Metallocene-catalyzed olefin polymerization in the absence of aluminoxane

• US 6,121,394 A
• Filed: 05/25/1995
• Issued: 09/19/2000
• Est. Priority Date: 07/24/1990
• Status: Expired due to Term

• Current Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Original Assignee: Mitsui Chemicals Incorporated (Mitsui Chemicals)
• Inventors: Takeuchi, Katsumi, Uchida, Osamu, Asanuma, Tadashi, Sugimoto, Ryuichi, Iwatani, Tutomu
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): Rabago, Roberto
• Application Number:
  US08/450,735
• Time in Patent Office: 1,944 Days
• Field of Search: 526/97, 526/124, 526/125, 526/129, 526/156, 526/132, 526/133, 526/160, 526/943, 526/124.1, 526/124.2, 526/124.3
• US Class Current: 526/124.3
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/15 Isotactic
• CPC Class Codes: C08F 2500/16 Syndiotactic
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/18 Bulk density
• CPC Class Codes: C08F 4/61908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/61912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/61916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/61922 containing at least two cyclopentadienyl rings, fused or not
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65922 containing at least two cyclopentadienyl rings, fused or not
• CPC Class Codes: C08F 4/74 selected from refractory metals
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

The present invention is directed to a method for polymerizing an α-olefin characterized by using a catalyst system which is obtained by reacting a halogenated metallocene compound with an organometallic compound, and then bringing the resultant reaction product into contact with a compound which will be a stable anion by reaction with the reaction product of the halogenated metallocene compound and the organometallic compound.

When the method of the present invention is carried out, a polyolefin can be obtained by the use of the inexpensive catalyst in a high activity per unit amount of the catalyst.

Claims

1. A method for polymerizing an α

-olefin comprising by bringing the α

-olefin into contact with a catalyst which is obtained by reacting a halogenated metallocene compound with an organometallic compound, and then bringing the resultant reaction product into contact with an ionic compound or an electrophilic compound;

wherein the halogenated metallocene compound is a compound represented by the formula (I) or (II) ##STR4## wherein A and B or A'"'"' and B'"'"' are mutually identical or different and are unsaturated hydrocarbon residues coordinated to a central atom;

R is a divalent straight-chain hydrocarbon residue which may have a side chain;

or a residue in which a part or all of the carbon atoms of the straight-chain may be substituted by silicon atoms, germanium atoms or tin atoms;

X is a halogen atom; and

M is a zirconium atom or a hafnium atom;

the organometallic compound is triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, triheptylaluminum, trioctylaluminum, tridecylaluminum, isoprenylaluminum, diethylaluminum hydride, diisopropylaluminum hydride, diisobutylaluminum hydride, diethylzinc, diphenylzinc, divinylzinc, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, dihexylmagnesium or butylethylmagnesium;

the ionic compound is represented by the formula (V)

space="preserve" listing-type="equation">[Q].sub.m [Y].sub.m- (V)

wherein Q is a cationic component of the ionic compound, and is selected from carbonium cation, tropylium cation, ammonium cation, oxonium cation, sulfonium cation and phosphonium cation, cations of metals and cations of organometals which are easily reduced, Y is an anionic component of the ionic compound selected from the anionic components of an ionic organoboron, organoaluminum, organogallium, organophosphorus, organoarsenic and organoantimony, and m denotes valency and the electrophilic compound comprises magnesium halides or inorganic oxides having Lewis acidity, which method is performed in the absence of an aluminoxane.

2. The method of claim 1, wherein the ionic compound or the electrophilic compound is brought into contact with the reaction product of the metallocene compound and the organometallic compound, said reaction product having been supported on a carrier prior to the contact with the ionic compound or the electrophilic compound.

3. The method of claim 1, wherein the halogenated metallocene compound is a compound represented by the formula (IV) ##STR5## wherein each of E and F is a di- or tri-substituted cyclopentadienyl group having a hydrocarbon residue having 1 to 10 carbon atoms, a silyl group or a halogen atom as a substituent;

R¹ and R² may be identical or different and bonded to silicon which is linked with the two cyclopentadienyl groups, and each of R¹ and R² is a hydrogen atom or a hydrocarbon residue having 1 to 10 carbon atoms;

X is a halogen atom; and

M is, a zirconium atom or a hafnium atom.

4. The method of claim 3, wherein R¹ is a hydrocarbon residue selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl and phenyl.

5. The method of claim 3, wherein R² is a hydrocarbon residue selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl and phenyl.

6. The method of claim 3, wherein X is selected from the group consisting of fluorine, chlorine, bromine and iodine.

7. The method of claim 1, wherein the electrophilic compound is water-free aluminum oxide having a specific surface area of from 15 to 500 m² /g.

8. The method of claim 1 wherein the organometallic compound is selected from the group consisting of methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, propylmagnesium chloride and butylmagnesium chloride.