JP2001048912A - Production of prepolymerization catalyst for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a prepolymerization catalyst for olefin polymerization resistant to the lowering of the polymerization activity, having excellent catalyst fluidity in polymerization and stably usable for polymerization over a long period. SOLUTION: Prepolymerization of 7-50 g of an olefin per 1 g of a solid catalyst component A for olefin polymerization can be carried out by prepolymerizing 0.5-6 g of an olefin based on 1 g of a solid catalyst component A for olefin polymerization to obtain a prepolymerization catalyst component B, bringing the component B into contact with an antistatic agent C and again carrying out the prepolymerization of the olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a prepolymerized catalyst component for olefin polymerization, and more particularly to a method for producing a highly active prepolymerized catalyst having a large amount of prepolymerized and carrying an antistatic agent. . The prepolymerization catalyst component provided in the present invention can suppress the decrease in polymerization activity, have excellent catalyst fluidity during polymerization, and can be stably used for polymerization for a long period of time.

[0001]

BACKGROUND OF THE INVENTION Conventionally, olefin polymers such as polyethylene, polypropylene, ethylene / α-olefin copolymer, and propylene / α-olefin copolymer have been prepared from metallocene compounds of Group 4 metals such as zirconium. It is produced by (co) polymerizing an olefin in the presence of a metallocene-based solid catalyst comprising a solid catalyst containing an organic aluminum component.

When an olefin is subjected to gas-phase polymerization using a fluidized-bed reactor in the presence of the above-mentioned metallocene-based solid catalyst, polymer lumps, sheet-like substances, etc. are generated in the fluidized bed, , The mixing state in the fluidized bed becomes non-uniform, and it may not be possible to stably operate continuously for a long period of time.

When slurry polymerization is carried out in the presence of a metallocene-based solid catalyst as described above, polymer lumps and sheet-like substances are generated in the polymerization vessel, and the polymer adheres to the stirring blades and is stable for a long time. In some cases, continuous operation could not be performed.

[0004] Further, the solid catalyst as described above often has low fluidity, which makes it difficult to supply it to a polymerization reactor.

[0005] The present inventors have conducted studies in view of such prior art, and as a result, have found that a solid catalyst in which a specific surfactant is supported can reduce the above-mentioned problems, and have achieved the present invention. It was completed.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above prior art, and has a high polymerization activity, excellent fluidity, and a solid catalyst for olefin polymerization which does not easily generate a heat spot during polymerization. The purpose of the present invention is to provide a manufacturing method.

[0007]

SUMMARY OF THE INVENTION The present invention relates to a prepolymerized catalyst component (B) obtained by prepolymerizing 0.5 to 6 g of olefin per 1 g of a solid catalyst component for olefin polymerization (A).
After contacting the antistatic agent (C), the olefin is prepolymerized again to prepolymerize 7 to 500 g of olefin per 1 g of the solid catalyst component for olefin polymerization (A). This is a method for producing a polymerization catalyst.

In the solid catalyst for olefin polymerization according to the present invention, the catalyst component (A) for olefin polymerization comprises (A-1) a transition metal compound belonging to Group 4 of the periodic table having a cyclopentadienyl skeleton; It is preferable that the catalyst component is a) an organoaluminum oxy compound and (A-3) a particulate carrier.

The solid catalyst for olefin polymerization according to the present invention is excellent in fluidity, hardly generates heat spots during polymerization, can prevent sheeting and generation of polymer lumps, and stably converts olefins over a long period of time. Can be polymerized.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing a solid catalyst for olefin polymerization according to the present invention will be specifically described.

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

According to the present invention, an antistatic agent (C) is brought into contact with a prepolymerized catalyst component (B) obtained by prepolymerizing 0.5 to 6 g of olefin per 1 g of a solid catalyst component for olefin polymerization (A). And then preliminarily polymerizing the olefin again to prepolymerize 7 to 500 g of the olefin per 1 g of the solid catalyst component (A) for olefin polymerization.

Hereinafter, first, each component forming the solid catalyst for olefin polymerization according to the present invention will be described. (A) Catalyst Component for Olefin Polymerization As the catalyst component for olefin polymerization (A), Periodic Table 3
A catalyst component containing a compound of a transition metal selected from Group 4 to Group 12; a metallocene catalyst component of a carrier supported type in which a metallocene compound of a transition metal selected from Group 4 of the periodic table is supported on a particulate carrier; Examples include a solid titanium-based catalyst component comprising a solid titanium catalyst component and an organoaluminum compound, and a so-called Phillips catalyst component in which an arbitrary chromium compound capable of being oxidized to chromium trioxide is supported on an inorganic oxide solid such as silica. Is done. Among them, a metallocene catalyst component of a carrier-carrying type is preferable, and in particular, (A-1) a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl skeleton, and (A-2) an organic aluminum oxy compound And a carrier-supported metallocene-based catalyst component comprising (A-3) a particulate carrier. Next, each component forming the carrier-supported metallocene catalyst preferably used in the present invention will be described. (A-1) Transition metal compound (A-1) As the transition metal compound belonging to Group 4 of the periodic table having a cyclopentadienyl skeleton, a compound represented by the following general formula (I) can be exemplified.

ML _X (I) In the formula, M is a transition metal of Group 4 of the periodic table, specifically, zirconium, titanium or hafnium.

L is a ligand (group) that coordinates to the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and a ligand having a cyclopentadienyl skeleton. the L other than the child, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, trialkylsilyl group, -SO ₃ R (wherein, R is substituted such as a halogen And a hydrocarbon group having 1 to 8 carbon atoms.) Or a hydrogen atom.

X is the valence of the transition metal, and indicates the number of L. Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group; a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, a tetramethylcyclopentadienyl group, Methylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl Groups, alkyl-substituted cyclopentadienyl groups such as hexylcyclopentadienyl group; indenyl group; 4,5,6,
7-tetrahydroindenyl group; fluorenyl group and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among the ligands that coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferred. When the compound represented by the general formula (I) contains two or more groups having a cyclopentadienyl skeleton, two of the groups having a cyclopentadienyl skeleton are alkylene groups such as ethylene and propylene; It may be bonded through an alkylidene group such as isopropylidene or diphenylmethylene; a silylene group; a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group. Further, the groups having two or more cyclopentadienyl skeletons are preferably the same.

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

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

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

When the valence of the transition metal is 4, for example, the compound represented by the general formula (I) is more specifically represented by the following general formula (I '). R ¹ R ² R ³ R ⁴ M (I ′) (wherein M is zirconium, titanium or hafnium, R ¹ is a group having a cyclopentadienyl skeleton, and R ² , R ³ and R ⁴ may be the same or different from each other, a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, -SO ₃ R or a hydrogen atom.) In the present invention, R ² ,
A transition metal compound in which one of R ³ and R ⁴ is a group having a cyclopentadienyl skeleton, for example, R ¹ and R
^A transition metal compound in which ² is a group having a cyclopentadienyl skeleton is preferably used. In this case, these groups having a cyclopentadienyl skeleton are an alkylene group,
It may be bonded via a substituted alkylene group, an alkylidene group, a silylene group, a substituted silylene group, or the like. Also,
R ³ and R ⁴ represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, —SO ₃ R
Or a hydrogen atom.

Specific examples of the transition metal compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato), bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dichloride, Ethylene bis (indenyl) zirconium dibromide, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) zirconium bis (methanesulfonate), ethylene bis (Indenyl) zirconium bis (p-toluenesulfonate), ethylenebis (indenyl) zirconium bis (trifluoromethanesulfonate). Ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride. Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride , Dimethylsilylenebis (indenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconiumbis (trifluoromethanesulfonato), rac-dimethylsilylenebis {1- (2-methyl-4,5-acenaphthocyclopentadienyl)} Zirconium dichloride, rac-dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride, rac-dimethylsilylenebis {1- (2-methyl-4-isopropyl) -7-methylindenyl)｝ zirconium dichloride, rac-dimethylsilylenebis ｛1- (2-methyl-4-phenylindenyl)｝ zirconium dichloride, rac-dimethylsilylenebis ｛1- (2-
Methylindenyl) zirconium dichloride, dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride,
Diphenylsilylenebis (indenyl) zirconium dichloride, methylphenylsilylenebis (indenyl)
Zirconium dichloride. Bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride,
Bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (Cyclopentadienyl) methyl zirconium monohydride, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) dibenzyl zirconium. Bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxychloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluene Sulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) Zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (meth Ruethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopenta Dienyl) 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 and the like.

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

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

(A-2) Organoaluminum oxy compound (A-2) As the organoaluminum oxy compound, specifically, a conventionally known aluminoxane may be used, and it is disclosed in JP-A-2-276807. Such a benzene-insoluble organic aluminum oxy compound may be used.

A conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method in which an organoaluminum compound such as a trialkylaluminum is added to a hydrocarbon medium suspension of the above, and the organoaluminum compound is reacted with adsorbed water or crystal water.

(2) A method in which water, ice or steam 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 aluminoxane solution by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, and tri-n-aluminum.
Trialkylaluminum such as butylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; tricyclohexylaluminum, tricyclooctylaluminum Tricycloalkyl aluminum. Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and diisobutylaluminum chloride; dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride. Dialkylaluminum alkoxides such as dimethylaluminum methoxide and diethylaluminum ethoxide; and dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkyl aluminum and tricycloalkyl aluminum are particularly preferred. Further, as the organoaluminum compound, represented by the following general formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z (x, y, z are each a positive number, the z ≧ 2x) Isoprenyl aluminum can also be used.

The organoaluminum compound as described above is
Used alone or in combination. As the solvent used in the preparation of the aluminoxane, benzene, toluene, xylene, cumene, aromatic hydrocarbons such as cymene,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum distillates such as gasoline, kerosene and light oil And hydrocarbon solvents such as halides of the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorinated products and brominated products. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

(A-3) Particulate carrier (A-3) Specific examples of the particulate carrier include SiO ₂ , Al ₂
O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO,
ZnO, BaO, ThO _{2 and the} like, or a mixture containing them, for example, SiO ₂ —MgO, SiO ₂ —Al ₂ O
₃ , SiO ₂ —TiO ₂ , SiO ₂ —V ₂ O ₅ , SiO ₂ —C
inorganic carriers such as r ₂ O ₃ , SiO ₂ —TiO ₂ —MgO, or polyethylene, polypropylene, poly 1-butene,
Organic carriers such as poly 4-methyl-1-pentene and styrene-divinylbenzene copolymer can be mentioned.

It is desirable that the fine particle carrier (A-3) has an average particle diameter in the range of 1 to 300 μm, preferably 10 to 200 μm.

(C) Antistatic Agent The antistatic agent (C) is not particularly limited, but it is preferred to prevent a decrease in polymerization activity and to provide excellent catalyst fluidity during polymerization.
Among them, nonionic surfactants are preferred. As such nonionic surfactants, (C-1) polyalkylene oxide block (C-2) higher aliphatic amide (C-3) polyalkylene oxide (C-4) polyalkylene oxide alkyl ether (C -5) Alkyl diethanolamine, among which (C-
4) is particularly preferred. Hereinafter, each surfactant will be described.

[0036](C-1) polyalkylene oxide block (C-1) polyalkylene oxide used in the present invention
Locks are commonly used as nonionic surfactants.
And a conventionally known polyalkylene oxide
Blocks can be used without any restrictions. Polyalkyl
As the lenoxide block, the general formula HO- (C
H_TwoCH_TwoO) _m− ｛CH_TwoCH (CH_Three) O｝_n− (CH_Two
CH_TwoO)_pPolyethylene oxide represented by H 2
Lipropylene oxide-polyethylene oxide blow
Are preferred. In the above general formula (CH_TwoCH_Two
O) represents the average chain length of oxyethylene units represented by
m is 1 to 30, preferably 1 to 20, more preferably
Desirably, it is in the range of 1 to 10, and p is 1 to 3.
0, preferably 1-20, more preferably 1-10.
｛CH_TwoCH (CH_Three) O｝
N representing the average chain length of the represented oxypropylene units
Is 2 to 50, preferably 3 to 45, more preferably 4
It is desirably in the range of ~ 40. Also, polyalkyl
As suitable as a lenoxide block, general
Formula HO- ｛CH_TwoCH (CH_Three) O｝_a− (CH_TwoCH_Two
O)_b− ｛CH_TwoCH (CH_Three) O｝_cPoly represented by H
Propylene oxide-polyethylene oxide-poly
A propylene oxide block. General above
Where (CH_TwoCH_TwoO) of the oxyethylene unit represented by
B indicating the average chain length is 1 to 30, preferably 1 to 2
5, more preferably in the range of 2 to 20.
｛CH_TwoCH (CH_Three) Oxypropyl represented by O｝
A indicating the average chain length of the len unit is 2 to 30, preferably
Is in the range of 3 to 25, more preferably 4 to 20
Is desirable, c is 2 to 30, preferably 3 to 25, and
More preferably, it is desirable to be in the range of 4 to 20.

(C-2) Higher aliphatic amide (C-2) The higher aliphatic amide used in the present invention is generally used as a nonionic surfactant,
Any conventionally known higher aliphatic amide can be used without any limitation. As the higher aliphatic amide, a compound represented by the general formula (C _m H
_2m + 1 CO) N (alkyl diethanolamide represented by CH ₂ CH ₂ OH) ₂ is preferably used. M representing the number of carbon atoms of the alkyl group represented by (C _m H _{2m + 1} ) in the above general formula is preferably in the range of 1 to 30, preferably 6 to 20, and more preferably 8 to 18. . Specific examples of the higher aliphatic amide include lauryl diethanolamide, cetyl diethanolamide, stearyl diethanolamide, octyl diethanolamide, nonyl diethanolamide, sec-lauryl diethanolamide, and the like. Of these, lauryl diethanolamide is preferred.

[0038](C-3) polyalkylene oxide (C-3) polyalkylene oxide used in the present invention
Is any known polyalkylene oxide
Can be used without restrictions. As polyalkylene oxide
Preferred is HO- (CH_TwoCH_TwoO) _m-H
Polyethylene oxide and HO-CH_Two
CH (CH_Three) O｝_nPolypropylene oxa represented by H
Id. Average of the above polyethylene oxide
M indicating the degree of polymerization is 2 to 30, preferably 3 to 20, and
More preferably, it is preferably in the range of 4 to 8,
N indicating the average degree of polymerization of propylene oxide is 2 to 8
0, preferably 3 to 50, more preferably 4 to 40.
It is desirable that it is an enclosure. Polyalkylene oxide and
The above-mentioned polyethylene oxide and polypropylene
Other than oxides, for example, ethylene oxide and
Polyal randomly copolymerized with propylene oxide
Cylene oxide is also preferably used. Also, Polya
Glyceryl is preferred as a preferred alkylene oxide.
, Trimethylolpropane, and other polyhydric alcohols
Obtained by adding an alkylene oxide to
Alkylene polyols are exemplified. Polyoxyalkyl
As the len polyol, a monofunctional group of polyhydric alcohols
Ethylene oxide is preferably 2 to 30 moles, more preferably
Or 3 to 20 mol, more preferably 4 to 8 mol.
Or the number of functional groups of polyhydric alcohols
2-30 moles, preferably 3 moles, of propylene oxide
To 20 mol, more preferably 4 to 8 mol
desirable.

(C-4) Polyalkylene oxide alkyl
Ether The (C-4) polyalkylene oxide alkyl ether used in the present invention is generally used as a nonionic surfactant, and can be used without any limitation as long as it is a conventionally known polyalkylene oxide alkyl ether. . As examples of suitable polyalkylene oxide alkyl _{ether, - (CH 2 CH 2 O} ) n H or _{- {CH 2 CH (CH 3} ) O} n H ( where, n is 2-3
0), and specifically,
The following compounds can be exemplified.

General formula C _m H _{2m + 1} O (CH ₂ CH ₂ O) _n H
A polyoxyethylene alkyl ether represented by the general formula C _m H _{2m + 1} O ｛CH ₂ CH (CH ₃ ) O｝ _n H; a polyoxypropylene alkyl ether represented by the general formula C _m H _{2 m + 1} Polyoxyethylene alkylphenyl ether represented by C ₆ H ₄ O (CH ₂ CH ₂ O) _n H, general formula C _m H _{2m + 1} C ₆ H ₄ O ｛CH ₂ CH (CH ₃ ) O｝ _n H
A polyoxypropylene alkylphenyl ether represented by the general formula (C _m H _{2m + 1} ) ₂ CHO (CH ₂ CH ₂ O)
polyoxyethylene sec-alkyl ether represented by _n H, a general formula (C _m H _{2m + 1} ) ₂ CHO ｛CH ₂ CH (C
H ₃₎ O} polyoxypropylene sec- alkyl ether represented by _n H, the general formula _{(C m H 2m + 1)} 3 CO (CH 2
Polyoxyethylene tert-alkyl ether represented by CH ₂ O) _n H; polyoxypropylene tert represented by the general formula (C _m H _{2m + 1} ) ₃ CO ｛CH ₂ CH (CH ₃ ) O｝ _n H -Alkyl ether.

In the above general formula, _m representing the number of carbon atoms of the alkyl group represented by (C _m H _{2m + 1} ) is preferably 1 to 30, preferably 6 to 20, and more preferably 8 to 18. . Further, n indicating an average chain length of oxyethylene units represented by (CH ₂ CH ₂ O), and ｛CH ₂ CH (C
N representing the average chain length of the oxypropylene unit represented by H ₃ ) O} is preferably 2 to 30, preferably 3 to 20, and more preferably 4 to 10.

Among the ether compounds represented by the above general formula, polyoxyethylene lauryl ether,
Polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl phenyl ether,
Polyoxyethylene sec-lauryl ether and the like are preferable, and among these compounds, compounds in which the number of repeating oxyethylene units is 4 to 10 are particularly preferable.

(C-5) Alkyldiethanolamine (C-5) Alkyldiethanolamine used in the present invention is generally used as a nonionic surfactant, and is not limited as long as it is a conventionally known alkyldiethanolamine. Can be used without.

Examples of the alkyldiethanolamine include those represented by the general formula (C _m H _{2m + 1} ) N (CH ₂ CH ₂ OH) ₂ . In the above general formula, _m representing the number of carbon atoms of the alkyl group represented by (C _m H _{2m + 1} ) is 1 to 30,
Preferably, it is in the range of 6 to 20, more preferably 8 to 18. Specific examples of the alkyldiethanolamine include lauryldiethanolamine, cetyldiethanolamine, stearyldiethanolamine, octyldiethanolamine, nonyldiethanolamine, and sec-lauryldiethanolamine. Of these, lauryl diethanolamine is preferred.

The olefin polymerization prepolymerization catalyst component provided by the present invention contains the olefin polymerization catalyst component (A) and the surfactant (C) as essential components. Accordingly, the composition may further contain an organoaluminum compound (D). As the organoaluminum compound (D), one or two as required from the above-mentioned (A-2) organoaluminum oxy compounds, among which, as required, the organoaluminum compounds used as raw materials in preparing conventionally known aluminoxanes The above is used. In the method for producing a prepolymerization catalyst for olefin polymerization according to the present invention, the prepolymerization is performed by first supplying the olefin polymerization solid catalyst component (A) with an olefin in the presence of an inert hydrocarbon solvent. Examples of the olefin include α-olefins such as ethylene and propylene.
Among them, ethylene is preferred. Prepolymerized catalyst component (B) obtained by prepolymerizing 0.5 to 6 g of olefin per 1 g of solid catalyst component for olefin polymerization (A)
, After contacting the antistatic agent (C) with the olefin, the olefin is preliminarily polymerized again, so that it is usually 7 to 500 g, preferably 7.5 to 300 g, particularly preferably 1 g per gram of the solid catalyst component (A) for olefin polymerization. By pre-polymerizing 8 to 50 g of olefin, a pre-polymerization catalyst for olefin polymerization can be obtained. By prepolymerizing 7 to 500 g of olefin per 1 g of the solid catalyst component for olefin polymerization (A), a prepolymerization catalyst for olefin polymerization is obtained. As the solid catalyst component (A) for olefin polymerization used in the present invention, the (A-1) transition metal compound,
A compound comprising (A-2) an organic aluminum oxy compound and the above (A-3) a particulate carrier is preferred. Such a solid catalyst for olefin polymerization, (A-1) transition metal compound, (A-2)
It can be prepared by mixing and contacting the organoaluminum oxy compound and (A-3) a particulate carrier.

The order of contact of each component is arbitrarily selected.
(A-1) transition metal compound, (A-2) organoaluminum oxy compound, (A-3) particulate carrier, or further mixed with organoaluminum compound (D) in an inert hydrocarbon solvent or olefin medium The contact is performed.

Specific examples of the inert hydrocarbon solvent used for preparing the solid catalyst component include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane and cyclohexane And 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 (A),
(A-1) The transition metal compound is equivalent to transition metal atoms, and (A-3) 1 g of the fine particle carrier, usually 0.001 to 1.0 mmol,
It is preferably used in an amount of 0.005 to 0.5 mmol, and (A-2) the organoaluminum oxy compound is usually 0.1 to 100 mmol, preferably 0.5 to 20 mmol in terms of aluminum atom. Used. When the organoaluminum compound (D) is used, it is used in an amount of usually from 0.001 to 1000 mmol, preferably from 2 to 500 mmol, per 1 g of the finely divided carrier (A-3).

The temperature for mixing and contacting the above components is as follows:
The temperature is usually -50 to 150C, preferably -20 to 120C, and the contact time is 1 to 1000 minutes, preferably 5 to 6 minutes.
00 minutes. As a method for preparing a prepolymerization catalyst for olefin polymerization, for example, (A-1) a transition metal compound, (A
-2) A solid catalyst component (B) obtained by mixing and contacting an organoaluminum oxy compound and (A-3) a particulate carrier in an inert hydrocarbon solvent or an olefin medium, a small amount of ethylene, propylene, etc. Olefin, preferably ethylene.

It is preferable to use an organic aluminum compound (D) such as dimethyl aluminum chloride or triisobutyl aluminum at the time of prepolymerization. Examples of the inert hydrocarbon solvent used for preparing the prepolymerization catalyst for olefin polymerization include the same inert hydrocarbon solvents used for preparing the solid catalyst component.

In preparing the prepolymerization catalyst for olefin polymerization, (A-1) the transition metal compound is usually 0.001 to 1 per g of the fine particle carrier (A-3) in terms of transition metal atom.
1.0 mmol, preferably used in an amount of 0.005 to 0.5 mmol, (A-2) the organic aluminum oxy compound is usually 0.1 to 100 mmol, preferably 0.5 to 0.5 mmol in terms of aluminum atom. Used in an amount of 20 mmol. When the organoaluminum compound (D) is used, (A
-3) Usually 0.001 to 1000 per 1 g of particulate carrier
It is used in an amount of mmol, preferably 0.01-500 mmol. The temperature of the prepolymerization is usually -50 to 100.
° C, preferably in the range of 0 to 90 ° C.

The prepolymerization catalyst component (B) for olefin polymerization having been subjected to the prepolymerization in this manner is brought into contact with a surfactant (C). The surfactant (C) is used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, more preferably 0.4 to 10 parts by weight, based on 100 parts by weight of the prepolymerization catalyst component (B). Used in amounts.

The prepolymerization catalyst (B) for olefin polymerization brought into contact with the surfactant (C) is obtained as a suspension of a hydrocarbon solvent. In the present invention, the solvent is removed and the resulting olefin polymerization catalyst (B) is removed. After drying the pre-polymerization catalyst (B), it can be used again for pre-polymerization,
Pre-polymerization may be performed again. The olefin used for the prepolymerization includes ethylene, propylene and the like, and the olefin used for the second prepolymerization is preferably the same as the olefin used for the first prepolymerization. Among them, ethylene is preferred. Drying is performed in an inert gas atmosphere, preferably under a nitrogen stream, at 0 to 100 ° C., preferably 20 to 6 ° C.
It is desirable to carry out at a temperature of 0 ° C. for 1 to 50 hours, preferably 1 to 20 hours.

The prepolymerization catalyst for olefin polymerization obtained by dividing the prepolymerization into two as described above is characterized in that (A-3) the transition metal compound is equivalent to the transition metal atom per 1 g of the particulate carrier (A-3). About 5 × 10 ^-6 to 10 ^-3 mol, preferably 10 ^-5 to
(A-2) The organic aluminum oxy compound is supported in an amount of 3 × 10 ^-4 mol, and the organic aluminum oxy compound is about 10 ^-3 to 1 in terms of aluminum atom.
0 ^-1 mole, preferably be carried in an amount of 2 × 10 ^-3 ~5 × 10 ^-2 mol, compound (B) is 0.5 to 500 mg, preferably supported in an amount of 25 to 250 mg, by prepolymerization The resulting olefin polymer is supported in an amount of about 7 to 500 g, preferably 7.5 to 300 g, particularly preferably 8 to 50 g.

When the prepolymerized catalyst component (B) and the surfactant (C) are mixed and contacted, the surfactant (C)
Is 0.1 parts by weight with respect to 100 parts by weight of the solid catalyst component (A).
It is used in an amount of up to 20 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.4 to 5 parts by weight.

The mixed contact between the prepolymerized catalyst component (B) and the surfactant (C) can be carried out in an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvent include the same ones as described above. Can be

When the prepolymerization catalyst component (B) and the surfactant (C) are mixed and contacted in an inert hydrocarbon solvent, the solid catalyst for olefin polymerization is obtained as a suspension of the hydrocarbon solvent. It may be used as it is for the next prepolymerization, or it may be used again for the prepolymerization after removing the solvent and drying the obtained prepolymerization catalyst (B) for olefin polymerization. Drying is performed in an inert gas atmosphere, preferably under a nitrogen stream, at 0 to 60 ° C, preferably 20 to 40 ° C.
At a temperature of 1 to 50 hours, preferably 1 to 20 hours. The pre-polymerization of the olefin again can be performed in the same manner as the above-mentioned pre-polymerization except that the olefin polymerization catalyst component after contact with the surfactant (C) is used.
At that time, it is desirable to use an organic aluminum compound (D) in combination. The olefin used is preferably the same as that used in the first prepolymerization.

The prepolymerized catalyst for olefin polymerization obtained in this manner is obtained by adding (A-1)
When the transition metal compound is about 5 × 10 ^-6 to 1 in terms of transition metal atom
0 ^-3 mol, preferably supported in an amount of 10 ^-5 to 3 × 10 ^-4 mol, (A-2) from about 10 ^-3 to 10 ^-1 mol organoaluminum oxy-compound is an aluminum atom in terms, preferably 2
It is supported in an amount of × 10 ^{-3 to} 5 × 10 ^-2 mol, and the surfactant (C) is contained in an amount of 0.5 to 500 mg, preferably 25 to 250 mg.
Desirably, it is carried in an amount of mg.

The prepolymerization catalyst for olefin polymerization of the present invention is easy to handle because of its excellent fluidity, and is easy to supply to a polymerization vessel. In addition, heat spots are hardly generated at the time of polymerization, sheeting and generation of a polymer lump can be prevented, and olefin can be polymerized stably for a long period of time.

Polymerization The olefin polymerization using the prepolymerization catalyst for olefin polymerization provided by the present invention is carried out by slurry polymerization or gas phase polymerization. Examples of the inert hydrocarbon medium used in the slurry polymerization include those similar to the inert hydrocarbon solvents used when preparing the solid catalyst component. Among these inert hydrocarbon solvents, aliphatic hydrocarbons and alicyclic hydrocarbons are preferred. At the time of polymerization, (A-3) an organic aluminum oxy compound and / or an organic aluminum compound (D) not supported on a fine particle carrier can be used.

The olefin polymerization temperature is usually -50 to 100 ° C., preferably 0 to 100 ° C. when slurry polymerization is carried out.
It is desirable that the temperature be in the range of 90C to 90C. When carrying out the gas phase polymerization, the polymerization temperature is usually in the range of 0 to 120 ° C, preferably 20 to 100 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² , and the polymerization reaction may be performed in any of a batch system, a semi-continuous system, and a continuous system. It can be carried out.

The olefins that can be polymerized by the prepolymerization catalyst for olefin polymerization according to the present invention include α-olefins having 2 to 20 carbon atoms, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene. , 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-
Eicosene; a cyclic olefin having 3 to 20 carbon atoms such as cyclopentene, cycloheptene, norbornene, 5-
Methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like can be mentioned. . Further, styrene, vinylcyclohexane, diene and the like can be used. Among them, it is suitable for producing a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, and a copolymer containing ethylene and a main monomer is obtained.

[0063]

Industrial Applicability The prepolymerization catalyst for olefin polymerization according to the present invention has excellent fluidity, hardly generates heat spots during polymerization, and can prevent the formation of sheet-like materials and polymer lumps for a long time. Olefin can be polymerized stably.

[0064]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

Example 1 Preparation of Solid Catalyst Component (a) 10 kg of silica dried at 250 ° C. for 10 hours
After suspending in 1 liter of toluene, it was cooled to 0 ° C.
Thereafter, 50.5 liter of a toluene solution of methylaluminoxane (Al = 1.52 mol / liter) was added dropwise to this suspension over 1 hour. At this time, the temperature in the system is set to 0
５5 ° C. Subsequently, the reaction was carried out at 0 ° C. for 30 minutes, then the temperature was raised to 95 ° C. over 1.5 hours, and the reaction was carried out at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene to make the total amount 160 liters.

22.0 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr = 25.7 mmol / l) was added to the suspension thus obtained. The solution was added dropwise at 80 ° C. over 30 minutes, and further reacted at 80 ° C. for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst component (a) containing 3.2 mg of zirconium per 1 g of the solid catalyst component. Preparation of Prepolymerized Catalyst Component (b-1) A 350-liter reactor sufficiently purged with nitrogen was charged with 7.0 kg of the solid catalyst component (a) prepared above and hexane to make the total volume 285 liters. . After cooling the system to 10 ° C., ethylene was blown into hexane at a flow rate of 8 Nm ³ / h for 5 minutes. During this time, the temperature in the system was 10
It was kept at 15 ° C. After that, stop supplying ethylene,
2.4 mol of triisobutylaluminum and 1.2 kg of 1-hexene were charged. After making the inside of the system closed, 8
The supply of ethylene was restarted at a flow rate of Nm ³ / h. 1
After 5 minutes, the flow rate of ethylene was reduced to 2 Nm ³ / h, 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. Then, the temperature in the system is reduced to 32
Ethylene was supplied at a flow rate of 4 Nm ³ / h for 3.5 hours while adjusting to ３５35 ° C. During this time, the pressure in the system was 0.7
０．８0.8 kg / cm ² -G. Next, after the inside of the system was replaced with nitrogen, the supernatant was removed and the system was washed twice with hexane. Thus, the solid catalyst component
(a) A prepolymerized catalyst component (b-1) in which 3 g of polymer was prepolymerized per 1 g was obtained. Preparation of Prepolymerized Catalyst Component (b-1E) 300 ml of hexane and a prepolymerized catalyst component (b
-1) 30 g (7.5 g in terms of solid catalyst component (a)) were charged. 0.45 g of polyethylene oxide lauryl ether (trade name: Emulgen 108, manufactured by Kao) is added into the system.
The mixture was added and reacted at 35 ° C. for 4 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a prepolymerized catalyst component (b-1E). Preparation of Preliminary Polymerization Catalyst (c-1) 600 ml of hexane was charged into a 2-liter internal stainless steel autoclave sufficiently purged with nitrogen, and the system was purged with ethylene. Thereafter, 9.5 ml of 1-hexene and 25 g of the prepolymerized catalyst component (b-1E) prepared above were charged, and the temperature in the system was raised to 40 ° C. Then, while continuously supplying ethylene, 1.5 kg / cm ² -G,
Preliminary polymerization was performed at 0 ° C. for 31 minutes to obtain a prepolymerized catalyst (c-1) in which a total of 20 g of polymer was prepolymerized per 1 g of the solid catalyst component (a). Polymerization sufficiently was charged with 1 liter of hexane in a nitrogen-purged 2-liter stainless steel autoclave, in the system was replaced with ethylene. Thereafter, 40 ml of 1-hexene, 0.75 mmol of triisobutylaluminum and 4.2 g of the prepolymerized catalyst (c-1) prepared above (solid catalyst component (a)
(In terms of 0.2 g), and the temperature in the system was raised to 70 ° C. Then, the polymerization was started by introducing ethylene. Then, while continuously supplying ethylene, 8
Polymerization was performed for 1.5 hours under the polymerization conditions of kg / cm ² -G and 80 ° C. The polymer is recovered by filtration, and the pressure is reduced to 80 ° C.
Drying overnight at a melt flow rate (MF
R) is 0.14 g / 10 min and the density is 0.926 g
/ Cm ³ , and 371 g of an ethylene / 1-hexene copolymer having a bulk specific gravity of 0.40 g / cm ³ were obtained. Table 1 shows the results
Shown in

Example 2 Preparation of Prepolymerization Catalyst (c-2) 600 ml of hexane was charged into a 2-liter stainless steel autoclave sufficiently purged with nitrogen, and the system was purged with ethylene. Thereafter, 0.38 g of Emulgen 108 (manufactured by Kao), 9.5 ml of 1-hexene and 25 g of the prepolymerized catalyst component (b-1) prepared in Example 1 (6.25 g in terms of the solid catalyst component (a)) And the temperature in the system was raised to 40 ° C. Next, while continuously supplying ethylene, prepolymerization was performed for 40 minutes under the conditions of 1.5 kg / cm ² -G and 50 ° C., whereby a total of 20 g of polymer was prepolymerized per 1 g of the solid catalyst component (a). Prepolymerized catalyst
(c-2) was obtained. In the polymerization of Polymerization Example 1, 4.2 g (0.2 g in terms of solid catalyst component (a)) of the prepolymerized catalyst (c-2) prepared above was used instead of the prepolymerized catalyst (c-1). Except for this, copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1. Table 1 shows the results.

Example 3 Preparation of Prepolymerization Catalyst Component (b-2) In the preparation of the prepolymerization catalyst component (b-1) of Example 1, the charge amount of 1-hexene was 0.8 kg, and the prepolymerization amount was Solid catalyst component (a) Solid catalyst component (a) was prepared in the same manner as in Example 1 except that ethylene was supplied at 2 g per 1 g of solid catalyst component (a).
A prepolymerized catalyst component (b-2) in which 2 g of polymer was prepolymerized per 1 g was obtained. Preparation of Prepolymerization Catalyst Component (b-2E) In the preparation of the prepolymerization catalyst component (b-1E) of Example 1, the prepolymerization catalyst component (b) prepared above was used instead of the prepolymerization catalyst component (b-1). -2) In the same manner as in Example 1 except that 22.5 g (7.5 g in terms of solid catalyst component (a)) was used,
A pre-polymerization catalyst component (b-2E) was obtained. Preparation of Prepolymerized Catalyst (c-3) In the preparation of the prepolymerized catalyst (c-1) of Example 1, the charged amount of 1-hexene was 10.0 ml, and instead of the prepolymerized catalyst component (b-1E), The prepolymerized catalyst component (b-2E) prepared above was mixed with 1
A prepolymerized catalyst (c-3) in which a total of 20 g of polymer was prepolymerized per 1 g of the solid catalyst component (a) in the same manner as in Example 1 except that 8.8 g was used and the prepolymerization time was set to 33 minutes.
I got In the polymerization of Polymerization Example 1, 4.2 g (0.2 g in terms of solid catalyst component (a)) of the prepolymerized catalyst (c-3) prepared above was used instead of the prepolymerized catalyst (c-1). Except for this, copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 1 Preparation of Prepolymerized Catalyst Component (aE) Example 1 was placed in a 350-liter reactor sufficiently purged with nitrogen.
8.0 kg of the solid catalyst component (a) prepared in 1 and hexane were charged to bring the total volume to 250 liters. 480 g of Emulgen 108 (made by Kao) is added to the system,
Allowed to react for hours. After that, remove the supernatant and remove with hexane.
By washing twice, a solid catalyst component (aE) was obtained. Preparation of Prepolymerized Catalyst Component (b-3) In the preparation of the prepolymerized catalyst component (b-1) of Example 1, the solid catalyst component (a-
E) 7.0 kg, and the amount of prepolymerized solid catalyst component (a) 1
In the same manner as in Example 1 except that ethylene was supplied so as to be 3 g per g, 3 g per 1 g of the solid catalyst component (a) was used.
g polymer was prepolymerized and the prepolymerized catalyst component (b-3)
I got Preparation of Preliminary Polymerization Catalyst (c-4) 600 ml of hexane was charged into a 2-liter internal stainless steel autoclave sufficiently purged with nitrogen, and the system was purged with ethylene. Thereafter, 9.5 ml of 1-hexene and 25 g of the prepolymerized catalyst component (b-3) prepared above were charged, and the temperature in the system was raised to 40 ° C. Then, while continuously supplying ethylene, 1.5 kg / cm ² -G,
Preliminary polymerization was carried out at 0 ° C. for 56 minutes to obtain a prepolymerized catalyst (c-4) in which a total of 20 g of polymer was prepolymerized per 1 g of the solid catalyst component (a). In the polymerization of Polymerization Example 1, 4.2 g (0.2 g in terms of solid catalyst component (a)) of the prepolymerized catalyst (c-4) prepared above was used instead of the prepolymerized catalyst (c-1). Except for this, copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 Preparation of Prepolymerization Catalyst Component (b-4) In the preparation of the prepolymerization catalyst (c-1) in Example 1, the prepolymerization catalyst component (b-1E) was replaced with the prepolymerization catalyst component (b-1E). b-1) 2
In the same manner as in Example 1 except that 5 g was used and the prepolymerization time was set to 29 minutes, 20 g per 1 g of the solid catalyst component (a) was used.
g polymer was prepolymerized and the prepolymerized catalyst component (b-4)
I got Preparation of Prepolymerized Catalyst (c-5) 300 ml of hexane and a prepolymerized catalyst component (b
-4) 52.5 g (2.5 g in terms of solid catalyst component (a)) was charged. Emulgen 108 (manufactured by Kao) was added to this system.
15 g was added and reacted at 35 ° C. for 4 hours. Thereafter, the supernatant was removed and the resultant was washed twice with hexane to obtain a prepolymerized catalyst (c-5). In the polymerization of Polymerization Example 1, 4.2 g (0.2 g in terms of solid catalyst component (a)) of the prepolymerized catalyst (c-5) prepared above was used instead of the prepolymerized catalyst (c-1). Except for this, copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1. Table 1 shows the results.

Example 4 Preparation of Prepolymerized Catalyst (c-6) In the preparation of the prepolymerized catalyst (c-1) of Example 1, the charged amount of 1-hexene was 3.9 ml, and the prepolymerization time was 15 minutes. A prepolymerized catalyst (c-6) was obtained in the same manner as in Example 1, except that a total of 10 g of the polymer was prepolymerized per 1 g of the solid catalyst component (a). In the polymerization of Polymerization Example 1, 2.2 g (0.2 g in terms of solid catalyst component (a)) of the prepolymerized catalyst (c-6) prepared above was used instead of the prepolymerized catalyst (c-1). Except for this, copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 3 Preparation of Prepolymerized Catalyst (c-7) In the preparation of the prepolymerized catalyst (c-4) of Comparative Example 1, the charge amount of 1-hexene was 3.9 ml, and the prepolymerization time was 30 minutes. Solid catalyst component in the same manner as in Comparative Example 1 except that
(a) A prepolymerized catalyst (c-7) in which a total of 10 g of polymer was prepolymerized per gram was obtained. In the polymerization of Polymerization Example 1, 4.2 g (0.2 g in terms of solid catalyst component (a)) of the prepolymerized catalyst (c-7) prepared above was used instead of the prepolymerized catalyst (c-1). Except for this, copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 4 Preparation of Prepolymerized Catalyst Component (b-5) In the preparation of the prepolymerized catalyst (c-1) in Example 1, the charged amount of 1-hexene was 3.9 ml, and the amount of the prepolymerized catalyst component (b-5) was changed. In the same manner as in Example 1 except that 25 g of the pre-polymerization catalyst component (b-1) was used in place of -1E) and the pre-polymerization time was set to 14 minutes, 10 g of the polymer was mixed with 1 g of the solid catalyst component (a). Was prepolymerized to obtain a prepolymerized catalyst component (b-5). Preparation of Prepolymerized Catalyst (c-8) In the preparation of the prepolymerized catalyst (c-5) of Comparative Example 2, 0.3 g of Emulgen 108 (manufactured by Kao) was charged, and the prepolymerized catalyst component (b-4) was used. Was replaced with the prepolymerized catalyst (c-5) in the same manner as in Example 1 except that 55 g of the prepolymerized catalyst component (b-5) prepared above (5.0 g in terms of the solid catalyst component (a)) was used.
8) was obtained. In the polymerization of Polymerization Example 1, 4.2 g (0.2 g in terms of solid catalyst component (a)) of the prepolymerized catalyst (c-8) prepared above was used instead of the prepolymerized catalyst (c-1). Except for this, copolymerization of ethylene and 1-hexene was carried out in the same manner as in Example 1. Table 1 shows the results.

 ──────────────────────────────────────────────────の Continued on the front page F-term (reference) 4J028 AA01A AA02A AB00A AB01A AB02A AC01A AC03A AC09A AC23A AC27A AC32A BA01A BA01B BA02A BB01A BB01B BC15B BC16B BC20B BC24B BC28A CA24A CA25A CA26ACACB CBCAB CB28 EB04 EB05 EB07 EB08 EB09 EB10 EB11 EB18 EB21 EC01 EC03 FA02 FA04 FA07 GA26

Claims (3)

[Claims] 1 g of a solid catalyst component (A) for olefin polymerization
An antistatic agent (C) is brought into contact with the prepolymerized catalyst component (B) obtained by prepolymerizing 0.5 to 6 g of olefin per unit, and then the olefin is prepolymerized again to obtain a solid for olefin polymerization. 1 g of catalyst component (A)
A method for producing a prepolymerized catalyst for olefin polymerization, comprising prepolymerizing 7 to 500 g of olefin per olefin. 2. A solid catalyst component (A) for olefin polymerization, comprising: (A-1) a Group 4 transition metal compound having a cyclopentadienyl skeleton; (A-2) an organoaluminum oxy compound; and (A-3) 2. The process for producing a prepolymerization catalyst component for olefin polymerization according to claim 1, which is a solid catalyst component (A) for olefin polymerization, comprising: (a) a particulate carrier. 3. An antistatic agent (C) comprising: (C-1) a polyalkylene oxide block; (C-2) a higher aliphatic amide; (C-3) a polyalkylene oxide; and (C-4) a polyalkylene oxide alkyl ether. The method for producing a prepolymerization catalyst component for olefin polymerization according to claim 1, which is at least one compound selected from (C-5) alkyldiethanolamines.