, preferably 10 ^-5 to 2 × 10 ^-4
It is supported in an amount of gram atom, and the component (C) and the component (D) are converted into aluminum atoms in the component (C) and the component (D) in an amount of 10 ^{−3 to} 5 × 1 per 1 g of the carrier.
It is desirable to support in an amount of 0 ^-2 gram atom, preferably 2 x 10 ^-3 to 2 x 10 ^-2 gram atom.

The olefin polymerization catalyst of the present invention is prepared by preliminarily preparing an olefin in the presence of the above-mentioned carrier, the transition metal compound (B), the organoaluminum oxy compound (C) and, if necessary, the organoaluminum compound (D). It may be a prepolymerized solid catalyst obtained by polymerization.

The prepolymerization is carried out by introducing the olefin into the inert hydrocarbon medium in the presence of the carrier, the component (B) and the component (C) as described above, and optionally in the coexistence of the component (D). Can be done by. The above carrier,
The solid catalyst (component) is preferably formed from the component (B) and the component (C). In this case, in addition to the solid catalyst (component), component (C) and / or component (D) not supported on the carrier may be added. Examples of the inert hydrocarbon medium used for the preparation of the prepolymerized solid catalyst include the same ones as described above.

The olefin used in the prepolymerization is an α-olefin having 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene. , 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and the like. Among these, ethylene or a combination of ethylene and an α-olefin used in the polymerization is particularly preferable.

In the prepolymerization, the above component (B) is
It is usually 10 ⁻⁶ to when converted to the transition metal atom in the component (B).
2 × 10 ^-2 mol / liter (medium), preferably 5 × 1
Used in an amount of 0 ^-5 to 10 ^-2 mol / liter (medium),
The component (B) is usually 5 × 10 ^{−6 to} 5 × 10 per 1 g of the carrier.
^-4 mol, preferably used in an amount of 10 ^-5 to 2 × 10 ^-4 mol. The atomic ratio of the aluminum in the component (C) to the transition metal in the component (B) (Al / transition metal) is usually 10 to 10.
It is 500, preferably 20 to 200. Aluminum atom (Al _d ) in component (D) used as necessary
The atomic ratio (Al _d / Al _c ) of aluminum atoms (Al _c ) in the component (C) is usually 0.02 to 3, preferably 0.05 to 1.5.

The prepolymerization temperature is -20 to 80 ° C, preferably 0 to 60 ° C, and the prepolymerization time is 0.5 to 10 ° C.
It is 0 hours, preferably about 1 to 50 hours. The olefin polymer produced by the prepolymerization is 0.1 to 1 g of the carrier.
It is desirable that the amount is 500 g, preferably 0.2 to 300 g, and more preferably 0.5 to 200 g. Also,
The prepolymerized solid catalyst is the component (B) per 1 g of the carrier.
Is about 5 × 1 in terms of the transition metal atom in the component (B).
0 ^{−6 to} 5 × 10 ⁻⁴ gram atom, preferably 10 ⁻⁵ to 2 ×
The component (C) and the component (D) are supported in an amount of 10 ⁻⁴ gram atom, and the component (C) and the component (D) are aluminum atoms (Al) and the component (B) is a transition metal atom. It is desirable that the carrier is supported in an amount of 5 to 200, preferably 10 to 150 in terms of molar ratio (Al / M) to (M).

The prepolymerization can be carried out batchwise or continuously, and can be carried out under reduced pressure, normal pressure or under pressure. In the prepolymerization,
Producing a prepolymer having an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.2 to 7 dl / g, preferably 0.5 to 5 dl / g, in the presence of hydrogen. Is desirable.

The prepolymerized solid catalyst has a bulk density of
0.25 g / cm ³ or more, preferably 0.3 to 0.5 g
/ Cm ³ , and the average particle size is 100 to 80,0.
00 μm, preferably in the range of 100 to 50,000 μm, and the angle of repose is 70 ° or less, preferably 30 to 60.
It is desirable to be in the range of °.

The catalyst for olefin polymerization according to the present invention may contain other components useful for olefin polymerization in addition to the above components. Hereinafter, the term "solid catalyst" may be used to include a prepolymerized solid catalyst.

In the present invention, an olefin is polymerized using the above-mentioned olefin polymerization catalyst (solid catalyst).
When carrying out the polymerization of olefins, the catalyst for olefin polymerization is usually 10 ^-8 to 10 ^-3 gram atom, preferably 10 ^-7 to 10 ^-4 in terms of the transition metal atom in the catalyst per 1 liter of the polymerization volume. It is preferably used in amounts of gram atoms.

Further, in the polymerization, in addition to the organoaluminum oxy compound [component (C)] and the organoaluminum compound [component (D)] supported on the carrier, the organoaluminum oxy compound and / or the organic aluminum oxy compound and / or the organic aluminum oxy compound not supported are further added. An aluminum compound may be used. At this time, the atomic ratio between the aluminum atom (Al) in the unsupported organoaluminum oxy compound and / or the organoaluminum compound and the transition metal atom (M) in the transition metal compound (B) supported on the carrier. (Al / M)
Is in the range of 5 to 300, preferably 10 to 200, and more preferably 15 to 150.

As olefins which can be polymerized by such an olefin polymerization catalyst, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1- Α-olefins having 2 to 20 carbon atoms such as pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene , Cyclopentene, cycloheptene, norbornene, 5-methyl
-2-norbornene, tetracyclododecene, 2-methyl 1,
Cycloolefins having 3 to 20 carbon atoms such as 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene can be mentioned. Further, styrene, vinylcyclohexane, diene and the like can be used.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method.
In the liquid phase polymerization method, the same inert hydrocarbon medium as used in the preparation of the solid catalyst can be used, and the olefin itself can also be used as the medium.

The polymerization temperature of the olefin in the liquid phase polymerization method is usually -50 to 150 ° C, preferably 0 to 100 ° C. Polymerization pressure is usually normal pressure to 100 kg / cm
² , preferably under normal pressure to 50 kg / cm ² .

The polymerization reaction can be carried out by any of a batch system, a semi-continuous system and a continuous system. It is also possible to carry out the polymerization in two or more stages under different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.

By carrying out suspension polymerization using the olefin polymerization catalyst according to the present invention as described above, an olefin polymer having high polymerization activity and excellent particle properties can be produced. Further, when suspension polymerization is carried out using a catalyst for olefin polymerization in which a catalyst component is supported on a carrier having an average particle size in the range of 100 to 1000 μm, a polymer having a large particle size is obtained. Such a polymer having a large particle size is easy to handle, and in some cases, pelletizing is unnecessary.

The polymerization temperature of the olefin in the suspension polymerization method is usually -50 to 150 ° C, preferably 0 to 100 ° C. Polymerization pressure is usually normal pressure to 100 kg / cm
² , preferably under normal pressure to 50 kg / cm ² .

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

Here, the olefin polymerization method by the continuous fluidized bed gas phase polymerization method will be described with reference to FIG. The olefin polymerization catalyst (solid catalyst) 1 as described above is continuously supplied to the fluidized bed reactor 3 from, for example, a line 2. Gaseous olefins, non-polymerizable hydrocarbons, etc. are continuously supplied from, for example, a line 9, and a circulating gas blower 7 is provided via a circulation line 6 from below the fluidized bed reactor 3 to a gas dispersion plate 4 such as a porous plate. Is blown through.
As a result, the fluidized bed (reaction system) 5 is kept in a fluidized state.

The olefin blown into the fluidized bed 5 in which the solid catalyst 1 is kept in a fluidized state undergoes a polymerization reaction here to produce polymer particles [olefin (co) polymer].
Is generated. The produced polymer particles are continuously withdrawn from the fluidized bed reactor 3 via the line 11. Unreacted gaseous olefins, non-polymerizable hydrocarbons, etc. that have passed through the fluidized bed 5 are decelerated in the deceleration region 3a provided above the fluidized bed reactor 3 and discharged to the outside of the fluidized bed reactor 3 to generate heat. The heat of polymerization is removed in the exchanger 8 and is circulated again through the circulation line 6 to the fluidized bed 5.

The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature. By carrying out gas phase polymerization using the above-mentioned olefin polymerization catalyst, an olefin polymer having high polymerization activity and excellent particle properties can be produced. The average particle size is 100 to 1000.
When the gas phase polymerization is carried out using an olefin polymerization catalyst in which a catalyst component is supported on a carrier having a range of μm, a polymer having a large particle size is obtained. Such a polymer having a large particle size is easy to handle, and in some cases, pelletizing is unnecessary.

Since the olefin polymerization catalyst of the present invention has excellent fluidity, it can be smoothly supplied to the reactor. Further, the generated polymer is locally agglomerated into a polymer lump, or is less likely to adhere and agglomerate to the wall surface of the polymerization vessel to form a sheet-like lump, which is excellent in operation stability and for a long time. Continuous operation becomes possible.

Further, the average particle diameter is 100 to 1000 μm.
When an olefin polymerization catalyst in which a catalyst component is carried on a carrier in the range of m is used, it is possible to operate at a high gas linear velocity, so that the heat removal effect is enhanced and the productivity is improved.

[0083]

The olefin polymerization catalyst according to the present invention is
Since the specific transition metal compound and the organoaluminum oxy compound are supported on the specific carrier, an olefin polymer having high polymerization activity and excellent particle properties can be produced.

Since the olefin polymerization method according to the present invention uses the above-mentioned olefin polymerization catalyst,
It is possible to produce an olefin polymer having high polymerization activity and excellent particle properties.

[0085]

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

[0086]

Example 1 Preparation of solid catalyst Silica dried at 250 ° C. for 10 hours (specific surface area: 324)
m ² / g, average particle size; 235 μm, pore volume; 1.04
cm ³ / g, specific strength; 0.95, bulk density; 0.35 g /
cm ³ , adsorbed water amount; 0.1% by weight, surface hydroxyl group amount;
(69% by weight) was suspended in 154 liters of toluene, and then cooled to 0 ° C. Then, 50.5 liters of a toluene solution of methylaluminoxane (1.52 mol / liter in terms of Al atom) was added dropwise over 1 hour.
At this time, the temperature in the system was kept in the range of 0 to 5 ° C. Continue to react at 0 ° C for 30 minutes, then 95 hours over 95 hours
The temperature was raised to 0 ° C., and the reaction was carried out at that temperature for 4 hours. afterwards,
The temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. 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. Into this system, a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (25.
22 liters (7 mmol / liter) were added dropwise at 80 ° C. over 30 minutes, and further reacted 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.

[0087] was charged with solid catalyst component 7.0kg and hexane to the reactor 350 liters of prepolymerized thoroughly purged with nitrogen, the total volume 285
I made it to liters. After cooling the system to 10 ° C., ethylene was blown into hexane at a flow rate of 8 N-m ³ / hr for 5 minutes. During this time, the temperature in the system was maintained at 10 to 15 ° C. After that, the supply of ethylene was stopped, 2.4 liters of triisobutylaluminum and 1.2 kg of 1-hexene were added.
Charged. After making the system a closed system, the supply of ethylene was restarted at a flow rate of 8 N-m ³ / hr. After 15 minutes, the flow rate of ethylene was reduced to 2 N-m ³ / hr and the pressure in the system was 0.8 kg.
/ Cm ² -G. During this time, the temperature in the system rose to 35 ° C. Then, ethylene was supplied at a flow rate of 4 N-m ³ / hr for 3.5 hours while adjusting the temperature in the system to 32 to 35 ° C. During this time, the pressure in the system is 0.7 to 0.8 kg / c.
It was held at m ² -G. Next, the system was replaced with nitrogen, the supernatant was removed, and the system was washed twice with hexane. In this way, a prepolymerized solid catalyst in which 3 g of the polymer was prepolymerized per 1 g of the solid catalyst was obtained.
The intrinsic viscosity [η] of this prepolymerized polymer is 2.1 dl /
and the content of 1-hexene was 4.8% by weight.

The supernatant liquid after the prepolymerization was colorless and transparent, and the prepolymerized solid catalyst had a good shape and had a bulk specific gravity of 0.40 g / cm ³ . Polymerization Continuous type fluidized bed gas phase polymerizer, total pressure 20kg / cm
Copolymerization of ethylene and 1-hexene was carried out at ^2- G, a polymerization temperature of 85 ° C, and a gas linear velocity of 0.7 m / sec. The pre-polymerized solid catalyst prepared above is dried and continuously fed at a rate of 60 g / hr, and ethylene, 1-hexene, hydrogen and nitrogen are continuously supplied to maintain a constant gas composition during the polymerization. Supplied (gas composition; 1-hexene / ethylene = 0.025,
Hydrogen / ethylene = 1.5 × 10 ⁻⁴ , ethylene concentration; 71
%).

The yield of the obtained ethylene / 1-hexene copolymer was 80 kg / hr, and the density of the copolymer was 0.9.
15 g / cm ³ and a melt flow rate of 0.61
g / 10 minutes, and the bulk density of the copolymer particles is 0.44 g /
cm ³ , the average particle size is 1050 μm, and 100
The proportion of finely divided polymer having a particle size of μm or less was 0.1% by weight or less.

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

[0091]

Example 2 Preparation of solid catalyst Silica (average particle size; 247 μm, specific surface area; 352) dried at 250 ° C. for 10 hours in a reactor which was sufficiently purged with nitrogen.
m ² / g, pore volume; 1.12 cm ³ / g, specific strength;
0.93, bulk density; 0.37 g / cm ³ , adsorbed water amount;
0.1% by weight, surface hydroxyl group amount; 2.77% by weight) 8.4
g, and after suspending with 130 ml of toluene,
Cooled to 0 ° C. Then, a toluene solution of methylaluminoxane (1.54 mol / liter in terms of Al atom)
41.7 ml was added dropwise in 20 minutes. At this time, the temperature in the system was kept at 0 ° C. Subsequently, the mixture was reacted at 0 ° C for 30 minutes, then heated to 95 ° C over 1 hour, and reacted at that temperature for 4 hours. Then, the temperature was lowered to 60 ° C., and the supernatant was removed by the decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in toluene to a total volume of 150 ml.

50 of the suspension thus obtained
ml was transferred to another reactor and 10 m of toluene was put into the system.
and 3.5 ml of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (35.4 mmol / liter in terms of Zr atom) were added. Then, the temperature was raised to 80 ° C., and the reaction was further performed at 80 ° C. for 2 hours. Then, the supernatant liquid was removed and washed twice with hexane to obtain a solid catalyst component containing 3.0 mg of zirconium per 1 g.

[0093] The total volume of 125ml The solid catalyst component obtained in the preliminary polymerization described above and resuspended in hexane, (1 mol / l in terms of Al atom) decane solution of triisobutyl aluminum in the suspension 6. 2 ml and 1-hexene 0.5 ml were added (room temperature). Then, while continuously supplying ethylene into the system, prepolymerization was carried out at 35 ° C. for 3.5 hours under normal pressure.
Then, by washing twice with hexane, a prepolymerized solid catalyst was obtained. At this time, no adhesion of the prepolymerized solid catalyst to the reactor wall was observed.

Polymerization 1 liter of hexane and 40 parts of 1-hexene were placed in a stainless steel autoclave having an internal volume of 2 liters, which had been sufficiently replaced with nitrogen.
ml and 0.75 ml of a decane solution of triisobutylaluminum (1 mol / liter in terms of Al atom) were charged, and the temperature inside the system was raised to 70 ° C. Next, 0.005 milligram atom in terms of zirconium atom of the pre-polymerized solid catalyst obtained above was introduced together with ethylene,
Polymerization started. The temperature in the system immediately rose to 80 ° C. After that, while continuously supplying ethylene, the total pressure is 8
Polymerization was carried out at 80 ° C. for 3 hours while maintaining kg / cm ² -G.

The yield of the ethylene / 1-hexene copolymer obtained was 313 g, and the density of the copolymer was 0.927 g.
/ Cm ³ , and the melt flow rate is 0.18 g / 10
And the bulk density of the copolymer particles is 0.41 g / cm ³
And the average particle size was 1470 μm. After the reaction was completed, there was no attached polymer on the side wall of the reaction vessel.

[0096]

Comparative Example 1 The silica used as the carrier in Example 1 has an average particle size of 24 μm and a specific surface area of 298 m ² /
g, pore volume; 1.03 cm ³ / g, specific strength; 0.9
0, bulk density; 0.29 g / cm ³ , adsorbed water amount; 0.1% by weight, surface hydroxyl group amount; 2.38% by weight, except that silica was used to prepare a solid catalyst. And a prepolymerized solid catalyst was prepared.

Polymerization was carried out in the same manner as in Example 1 using a continuous type fluidized bed gas phase polymerization apparatus using the prepolymerized solid catalyst obtained above. As the support of some thermometers installed in the reactor gradually increased, the operation was stopped and the inside of the polymerization equipment was inspected. The produced polymer adhered and aggregated on the walls of the fluidized bed and the circulation line to form a sheet-like lump.

[Brief description of drawings]

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

FIG. 2 is an explanatory diagram showing a gas phase polymerization process of an olefin using a fluidized bed reactor.

Claims (5)

[Claims] 1. An (A-1) oxide of at least one element selected from Groups II, III and IV of the periodic table, (i)
The specific surface area is in the range of 50 to 1000 m ² / g, and (i
A carrier having i) a pore volume in the range of 0.3 to 2.5 cm ³ / g, (iii) a specific strength of 0.8 or more, and (iv) a bulk density of 0.25 g / cm ³ or more. An olefin polymerization catalyst comprising: (B) a transition metal compound having a coordination having a cyclopentadienyl skeleton and (C) an organoaluminum oxy compound. (A-2) An oxide of at least one element selected from Groups II, III, and IV of the periodic table, (i)
An average particle size in the range of 100 to 1000 μm, (ii)
An olefin characterized in that (B) a transition metal compound having a coordination having a cyclopentadienyl skeleton and (C) an organoaluminumoxy compound are supported on a carrier having a specific strength of 0.8 or more. Polymerization catalyst. (A-3) An oxide of at least one element selected from Groups II, III and IV of the periodic table, (i)
The specific surface area is in the range of 50 to 1000 m ² / g, and (i
i) the pore volume is in the range of 0.3 to 2.5 cm ³ / g, (iii) the specific strength is 0.8 or more, (iv) the bulk density is 0.25 g / cm ³ or more, (V) Average particle size is 1
For olefin polymerization, characterized in that (B) a transition metal compound having a coordination having a cyclopentadienyl skeleton and (C) an organoaluminum oxy compound are supported on a carrier having a range of from 00 to 1000 μm. catalyst. 4. A method for polymerizing an olefin, which comprises polymerizing an olefin in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 3. 5. A method for polymerizing an olefin, which comprises polymerizing an olefin by a continuous fluidized bed gas phase polymerization method in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 3.