US4128500A
Expired / Lapsed
US
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Polymerization catalyst and method
Assignee: Enron Chemical Co
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Filing: 1976-04-07
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Granted: 1978-12-05
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Expires: 1996-04-07
Abstract
Abstract A catalyst and the method of making same and a method of making polymers of 1-olefins with said catalyst in which the catalyst is prepared by chemically modifying a finely divided, difficultly reducible, inorganic support of the nature of silica, alumina, thoria, titania, magnesia and mixtures thereof by adding to the support a zirconium compound before dispersing on the modified support a chromium chelate derived from a beta-dicarbonyl compound that may be either acyclic or cyclic, the chelate being essentially of the formula <IMAGE> <IMAGE> <IMAGE> WHEREIN R is individually selected from hydrogen, alkyl, alkenyl, aryl, cycloalkyl and cycloalkenyl radicals and combinations of these radicals with each R containing 0-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, R' is selected from alkylene, alkenylene, arylene, cycloalkylene and cycloalkenylene radicals and combinations of these bivalent radicals with R' containing 1-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, m is a whole number of 1 to 3, n is a whole number of 0 to 2 and m plus n is 2 or 3 and X is an inorganic or organic negative group (relative to chromium) such as halide, alkyl, alkoxy and the like, followed by activating by heating to and at an elevated pyrolytic temperature of about 800 DEG -2000 DEG F. in a non-oxidizing (either inert or reducing) atmosphere. Typical compounds are chromium acetylacetonate, chromium benzoylacetonate, chromium 5,5-dimethyl-1,3-cyclohexanedionate, chromium 2-acetylcyclohexanonate, and the like.
Inventors
- 👤 Yu-Tang Hwang
- 👤 Howard L. Grimmett
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 08:56
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
226 words
A catalyst prepared by (1) dispersing on a finely divided, difficultly reducible, inorganic support of the class consisting of silica, alumina, thoria, titania, magnesia and mixtures and composites thereof a non-oxide zirconium compound capable of intimately associating with said support and convertible to the oxide form on calcination, in a stabilizing and promoting proportion, followed by calcining at a temperature within the range of about 400°-2000° F. to provide a zirconium modified support, (2) dispersing on the thusly modified support of (1) a chromium chelate of a beta-dicarbonyl compound essentially of the formula of the class consisting of ##STR3## wherein each R is individually selected from hydrogen, alkyl, alkenyl, aryl, cycloalkyl and cycloalkenyl radicals and combinations of these radicals with each R containing 0-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, R' is selected from alkylene, alkenylene, arylene, cycloalkylene and cycloalkenylene radicals and combinations of these bivalent radicals with R' containing 1-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, m is a whole number from 1 to 3, n is a whole number from 0 to 2 with m plus n being a whole number of 2 to 3 and X is a halide, alkyl or alkoxy, and (3) activating the resulting mixture by heating to and at an elevated temperature of from about 800°-2000° F. in a non-oxidizing atmosphere.
Claim 2
Dependent Claim
226 words
A catalyst prepared by (1) dispersing on a finely divided, difficultly reducible, inorganic support of the class consisting of silica, alumina, thoria, titania, magnesia and mixtures and composites thereof a non-oxide zirconium compound capable of intimately associating with said support and convertible to the oxide form on calcination, in a stabilizing and promoting proportion, followed by calcining at a temperature within the range of about 400°-2000° F. to provide a zirconium modified support, (2) dispersing on the thusly modified support of (1) a chromium chelate of a beta-dicarbonyl compound essentially of the formula of the class consisting of ##STR3## wherein each R is individually selected from hydrogen, alkyl, alkenyl, aryl, cycloalkyl and cycloalkenyl radicals and combinations of these radicals with each R containing 0-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, R' is selected from alkylene, alkenylene, arylene, cycloalkylene and cycloalkenylene radicals and combinations of these bivalent radicals with R' containing 1-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, m is a whole number from 1 to 3, n is a whole number from 0 to 2 with m plus n being a whole number of 2 to 3 and X is a halide, alkyl or alkoxy, and (3) activating the resulting mixture by heating to and at an elevated temperature of from about 800°-2000° F. in a non-oxidizing atmosphere.
Claim 3
Dependent Claim
13 words
The catalyst of claim 1 wherein said zirconium compound is a zirconium salt.
Claim 4
Dependent Claim
24 words
The catalyst of claim 1 wherein said dispersing of the zirconium on the support is by applying thereto a solution of the zirconium compound.
Claim 5
Dependent Claim
23 words
The catalyst of claim 1 wherein said dispersing of the zirconium on the support is by applying thereto the dry compound and heating.
Claim 6
Dependent Claim
13 words
The catalyst of claim 4 wherein said applying is in a fluidized bed.
Claim 7
Dependent Claim
14 words
The catalyst of claim 1 wherein said chelate is essentially of the formula ##STR4##
Claim 8
Dependent Claim
14 words
The catalyst of claim 1 wherein said chelate is essentially of the formula ##STR5##
Claim 9
Dependent Claim
14 words
The catalyst of claim 1 wherein said chelate is essentially of the formula ##STR6##
Claim 10
Dependent Claim
24 words
The catalyst of claim 1 wherein said chromium chelate is dissolved in a solvent and the resulting solution used to impregnate said modified support.
Claim 11
Dependent Claim
45 words
The catalyst of claim 1 wherein said dispersing of said chromium chelate is accomplished by dry blending with the finely divided modified support and activating by heating in a fluid bed maintained in suspension with a non-oxidizing gas flowing through the support during the heating.
Claim 12
Dependent Claim
43 words
The catalyst of claim 1 wherein said activating is in a fluid bed using a non-oxidizing gas to maintain the mixture of modified support and chromium chelate in a fluid condition while heating to a final activation temperature of from about 800°-2000° F.
Claim 13
Dependent Claim
19 words
The catalyst of claim 1 wherein said chromium chelate is chromium 2,4-hexanedionate which is the chromium derivative of 2,4-hexanedione.
Claim 14
Dependent Claim
19 words
The catalyst of claim 1 wherein said chromium chelate is chromium acetylacetonate which is the chromium derivative of 2,4-pentanedione.
Claim 15
Dependent Claim
19 words
The catalyst of claim 1 wherein said chromium chelate is chromium benzoylacetonate which is the chromium derivative of 1-phenyl-1,3-butanedione.
Claim 16
Dependent Claim
234 words
The process of preparing an active polymerization catalyst comprising the steps of (1) dispersing on a finely divided, difficultly reducible, inorganic support of the class consisting of silica, alumina, thoria, titania, magnesia and mixtures and composites thereof a non-oxide zirconium compound capable of intimately associating with said support and convertible to the oxide form on calcination, in a stabilizing and promoting proportion, followed by calcining at a temperature within the range of about 400°-2000° F. to provide a zirconium modified support, (2) dispersing on the thusly modified support of (1) a chromium chelate of a beta-dicarbonyl compound essentially of the formula of the class consisting of ##STR7## wherein each R is individually selected from hydrogen, alkyl, alkenyl, aryl, cycloalkyl and cycloalkenyl radicals and combinations of these radicals with each R containing 0-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, R' is selected from alkylene, alkenylene, arylene, cycloalkylene and cycloalkenylene radicals and combinations of these bivalent radicals with R' containing 1-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, m is a whole number from 1 to 3, n is a whole number from 0 to 2 with m plus n being a whole number of 2 to 3 and X is a halide, alkyl or alkoxy, and (3) activating the resulting mixture by heating to and at an elevated temperature of from about 800°-2000° F. in a non-oxidizing atmosphere.
Claim 17
Dependent Claim
234 words
The process of preparing an active polymerization catalyst comprising the steps of (1) dispersing on a finely divided, difficultly reducible, inorganic support of the class consisting of silica, alumina, thoria, titania, magnesia and mixtures and composites thereof a non-oxide zirconium compound capable of intimately associating with said support and convertible to the oxide form on calcination, in a stabilizing and promoting proportion, followed by calcining at a temperature within the range of about 400°-2000° F. to provide a zirconium modified support, (2) dispersing on the thusly modified support of (1) a chromium chelate of a beta-dicarbonyl compound essentially of the formula of the class consisting of ##STR7## wherein each R is individually selected from hydrogen, alkyl, alkenyl, aryl, cycloalkyl and cycloalkenyl radicals and combinations of these radicals with each R containing 0-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, R' is selected from alkylene, alkenylene, arylene, cycloalkylene and cycloalkenylene radicals and combinations of these bivalent radicals with R' containing 1-20 carbon atoms and a corresponding valence-satisfying number of hydrogen atoms, m is a whole number from 1 to 3, n is a whole number from 0 to 2 with m plus n being a whole number of 2 to 3 and X is a halide, alkyl or alkoxy, and (3) activating the resulting mixture by heating to and at an elevated temperature of from about 800°-2000° F. in a non-oxidizing atmosphere.
Claim 18
Dependent Claim
13 words
The process of claim 15 wherein said zirconium compound is a zirconium salt.
Claim 19
Dependent Claim
24 words
The process of claim 15 wherein said dispersing of the zirconium on the support is by applying thereto a solution of the zirconium compound.
Claim 20
Dependent Claim
23 words
The process of claim 15 wherein said dispersing of the zirconium on the support is by applying thereto the dry compound and heating.
Claim 21
Dependent Claim
13 words
The process of claim 15 wherein said applying is in a fluidized bed.
Claim 22
Dependent Claim
14 words
The process of claim 15 wherein said chelate is essentially of the formula ##STR8##
Claim 23
Dependent Claim
14 words
The process of claim 15 wherein said chelate is essentially of the formula ##STR9##
Claim 24
Dependent Claim
14 words
The process of claim 15 wherein said chelate is essentially of the formula ##STR10##
Claim 25
Dependent Claim
24 words
The process of claim 15 wherein said chromium chelate is dissolved in a solvent and the resulting solution used to impregnate said modified support.
Claim 26
Dependent Claim
45 words
The process of claim 15 wherein said dispersing of said chromium chelate is accomplished by dry blending with the finely divided modified support and activating by heating in a fluid bed maintained in suspension with a non-oxidizing gas flowing through the support during the heating.
Claim 27
Dependent Claim
43 words
The process of claim 15 wherein said activating is in a fluid bed using a non-oxidizing gas to maintain the mixture of modified support and chromium chelate in a fluid condition while heating to a final activation temperature of from about 800°-2000° F.
Claim 28
Dependent Claim
19 words
The process of claim 15 wherein said chromium chelate is chromium 2,4-hexanedionate which is the chromium derivative of 2,4-hexanedione.
Claim 29
Dependent Claim
19 words
The process of claim 1 wherein said chromium chelate is chromium acetylacetonate which is the chromium derivative of 2,4-pentanedione.
Claim 30
Dependent Claim
19 words
The process of claim 15 wherein said chromium chelate is chromium benzoylacetonate which is the chromium derivative of 1-phenyl-1,3-butanedione.
Claim 31
Dependent Claim
38 words
The catalyst of claim 1 wherein said support prior to the dispersing thereon of said zirconium compound is pretreated by heating at a temperature of from about 300°-2000° F. until volatile matter is at least partially driven off.
Claim 32
Dependent Claim
38 words
The process of claim 15 wherein said support prior to the dispersing thereon of said zirconium compound is pretreated by heating at a temperature of from about 300°-2000° F. until volatile matter is at least partially driven off.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-12-04 | 1982-06-05 | 1982-12-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-12-04 | 1986-06-05 | 1986-12-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-12-04 | 1990-06-05 | 1990-12-05 | $7700.00 | Window Closed / Lapsed |