Patent US4507449A successfully refreshed from Google Patents.
US4507449A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Olefin polymerization
Assignee: Phillips Petroleum Co
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Filing: 1983-08-16
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Granted: 1985-03-26
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Expires: 2003-08-16
Abstract
Abstract A process for producing a novel highly active vanadium catalyst comprising a particulate solid produced by reacting a vanadium compound, a phosphorus compound, and a metal halide compound and its use in the polymerization of olefins.
Inventors
- 👤 Joel L. Martin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 08:17
CPC Classifications
C; C08; C08F; C08F10/00; C08F10/02
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
233 words
A process for the production of ethylene polymers comprising polymerizing ethylene or mixtures of ethylene and minor amounts of higher mono-olefin containing 3 to 20 carbon atoms per molecule under suitable reaction conditions in the presence of a catalyst comprising a solid particulate catalyst produced by reacting in liquid reactants which allows the recovery of a solid particulate material (1) a vanadium compound havng a V-X linkage where X is halogen, (2) at least one metal halide selected from the group consisting of aluminum trichloride, aluminum tribromide, boron trichloride, silicon tetrachloride, tin tetrachloride, and antimony pentachloride and (3) an organophosphorus compound having a P-L linkage wherein L is selected from the group consisting of alkyl radicals, alkoxy radicals, aryl radicals, aryloxy radicals, cycloalkyl radicals, cycloalkoxy radicals, cycloalkylaryl radicals, alkylamino radicals, and haloalkoxy radicals, or (4) reacting a metal halide compound as defined in (2) and vanadium organophosphate-containing functionality of the formula ##STR2## wherein each L is individually selected from the group consisting of the L's as defined for (3), under conditions suitable for obtaining a particulate solid product, and (5) combining said particulate product with an organoaluminum cocatalyst compound having the formula AlR 1 n X 3-n wherein X is halogen, each R 1 is individually selected from the group consisting of alkyl, aryl, cycloalkyl and alkoxy radicals, and n is a number from 1 to 3 to form an active solid catalyst.
Claim 2
Dependent Claim
233 words
A process for the production of ethylene polymers comprising polymerizing ethylene or mixtures of ethylene and minor amounts of higher mono-olefin containing 3 to 20 carbon atoms per molecule under suitable reaction conditions in the presence of a catalyst comprising a solid particulate catalyst produced by reacting in liquid reactants which allows the recovery of a solid particulate material (1) a vanadium compound havng a V-X linkage where X is halogen, (2) at least one metal halide selected from the group consisting of aluminum trichloride, aluminum tribromide, boron trichloride, silicon tetrachloride, tin tetrachloride, and antimony pentachloride and (3) an organophosphorus compound having a P-L linkage wherein L is selected from the group consisting of alkyl radicals, alkoxy radicals, aryl radicals, aryloxy radicals, cycloalkyl radicals, cycloalkoxy radicals, cycloalkylaryl radicals, alkylamino radicals, and haloalkoxy radicals, or (4) reacting a metal halide compound as defined in (2) and vanadium organophosphate-containing functionality of the formula ##STR2## wherein each L is individually selected from the group consisting of the L's as defined for (3), under conditions suitable for obtaining a particulate solid product, and (5) combining said particulate product with an organoaluminum cocatalyst compound having the formula AlR 1 n X 3-n wherein X is halogen, each R 1 is individually selected from the group consisting of alkyl, aryl, cycloalkyl and alkoxy radicals, and n is a number from 1 to 3 to form an active solid catalyst.
Claim 3
Dependent Claim
31 words
A process according to claim 1 wherein at least 90 percent of said monomers are ethylene and the remaining monomers are other mono-olefins containing 3 to 6 carbon atoms per molecule.
Claim 4
Dependent Claim
53 words
A process according to claim 2 wherein said polymerization is conducted in the presence of a cocatalyst system comprising at least one organoaluminum compound selected from trialkylaluminum, alkylaluminum halides, and alkylaluminum alkoxides wherein each alkyl group is individually selected from the same or a different alkyl radical having 1 to 20 carbon atoms.
Claim 5
Dependent Claim
16 words
A process according to claim 3 wherein each said organoaluminum compound is selected from alkylaluminum dichlorides.
Claim 6
Dependent Claim
18 words
A process according to claim 3 wherein said monomer comprises ethylene or a mixture of ethylene and 1-hexene.
Claim 7
Dependent Claim
24 words
A process according to claim 4 wherein said particulate catalyst has been washed free of hydrocarbon soluble components prior to use in the polymerization.
Claim 8
Dependent Claim
54 words
A process according to claim 4 wherein said particulate catalyst is prepared from VCl 4 , at least one of AlCl 3 , AlBr 3 , BCl 3 , SiCl 4 , SnCl 4 and SbCl 5 , and at least one compound selected from triethyl phosphite, tributyl phosphate, triethyl phosphate, and trimethyl phosphite.
Claim 9
Dependent Claim
11 words
A polymer of ethylene produced by the process of claim 3.
Claim 10
Dependent Claim
18 words
A process according to claim 7 wherein said monomer comprises ethylene or a mixture of ethylene and 1-hexene.
Claim 11
Dependent Claim
20 words
A process according to claim 1 wherein the said particulate solid is produced in a liquid comprising a nonaromatic halocarbon.
Claim 12
Dependent Claim
71 words
A process according to claim 1 wherein the reaction is conductd at temperature in the range of about 0° C. to about 100° C., the P/V molar ratio of the reactants is in the range of about 0.2/1 to about 4/1, the moles of metal halide per mole of vandadium halide ranges from about 0.1 to about 10, and the polymerization temperature ranges from about 20° C. to about 200° C.
Claim 13
Dependent Claim
25 words
A process according to claim 1 wherein said organoaluminum cocatalyst additionally contains a halocarbon activator selected from halogen-substituted alkanes having 1 to 10 carbon atoms.
Claim 14
Dependent Claim
46 words
A process according to claim 1 wherein said particulate solid is produced in a liquid comprising a nonaromatic halocarbon and said active solid catalyst is washed with a hydrocarbon liquid until the solid is substantially free of compounds soluble in said hydrocarbon liquid prior to polymerization.
Claim 15
Dependent Claim
13 words
A process according to claim 10 wherein said halocarbon is methylene chloride (dichloromethane).
Claim 16
Dependent Claim
18 words
A process according to claim 10 wherein said halocarbon is selected from 1,1,2-trichlorotrifluorethane, dichloromethane, 1-chlorobutane, dibromomethane, and tetrachloroethylene.
Claim 17
Dependent Claim
12 words
A process according to claim 12 wherein said halocarbon is methylene chloride(dichloromethane).
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-03-25 | 1988-09-24 | 1989-03-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-03-25 | 1992-09-24 | 1993-03-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-03-25 | 1996-09-24 | 1997-03-26 | $7700.00 | Window Closed / Lapsed |