JP2001323010A - Method for preparing catalyst for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for preparing a catalyst for polymerizing an olefin, exhibiting a high polymerization activity even when an inexpensive organoaluminum compound such as triethylaluminum is used. SOLUTION: The catalyst for polymerizing the olefin is prepared by bringing (A) a cocatalyst component obtained by chemically bonding a non-coordinating ion-containing compound to a particulate carrier, into contact with (B) a component obtained by bringing a metallocene compound into contact with an organometallic compound, and (C) a specific organoaluminum compound while regulating the concentration of the component (C) so as to be within the range of 0.001-2.0 mol/l, and the temperature so as to be within the range of -20 to +25 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for preparing an olefin polymerization catalyst. The present invention particularly relates to a method for preparing an olefin polymerization catalyst which can provide an olefin polymer with high activity even when an inexpensive organoaluminum such as triethylaluminum is used.

[0002]

2. Description of the Related Art An olefin polymerization catalyst comprising a metallocene compound and an organoaluminum, a cocatalyst component in which a non-coordinating ion-containing compound is bonded to a fine particle carrier by a chemical bond, is disclosed in WO96 / 41808, Japanese Patent Application Laid-Open No. H07-139,197. -5
No. 01573 has been proposed. However, when an inexpensive compound such as triethylaluminum is used as the organoaluminum compound in such a catalyst, there has been a disadvantage that the polymerization activity is significantly reduced.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for preparing an olefin polymerization catalyst which exhibits high polymerization activity even when an inexpensive organoaluminum compound such as triethylaluminum is used. It is in.

[0004]

Means for Solving the Problems The present inventors have developed a co-catalyst component in which a non-coordinating ion-containing compound is bonded to a fine particle carrier by a chemical bond, a metallocene compound, and a compound having 1 to 2 carbon atoms such as triethylaluminum. In producing a catalyst comprising an organoaluminum compound having an alkyl group, a metallocene compound that has been previously contacted with an organometallic compound is used, and by contacting the specific organoaluminum compound under specific conditions, The inventors have found that an olefin polymerization catalyst having high polymerization activity can be prepared at low cost, and have completed the present invention.

That is, the present invention provides (A) a co-catalyst component in which a non-coordinating ion-containing compound is bonded to a fine particle carrier by chemical bonding, (B) a metallocene compound (b-1) and an organometallic compound (b- And (C) the following general formula (1): R _n AlX _3-n (1) (wherein R may be the same or different from each other) , Each selected from a methyl group and an ethyl group, X may be the same or different, and each is selected from a halogen atom, an alkoxy group, and an aryloxy group, and n is an integer of 1 to 3.) In preparing the catalyst for olefin polymerization by contacting the organoaluminum compound represented by the formula (1), the components (A), (B) and (C) are mixed under the condition that at least one of the following (i) and (ii) is satisfied. Contact To provide a process for the preparation of olefin polymerization catalyst comprising a. (I) The components (C) are brought into contact with each other at a concentration of 0.001 to 2.0 mol / liter. (Ii) Contact at a temperature in the range of -20 ° C to + 25 ° C.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail. The component (A) in the present invention is a compound in which a non-coordinating ion-containing compound used as a cocatalyst in a metallocene catalyst is chemically bonded to a fine particle carrier. Examples of the chemical bond include a covalent bond, an ionic bond, and a coordinate bond. Such a co-catalyst component is described, for example, in JP-T-7-501573, WO96.
/ 40796, WO96 / 41808, W
O97 / 19959.

[0007] In particular, as the component (A), a non-coordinating ion-containing compound represented by the following general formula (2) (a-
It is preferably obtained by bringing 1) into contact with the particulate carrier (a-2). [M ¹ (R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ −L) _d ] ⁻ · [K] ⁺ (2) wherein M ¹ is boron or aluminum; Preferably it is boron.

R ¹ , R ² and R ³ each have 1 carbon atom
To 20 hydrocarbons, halogenated hydrocarbons or alkoxy groups, phenoxy groups or halogen atoms, which may be the same or different. Here, as the hydrocarbon group and the halogenated hydrocarbon group,
For example, alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group, and aryl groups such as phenyl group, tolyl group, and dimethylphenyl group And a halogenated alkyl group such as a chloromethyl group and a chloroethyl group, and a halogenated aryl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Of these, preferred are an alkyl group, an aryl group and a halogenated aryl group, and particularly preferred are an aryl group and a halogenated aryl group.

Specific examples of the halogenated aryl group include:
A fluorophenyl group such as a 4-fluorophenyl group, 2,
Difluorophenyl groups such as 4-difluorophenyl group and 3,5-difluorophenyl group; trifluorophenyl groups such as 2,4,5-trifluorophenyl group and 2,4,6-trifluorophenyl group; Bis (e.g., tetrafluorophenyl group such as 5,5,6-tetrafluorophenyl group, pentafluorophenyl group, 3,4-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group) A tris (trifluoromethyl) phenyl group such as a trifluoromethyl) phenyl group, a 2,3,5-tris (trifluoromethyl) phenyl group, a 2,4,6-tris (trifluoromethyl) phenyl group, (Trifluoromethyl) such as a 5,5,6-tetrakis (trifluoromethyl) phenyl group
Examples thereof include a phenyl group, a pentakis (trifluoromethyl) phenyl group and the like, and those obtained by replacing these fluorine atoms with another halogen atom such as a chlorine atom or a bromine atom.

Among these halogenated aryl groups, a fluorophenyl group such as a trifluorophenyl group, a tetrafluorophenyl group and a pentafluorophenyl group is preferable, and a tetrafluorophenyl group and a pentafluorophenyl group are more preferable. A pentafluorophenyl group is preferred. In the non-coordinating ion-containing compound (a-1), R ⁴ is a hydrocarbon group which may contain a heteroatom having 1 to 20 carbon atoms, and specifically, for example, a methylene group, an ethylene group , Propylene group,
Butylene group, ethylidene group, propylidene group, o-phenylene group, m-phenylene group, p-phenylene group, 4-
Fluoro-m-phenylene group, fluorophenylene group such as 2-fluoro-p-phenylene group, difluorophenylene group such as 4,5-difluoro-m-phenylene group, 3,5-difluoro-p-phenylene group, 2, 4,5-trifluoro-m-phenylene group, 2,4,6-trifluoro-m-phenylene group, 4,5,6-trifluoro-
trifluorophenylene groups such as m-phenylene group, 2,3,5-trifluoro-p-phenylene group, 2,3,6-trifluoro-p-phenylene group, 3,4,5,6-
Tetrafluoro-o-phenylene group, 2,4,5,6-
Tetrafluoro-m-phenylene group, 2,3,5,6-
And a tetrafluorophenylene group such as a tetrafluoro-p-phenylene group.

Of these, preferred are 2, 4,
5-trifluoro-m-phenylene group, 2,4,6-trifluoro-m-phenylene group, 4,5,6-trifluoro-m-phenylene group, 2,3,5-trifluoro-
p-phenylene group, 2,3,6-trifluoro-p-phenylene group, 3,4,5,6-tetrafluoro-o-phenylene group, 2,4,5,6-tetrafluoro-m-phenylene group And 2,3,5,6-tetrafluoro-p
-Phenylene group, and particularly preferred are 2,4 and
5,6-tetrafluoro-m-phenylene group and 2,
3,5,6-tetrafluoro-p-phenylene group.

L in the non-coordinating ion-containing compound (a-1) is a silyl group, a hydroxyl group, a carboxyl group or an amino group, preferably a silyl group or a hydroxyl group. Examples of the silyl group represented by the following general formula (3) - [Si (Z 1 Z 2) -Z 6 -] n SiZ 3 Z 4
Z ⁵ ··· (3) ^{(wherein, Z 1, Z 2, Z} 3, Z 4
And Z ⁵ are each selected from a halogen atom, an alkoxy group, a phenoxy group, an acyloxy group and a hydrocarbon group having 1 to 20 carbon atoms, and at least one of Z ³ , Z ⁴ and Z ⁵ is a halogen atom, an alkoxy group , A phenoxy group or an acyloxy group, and Z ⁶ is an oxygen atom, an imino group, an alkylene group having 1 to 20 carbon atoms,
0 represents an arylene group or an oxaalkylene group having 1 to 20 carbon atoms, and n is an integer of 0 or 1 to 10).

Specific examples of the silyl group include trihalogenosilyl groups such as trichlorosilyl group, alkyldihalogenosilyl groups such as methyldichlorosilyl group and ethyldichlorosilyl group, dimethylchlorosilyl group, diethylchlorosilyl group and the like. Aryl dihalogenosilyl groups such as dialkylhalogenosilyl group, phenyldichlorosilyl group, and p-tolyldichlorosilyl group; trialkoxysilyl groups such as diarylhalogenosyl groups such as diphenylchlorosilyl group; , An alkyldialkoxysilyl group such as a methyldimethoxysilyl group, a dialkylalkoxysilyl group such as a dimethylmethoxysilyl group and a dimethylethoxysilyl group, and an aryl dialkoxy group such as a phenyldimethoxysilyl group and a tolyldimethoxysilyl group. Silyl group, diphenylmethoxysilyl group, ditolylmethoxysilyl group, alkoxy group-containing silyl group such as diarylalkoxysilyl group such as diphenylethoxysilyl group, triacyloxysilyl group such as triacetoxysilyl group, methyldiacetoxysilyl group and the like. Alkyl diacyloxysilyl group, dialkylacyloxysilyl group such as dimethylacetoxysilyl group, aryldiacyloxysilyl group such as phenyldiacetoxysilyl group, diarylacyloxysilyl group such as diphenylacetoxysilyl group, alkylhydroxysilyl such as dimethylhydroxysilyl group And the like.

Of these, preferred are trichlorosilyl, methyldichlorosilyl, dimethylchlorosilyl, trimethoxysilyl, methyldimethoxysilyl, dimethylmethoxysilyl, triethoxysilyl, methyldiethoxysilyl. Dimethylethoxysilyl group, triacetoxysilyl group, methyldiacetoxysilyl group, dimethylacetoxysilyl group, trihydroxysilyl group, methyldihydroxysilyl group and dimethylhydroxysilyl group, and particularly preferred are trichlorosilyl group, methyldichlorosilyl And a dimethylchlorosilyl group.

Further, the non-coordinating ion-containing compound (a-
In 1), a, b and c are 0 or an integer of 1 to 3, d is an integer of 1 to 4, and a + b + c + d =
4. Among them, compounds in which d = 1 are preferred.
In the non-coordinating ion-containing compound (a-1), K is 1
Is a multivalent cation. Specifically, proton, triarylcarbenium ion, triarylcarbenium ion such as tri (p-tolyl) carbenium ion, carbenium ion such as trimethylcarbenium ion, tropylium ion, ferrocenium ion, trimethyl Ammonium ion such as ammonium ion, tri-n-butylammonium ion, N, N-dimethylanilinium ion, pyridinium ion such as pyridinium ion, 4-methylpyridinium ion, 2-cyanopyridinium ion and 4-cyanopyridinium ion; trimethyl Oxonium ions such as oxonium ion and triethyloxonium ion, silylium ions such as trimethylsilylium ion and triethylsilylium ion, lithium, sodium, potassium, etc. Such as alkali metal ions, and the like. Of these, preferred are proton, triarylcarbenium ion, triarylcarbenium ion such as tri- (p-tolyl) carbenium ion, N, N-dimethylanilinium ion, N, N-diethylanilinium ion. A dialkylanilinium ion such as an ion; and a trialkyloxonium ion such as a trimethyloxonium ion and a triethyloxonium ion.

Specific examples of the non-coordinating ion-containing compound (a-1) which can be suitably used in the present invention include N,
N-dimethylanilinium [4- (chlorodimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate, N, N-dimethylanilinium (4-trichlorosilyl-2,3 ,
5,6-tetrafluorophenyl) tris (pentafluorophenyl) borate and the like, and the compounds described in WO 96/41808 are exemplified.

The fine particle carrier used in the method for preparing an olefin polymerization catalyst of the present invention includes metal oxides,
Metal halides, metal hydroxides, metal alkoxides,
Examples include carbonates, sulfates, acetates, silicates, and organic polymer compounds. These can be used alone or in combination as needed. These may be treated with an organoaluminum, an organosilicon compound, or the like.

Examples of the above-mentioned metal oxide include silica, alumina, titania, magnesia, zirconia, calcia, zinc oxide and the like. Examples of metal halides include, for example, magnesium chloride, calcium chloride,
Barium chloride, sodium chloride and the like can be mentioned. Examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide. Examples of the metal alkoxide include magnesium ethoxide, magnesium methoxide and the like. Examples of the carbonate include calcium carbonate, basic calcium carbonate, magnesium carbonate, basic magnesium carbonate, and barium carbonate. Examples of the sulfate include calcium sulfate, magnesium sulfate, barium sulfate and the like.
Examples of the acetate include calcium acetate, magnesium acetate and the like. Examples of the silicate include magnesium silicate such as mica and talc, calcium silicate, sodium silicate and the like. Of these, preferred are magnesium silicates such as silica, alumina, mica and talc, and silicates such as calcium silicate and sodium silicate.

Examples of the organic polymer compound include, for example,
Polyolefin such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl ester copolymer, partially saponified or completely saponified ethylene-vinyl ester copolymer and its modified products, heat of polyamide, polycarbonate, polyester, etc. Thermosetting resins such as a plastic resin, a phenol resin, an epoxy resin, a urea resin, and a melamine resin are exemplified.

Among these organic polymer compounds, those having a polar group such as a hydroxyl group, a carboxyl group, an amino group, an amide group and the like, and specifically, a hydroxyl group-containing unsaturated compound and an unsaturated carboxylic acid And the like. Modified polyolefins graft-modified with E.g. and the like, and partially saponified or completely saponified ethylene-vinyl ester copolymers, etc., are mentioned.

The average particle size of these fine particle carriers is not particularly limited, but is usually in the range of 0.1 to 2,000 μm, preferably 1 to 1,000 μm, and more preferably 5 to 100 μm. . The specific surface area is not particularly limited, it is usually in the range of 0.1~2,000m ² / g, preferably 10~1,500m ² / g,
More preferably, it is in the range of 100 to 1,000 m ² / g.

The contact between the non-coordinating ion-containing compound (a-1) and the fine-particle carrier (a-2) can be carried out by any method, even if the contact is made directly in the absence of an organic solvent. Good, but generally, the contacting takes place in an organic solvent.
Examples of the organic solvent used herein include aliphatic hydrocarbons such as pentane and hexane; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as methylene chloride and chlorobenzene; ethers such as diethyl ether and tetrahydrofuran; Amides such as N, N-dimethylformamide and N-methylpyrrolidone, alcohols such as methanol, ethanol, propanol and n-butanol, and mixtures thereof.

The contact between the non-coordinating ion-containing compound (a-1) and the particulate carrier (a-2) can be carried out at any temperature in consideration of the organic solvent used and other conditions. , Usually at a temperature in the range of -80 ° C to + 300 ° C. The preferred range of the contact temperature is from -50C to + 200C, and the more preferred range is from 0 to 150C. The amount of the non-coordinating ion-containing compound (a-1) to be used in the particulate carrier (a-2) is not particularly limited, but is usually (a-1) per 100 parts by weight of (a-2). Is 0.00
The range is from 01 to 1,000,000 parts by weight. (A-
The polymerization activity of the catalyst tends to increase as the amount used in 1) increases. However, considering the balance between the polymerization activity and the production cost, the amount used in (a-1) is 100% for the fine particle carrier (a-2).
It is preferably in the range of 0.1 to 10,000 parts by weight, more preferably in the range of 1 to 1,000 parts by weight, based on parts by weight.

As the metallocene compound (b-1) used as the component (B) in the present invention, known compounds can be used. For example, biscyclopentadienyl zirconium dichloride, bis (methylcyclopentadienyl) ) Zirconium dichloride, bis (1,2-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-propyl) Cyclopentadienyl) zirconium dichloride,
Bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1,2,3-trimethylcyclopentadienyl) zirconium dichloride, bis (1,
2,4-trimethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, (methylcyclopentadienyl) (indenyl) zirconium dichloride, (3-t-butylcyclopentadienyl) ( 1-indenyl) zirconium dichloride, (t-butylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium dichloride, and the like.

When the obtained catalyst is used for producing a propylene polymer, it is preferable to polymerize propylene in a stereoregular manner, and a metallocene compound which can be used to prepare such a preferable catalyst is used. More specifically, bis (2,3-dimethylcyclopentadienyl) dimethylsilane zirconium dichloride,
Bis (2,4-dimethylcyclopentadienyl) dimethylsilanezirconium dichloride, bis (2,3,5
-Trimethylcyclopentadienyl) dimethylsilane zirconium dichloride, (methylcyclopentadienyl) (1-indenyl) dimethylsilanezirconium dichloride, (3-t-butylcyclopentadienyl)
(1-indenyl) dimethylsilane zirconium dichloride and the like.

Also, (3-t-butylcyclopentadienyl) [4-t-butyl- (1-indenyl)] dimethylsilane zirconium dichloride, (methylcyclopentadienyl) (9-fluorenyl) dimethylsilane zirconium dichloride , (3-t-butylcyclopentadienyl) (9-fluorenyl) dimethylsilanezirconium dichloride, bis (1-indenyl) dimethylsilanezirconium dichloride, bis (2-methyl-1-indenyl) dimethylsilanezirconium dichloride, bis ( 2,4,7-trimethyl-1-indenyl) dimethylsilane zirconium dichloride, bis (2,4-dimethyl-1-indenyl) dimethylsilane zirconium dichloride, bis (2-ethyl-1-indenyl) dimethyl Run zirconium dichloride,
Bis (2-i-propyl-1-indenyl) dimethylsilane zirconium dichloride and the like can also be used.

Further, metallocene compounds having a structure in which a ring is further condensed to an indenyl skeleton, that is, bis (2-methyl-4,4) described in JP-A-6-184179 and JP-A-6-345809. 5-benzo-1-indenyl) dimethylsilane zirconium dichloride, bis (2-methyl-α-acenaphth-1-indenyl) dimethylsilane zirconium dichloride,
Bis (2-methyl-4,5-benzo-1-indenyl)
Methylphenylsilane zirconium dichloride, bis (2-methyl-α-acenaphth-1-indenyl) methylphenylsilanezirconium dichloride, 1,2-
Bis (2-methyl-4,5-benzo-1-indenyl)
Ethane zirconium dichloride, bis (4,5-benzo-1-indenyl) dimethylsilane zirconium dichloride and the like can also be used.

Further, metallocene compounds having an aryl group at the 4-position of the indenyl skeleton, ie, bis (2-methyl-4-), described in JP-A-6-100579 and JP-A-9-176222. Phenyl-1
-Indenyl) dimethylsilanezirconium dichloride, (2-methyl-4-phenyl-1-indenyl) dimethylsilanezirconium dichloride, bis [2-methyl-4- (1-naphthyl) -1-indenyl] dimethylsilanezirconium dichloride, bis [2-methyl-4- (2-naphthyl) -1-indenyl] dimethylsilanezirconium dichloride, bis [2-methyl-4
-(9-anthracenyl) -1-indenyl] dimethylsilane zirconium dichloride, bis [2-methyl-
4- (9-phenanthryl) -1-indenyl] dimethylsilanezirconium dichloride, bis [2-methyl-4- (3,5-di-i-propyl-phenyl) -6-
i-Propyl-1-indenyl] dimethylsilane zirconium dichloride, bis (2-methyl-4-phenyl-6-i-propyl-1-indenyl) dimethylsilanezirconium dichloride and the like can also be used.

Further, Japanese Patent Application Laid-Open No. 10-226712,
A metallocene compound having an azulene skeleton, that is, a bis (2
-Methyl-4-phenyl-4-hydro-1-azulenyl) dimethylsilanezirconium dichloride, bis (2-ethyl-4-phenyl-4-hydro-1-azulenyl) dimethylsilanezirconium dichloride, bis [2-methyl-4 -(Chlorophenyl) -4-hydro-
1-azulenyl] dimethylsilanezirconium dichloride, bis [2-methyl-4- (fluorophenyl)-
4-hydro-1-azulenyl] dimethylsilanezirconium dichloride, bis (2-methyl-4-phenyl-
4-hydro-1-azulenyl) (chloromethyl) methylsilanezirconium dichloride can also be used.

Further, bis [2-methyl- (η^Five-1-
Indenyl)] methylphenylsilane zirconium dic
Loride, 1,2-bis (η^Five-1-indenyl) eta
Zirconium dichloride, 1,2-bis [2-methyl
Le-(η^Five-1-indenyl)] ethanezirconiumdi
Chloride, 1,2-bis [2,4-dimethyl- (η ^Five
-1-indenyl)] ethanezirconium dichlory
, 1,2-bis [2,4,7-trimethyl- (η^Five−
1-indenyl)] ethanezirconium dichloride,
1,2-bis [2-ethyl- (η^Five-1- Indeni
Le)] ethane zirconium dichloride, 1,2-bis
[2-n-propyl- (η^Five-1-indenyl)] eta
Zirconium dichloride, [2-ethyl- (η^Five−
1-indenyl) [2-methyl- (η^Five-1- Indeni
Le)] ethane zirconium dichloride, 1,2-bis
(Η^Five-9-Fluorenyl) ethanezirconium dichloro
Ride, 2- (3-t-butylcyclopentadienyl)
−2− (η^Five-1-indenyl) propane zirconium
Dichloride, 2- (3-t-butylcyclopentadie)
Nil) -2- [4-t-butyl- (η^Five-1- Indeni
)] Propane zirconium dichloride, 2- (3-
Methylcyclopentadienyl) -2- (η^Five-9-full
Olenyl) propane zirconium dichloride, 2-
(3-t-butylcyclopentadienyl) -2- (η^Five
-9-Fluorenyl) propanezirconium dichlorai
Can also be used.

Among them, those having an aryl group at the 4-position of the indenyl skeleton described in JP-A-6-100579 and JP-A-9-176222, JP-A-6-184179 and JP-A-6-184179 A metallocene compound having a structure in which a ring is further condensed to an indenyl skeleton described in, for example, JP-A-345809, and JP-A-10-226712 and JP-A-10-279588.
Metallocene compounds having an azulene skeleton described in Japanese Patent Application Laid-open No.
5- benzo (eta ^{5-1-indenyl)]} dimethyl silane zirconium dichloride, bis [2-methyl-4-phenyl - (eta ^{5-1-indenyl)]} dimethyl silane zirconium dichloride, bis [2-methyl-4- ( 1
- naphthyl) - (eta ^{5-1-indenyl)]} dimethyl silane zirconium dichloride, bis (2-methyl-4
-Phenyl-4-hydro-1-azulenyl) dimethylsilanezirconium dichloride is preferred.

The metallocene compounds in which zirconium is replaced by another metal such as titanium or hafnium, the chlorine atom is replaced by another halogen, hydrogen atom, amide group,
Those substituted with a hydrocarbon group such as an alkoxy group, a methyl group or a benzyl group can be used without any limitation. The organometallic compound (b-2) used as the component (B) in the present invention can be generally selected from an organoaluminum compound, an organolithium compound, an organozinc compound and an organomagnesium compound. It is also possible. Of these, preferred are organoaluminum compounds and organolithium compounds, and particularly preferred are organoaluminum compounds.

Examples of the organoaluminum compound include those having one or more hydrocarbon groups having 3 to 10 carbon atoms.
For example, tri-n-propylaluminum, tri-i-
Examples thereof include trialkylaluminums such as butylaluminum, dialkylaluminum halides such as di-i-butylaluminum chloride, and dialkylaluminum hydrides such as diisobutylaluminum hydride. Of these, trialkylaluminum is preferable. Further, those having a straight-chain alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 6 to 10 carbon atoms can be exemplified. Specifically, tri-n-propylaluminum, tri-n-butylaluminum, Tri-n-hexyl aluminum, tri-n-octyl aluminum,
There are tri-n-decyl aluminum, tri-i-hexyl aluminum, tri-i-octyl aluminum and the like. These can be used alone or in combination as needed.

As the organic lithium compound, aryl lithium such as phenyl lithium, methyl lithium, n-
Examples thereof include alkyl lithium such as butyl lithium, i-butyl lithium, s-butyl lithium, and t-butyl lithium. Examples of the organic zinc compound include dimethyl zinc and diethyl zinc, and examples of the organic magnesium include di-n.
Dialkyl magnesium such as -butylmagnesium, n-butylethylmagnesium, methylmagnesium bromide, ethylmagnesium bromide, n-propylmagnesium bromide, i-propylmagnesium bromide, n-butylmagnesium chloride, i-
Alkyl magnesium halides such as butylmagnesium chloride, s-butylmagnesium chloride, t-butylmagnesium chloride, phenylmagnesium bromide, and those obtained by replacing these chlorine and bromine atoms with other halogens.

The component (B) used in the present invention is obtained by bringing the above components (b-1) and (b-2) into contact with each other by any method. The contact may be carried out in the absence of a solvent, but is usually carried out in the presence of a hydrocarbon solvent. Examples of the hydrocarbon solvent that can be used for the solvent include propane, butane, pentane, hexane, heptane, octane, decane, kerosene, aliphatic hydrocarbons such as light oil, cyclopentane,
Examples thereof include alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and ethers such as diethyl ether, tetrahydrofuran, and 1,4-dioxane. In addition, liquid paraffin, petrolatums such as white petrolatum and yellow petrolatum, aliphatic or aromatic process oils and greases can also be used. Preferred among these are aliphatic hydrocarbons and alicyclic hydrocarbons. Further, a plurality of such hydrocarbon solvents can be used in combination.

The contact between (b-1) and (b-2) is performed by contacting at an arbitrary temperature for an arbitrary time. The contact temperature is usually in the range of -50 ° C to + 150 ° C, preferably in the range of -20 ° C to + 80 ° C, more preferably 0 to 50 ° C.
It is in the range of ° C. The contact time is usually 10 seconds to 10 seconds.
It is in the range of time, preferably in the range of 1 minute to 5 hours, more preferably in the range of 2 minutes to 2 hours.

The amount of (b-2) used with respect to (b-1) is usually 1 to 100 with respect to 1 mol of a transition metal such as zirconium contained in (b-1). , 00
It is in the range of 0 mol, preferably in the range of 10 to 50,000 mol, more preferably in the range of 50 to 10,000 mol. The component (C) used in the present invention is an organoaluminum compound represented by the general formula (1), and specifically, dialkylaluminum such as trimethylaluminum, triethylaluminum, dimethylaluminum fluoride and diethylaluminum chloride. Examples thereof include alkyl aluminum dihalides such as halides and ethyl aluminum dichloride; alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride; dialkyl aluminum alkoxides such as diethyl aluminum ethoxide; and aryl oxides. Of these, those having an ethyl group are preferred, and triethylaluminum is particularly preferred.

In the process for preparing an olefin polymerization catalyst of the present invention, the above components (A), (B) and (C) are
At least one of the following (i) and (ii): contacting at a concentration of component (C) of 0.001 to 2.0 mol / liter (ii) contacting at a temperature of -20 to 25 ° C The catalyst for olefin polymerization is prepared by contacting under conditions satisfying the following conditions. When the components (A), (B) and (C) are brought into contact under conditions not satisfying any of the above (i) and (ii), the resulting catalyst has a remarkably low polymerization activity.

The concentration of the component (C) at the time of contact is preferably in the range of 0.01 to 1.5 mol / liter,
More preferably, it is in the range of 0.02 to 1.0 mol / l, particularly preferably in the range of 0.05 to 0.7 mol / l. The contact of the components (A), (B) and (C) is preferably carried out in the range of -10 ° C to + 20 ° C, more preferably in the range of -5 ° C to + 20 ° C,
Particularly preferably, it is in the range of 0 to 15 ° C. The contact time is optional, but is usually in the range of 30 seconds to 600 minutes, preferably in the range of 1 to 300 minutes, more preferably in the range of 2 to 180 minutes, and particularly preferably in the range of 3 to 120 minutes. is there.

The contacting method is optional as long as it satisfies at least one of the above conditions, but is usually carried out in a hydrocarbon solvent. Examples of the hydrocarbon solvent that can be used for this include propane, butane, pentane, hexane, heptane, octane, aliphatic hydrocarbons such as decane,
Examples thereof include alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. The contacting is preferably carried out in an aliphatic and / or cycloaliphatic hydrocarbon.

The order of contacting the components (A), (B) and (C) is arbitrary, (1) a method of simultaneously contacting all components, and (2) a contact of components (A) and (B). (3) a method of contacting the component (B) after contacting the components (A) and (C),
(4) Any method of contacting the component (A) after contacting the components (B) and (C) can be adopted.
Here, in the above cases (2) to (4),
Conditions for contacting the two components of the components (A), (B) and (C) are arbitrary, and the components may be contacted under the conditions of the above (i) and / or (ii). The above component (A),
After contacting (B) and (C), this may be used as it is for polymerization, or may be used after performing steps such as washing and drying.

The amount of component (A) used is usually the same as component (B)
The non-ligand ion-containing compound in the component (A) is added in an amount of 0.1 mol per mol of a transition metal such as zirconium contained therein.
In the range of 0.5 to 100 mol, preferably 0.1 to 100 mol.
The range is from 50 to 50 mol, more preferably from 1 to 10 mol, particularly preferably from 2 to 5 mol. Component (C) is used in an amount of usually 1 to 100, 0 to 1 mol of a transition metal such as zirconium contained in component (B).
00 mole, preferably 10-50,000.
It is in the range of moles, more preferably in the range of 50 to 10,000 moles.

The olefin polymerization catalyst obtained by the preparation method of the present invention can be used for producing any olefin polymer. Examples of the olefin include linear olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and vinylcyclohexane, and 3-methyl-1-butene and 4-methyl-.
Branched olefins such as 1-pentene, and cyclic olefins such as vinylcyclohexane, vinylcyclohexene, vinylnorbornane, vinylnorbornene, allylnorbornane, ethylidene norbornene, and dicyclopentadiene can be used. Of these, preferred are linear olefins such as ethylene, propylene, and 1-butene, and it is particularly desirable to include propylene as a main component.

The olefin polymerization catalyst obtained by the preparation method of the present invention can be applied to any polymerization method. Specifically, bulk polymerization performed in a liquid monomer,
Examples include solution polymerization and slurry polymerization performed in a liquid phase in the presence of an inert solvent, and gas phase polymerization performed in a gas phase monomer. Among them, preferred are bulk polymerization and gas-phase polymerization, and particularly preferred is bulk polymerization.

The polymerization temperature is optional considering the productivity and the molecular weight of the olefin polymer to be produced.
0 ° C., preferably 20 to 120 ° C., more preferably 40 to 100 ° C.,
Particularly preferably 56-95 ° C, most preferably 60-9.
It is in the range of 0 ° C. The pressure is generally in the range of normal pressure to 7.0 MPa in the polymerization in the liquid phase and in the range of normal pressure to 5.0 MPa in the gas phase, taking into account the properties and productivity of the propylene polymer to be obtained. Then, an appropriate range can be selected. At the time of polymerization, the molecular weight can be adjusted by any means such as introduction of hydrogen, selection of temperature and pressure, and the like.

When an olefin polymer is produced using the olefin polymerization catalyst obtained by the method of the present invention, a small amount of olefin may be prepolymerized prior to olefin polymerization or copolymerization. By performing the pre-polymerization, it is easy to suppress the generation of fouling and the formation of the bulk polymer. In the prepolymerization, the olefin is usually added in an amount of 0.1 to 1 g of the polymerization catalyst.
To 2,000 g, preferably 1.0 to 1,000 g, more preferably 10 to 500 g, particularly preferably 50 to
It is polymerized so as to have a range of 250 g. The olefin used here is not limited, and any of the above can be used. Among them, preferred are linear olefins such as ethylene, propylene and 1-butene, and cyclic olefins such as vinylcyclohexane, and it is particularly preferable to contain propylene as a main component.

The prepolymerization method is not particularly limited, and is carried out by contacting with a liquid or gaseous olefin in an arbitrary diluent or in the absence of a diluent.
The temperature of the prepolymerization is not particularly limited, and is usually from -80 ° C to +
150 ° C., preferably 0-100 ° C., more preferably 10-90 ° C., even more preferably 20-80 ° C.
It is in the range of ° C. After pre-polymerization, it may be used for polymerization as it is, or may be used after passing through steps such as washing and drying.

When olefin is polymerized using the olefin polymerization catalyst obtained by the method of the present invention, it is possible to add an organometallic compound such as an organoaluminum compound or an organolithium compound to a reactor for polymerization. .
These additions remove impurities in the polymerization reactor,
An olefin polymer can be obtained with higher activity.

[0049]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. Example 1 1) Preparation of Component (A) N, N-dimethylanilinium [4- as a non-coordinated ion-containing compound (a-1) was added to 6 ml of dichloromethane.
A solution of 0.3 g of (chlorodimethylsilyl) -2,3,5,6-tetrafluorophenyl] tris (pentafluorophenyl) borate in dichloromethane 30
A slurry obtained by adding 0.5 g of silica as the fine particle carrier (a-2) to the resulting mixture was mixed and refluxed for 2 hours with stirring. Thereafter, the supernatant was removed and washed with dichloromethane to obtain the component (A).

[0050] 2) under preparation nitrogen stream component (B), the flask 100ml, (b-1) as the bis [2-methyl-4-phenyl - (η ⁵ -1- indenyl)] dimethyl silane zirconium dichloride Was collected in an amount of 0.01 mmol. (B-
As 2), 20 ml of a 0.5 mol / l hexane solution of tri-n-butylaluminum was added, and the mixture was further stirred at room temperature for 3 hours to obtain a solution of the component (B).

3) Contact of Components (A), (B) and (C) (Preparation of Catalyst for Polymerization) Under a nitrogen stream, place the above-mentioned component (A) in a 30 ml flask.
After collecting 10 mg, 2.0 ml of hexane and 1.0 ml of a 0.5 mol / l triethylaluminum (hereinafter abbreviated as TEA) hexane solution as a component (C) were added thereto, followed by stirring at 30 ° C. for 1 minute. Next, 0.2 ml of the solution of the component (B) obtained above was added, and the mixture was further stirred at 30 ° C. for 10 minutes to prepare an olefin polymerization catalyst. The concentration of the component (C) at the time of contact was 0.16 mol /
Liters.

4) Copolymerization of propylene and ethylene In a 1.5 liter autoclave, 1 ml of a 0.5 mol / l TEA hexane solution and propylene 8
After adding mol and raising the temperature to 65 ° C., the polymerization catalyst was injected into an autoclave to initiate polymerization. One minute after the start of the polymerization, ethylene was introduced until the partial pressure became 0.25 MPa, and propylene and ethylene were copolymerized at 70 ° C. Fifteen minutes after the introduction of ethylene, the polymerization was stopped by injecting methanol. Next, unreacted propylene was removed to obtain a propylene polymer.

Table 1 shows the component (C) and its concentration, the contact temperature and time during the preparation of the catalyst, and the polymerization activity of the catalyst during the polymerization. Example 2 The operation of Example 1 was repeated in exactly the same manner except that hexane was not used. The concentration of component (C) at the time of contact in the preparation of the catalyst was 0.42 mol / L.

Table 1 shows the component (C) and its concentration, the contact temperature and time during the preparation of the catalyst, and the polymerization activity of the catalyst during the polymerization. Example 3 The procedure of Example 1 was repeated in exactly the same manner except that an olefin polymerization catalyst was prepared according to the following procedure.

Contact of Components (A), (B) and (C) (Preparation of Catalyst for Olefin Polymerization)
After collecting 10 mg of the above component (A) in a 1 l flask, 1.0 ml of a 1.6 mol / L TEA hexane solution as a component (C) and 0.1 mL of a solution of the above component (B) were added.
2 ml was added and stirred at 10 ° C. for 30 minutes to prepare an olefin polymerization catalyst. The concentration of the component (C) at the time of contact is 1.3.
Mol / l.

Table 1 shows the component (C) and its concentration, the contact temperature and time during the preparation of the catalyst, and the polymerization activity of the catalyst during the polymerization. Example 4 The procedure of Example 1 was repeated in exactly the same manner except that an olefin polymerization catalyst was prepared according to the following procedure.

Contact of Components (A), (B) and (C) (Preparation of Catalyst for Olefin Polymerization) In a 30 ml flask under a nitrogen stream, the above components (A) were added.
After collecting 10 mg of TEA, 0.3 m of TEA was used as the component (C).
1 and 0.2 ml of the solution of the component (B)
The mixture was stirred at 10 ° C. for 10 minutes to prepare an olefin polymerization catalyst. The concentration of the component (C) upon contact was 4.1 mol / L.

Table 1 shows the component (C) and its concentration, the contact temperature and the time for preparing the catalyst, and the polymerization activity of the catalyst during the polymerization. Example 5 The operation of Example 4 was repeated in exactly the same manner except that the preparation of the olefin polymerization catalyst was carried out at 20 ° C. for 5 minutes. The concentration of the component (C) upon contact was 4.1 mol / L.

Table 1 shows the component (C) and its concentration, the contact temperature and time during the preparation of the catalyst, and the polymerization activity of the catalyst during the polymerization. Example 6 The procedure of Example 4 was repeated in exactly the same manner except that the preparation of the catalyst for olefin polymerization was carried out at 5 ° C. for 20 minutes. The concentration of the component (C) upon contact was 4.1 mol / L.

Table 1 shows the component (C) and its concentration, the contact temperature and time during the preparation of the catalyst, and the polymerization activity of the catalyst during the polymerization. Example 7 The operation of Example 1 was repeated in exactly the same manner except that trimethylaluminum (TMA) was used instead of TEA. The concentration of the component (C) at the time of contact in the preparation of the catalyst was 0.16 mol / L.

Table 1 shows the component (C) and its concentration, the contact temperature and time during the preparation of the catalyst, and the polymerization activity of the catalyst during the polymerization. Comparative Example 1 The operation of Example 4 was repeated in exactly the same manner except that the contact during the preparation of the catalyst was performed at 30 ° C. The concentration of the component (C) upon contact was 4.1 mol / L.

Table 1 shows the component (C) and its concentration, the contact temperature and time during the preparation of the catalyst, and the polymerization activity of the catalyst during the polymerization. Comparative Example 2 The operation of Example 4 was repeated in exactly the same manner except that the contact during the preparation of the catalyst was performed at 30 ° C. for 30 minutes. The concentration of the component (C) upon contact was 4.1 mol / L.

Table 1 shows the component (C) and its concentration, the contact temperature and time during the preparation of the catalyst, and the polymerization activity of the catalyst during the polymerization. Comparative Example 3 The operation of Example 1 was repeated in exactly the same manner except that the contact at the time of preparing the catalyst was performed at -30 ° C. The concentration of the component (C) at the time of contact was 0.16 mol / L.

Table 1 shows the component (C) and its concentration, the contact temperature and time during the preparation of the catalyst, and the polymerization activity of the catalyst during the polymerization.

[0065]

[Table 1]

[0066]

According to the method of the present invention, an olefin polymerization catalyst having high polymerization activity can be provided even when an inexpensive organoaluminum compound such as triethylaluminum is used.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of an olefin polymerization process using a catalyst obtained in the present invention.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Tetsuya Sadaba Oita City Oita City Ota Nakanosu 2 Montelu SDC Sunrise Co., Ltd. Oita Research Center F term (reference) 4J028 AA01A AB01A AC08A AC09A AC26A AC27A BA01A BA02B BB01A BB02B BC01A BC01B BC05A BC05B BC06A BC06B BC09A BC09B BC15A BC15B BC16A BC16B CA00A CA00B CA07C CA08C CA09C CA14C CA16C CA19C CA22C CA36C CA38C CA46C CA49C CB08C CB09C EB01 EC02 EB03 EB02 EB03 EB02 EB03 EB02 EB03

Claims (2)

[Claims] 1. A co-catalyst component in which a non-coordinating ion-containing compound is bonded to a fine particle carrier by a chemical bond, (B)
The metallocene compound (b-1) and the organometallic compound (b-
And (C) the following general formula (1): R _n AlX _3-n (1) (wherein R may be the same or different from each other) , Each selected from a methyl group and an ethyl group, X may be the same or different, and each is selected from a halogen atom, an alkoxy group, and an aryloxy group, and n is an integer of 1 to 3.) In preparing the catalyst for olefin polymerization by contacting the organoaluminum compound represented by the formula (1), the components (A), (B) and (C) are mixed under the condition that at least one of the following (i) and (ii) is satisfied. A method for preparing an olefin polymerization catalyst comprising contacting. (I) The components (C) are brought into contact with each other at a concentration of 0.001 to 2.0 mol / liter. (Ii) Contact at a temperature in the range of -20 ° C to + 25 ° C. 2. Component (A) is represented by the following general formula (2): [M ¹ (R ¹ ) _a (R ² ) _b (R ³ ) _c (R ⁴ -L) _d ] ^- · [K] ⁺ ··· (2) (wherein, M ¹ represents boron or aluminum;
R ^1, R ² and R ³ may be different or mutually the same as each other, each represents a hydrocarbon, halogenated hydrocarbon or an alkoxy group, a phenoxy group or a halogen atom having 1 to 20 carbon atoms, R ⁴ Represents a hydrocarbon group which may contain a heteroatom having 1 to 20 carbon atoms, L represents a silyl group, a hydroxyl group, a carboxyl group or an amino group, and a, b and c are 0 or an integer of 1 to 3 , D is an integer of 1 to 4, and a + b + c + d = 4, and K represents a monovalent cation), and the non-coordinating ion-containing compound (a-1) and the particulate carrier (a 2. The method according to claim 1, wherein said method is brought into contact with -2).