Patent US4369295A successfully refreshed from Google Patents.
US4369295A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Impregnated second valence chromium compound in supported catalyst
Assignee: Phillips Petroleum Co
•
Filing: 1981-11-03
•
Granted: 1983-01-18
•
Expires: 2001-11-03
Abstract
Abstract A chromium catalyst supported on a silica-containing base is prepared having chromium present in both the hexavalent state and a lower valent state by anhydrously impregnating a second chromium compound onto the base which already has a chromium compound having a different chromium valence than said second chromium compound. For instance, a silica titanium cogel containing a chromium compound calcined to give hexavalent chromium can be anhydrously impregnated with a pi -bonded organochromium compound such as dibenzene chromium or dicumene chromium. Resulting polymers have broad molecular weight distribution and can be made in slurry systems at a sufficiently high melt flow to be useful in applications such as blow molding of bottles and other hollow articles.
Inventors
- 👤 Max P. McDaniel
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 11:03
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
133 words
A polymerization process comprising contacting at least one mono-1-olefin having 2 to 8 carbon atoms per molecule with a catalyst having chromium present in both the hexavalent state and a lower valence state, said catalyst being produced by a process comprising forming a silica-containing support containing hexavalent chromium, thereafter as a separate step anhydrously impregnating said support with a chromium component in an anhydrous solvent wherein the chromium has a valence of less than 6 , and thereafter removing said solvent by gentle heating at a temperature of no more than about 100° C. and recovering said catalyst as the finished product of the process and wherein a weight ratio of said hexavalent chromium to said chromium having a valence of less than 6 is within the range of about 0.1:1 to 10:1.
Claim 2
Dependent Claim
133 words
A polymerization process comprising contacting at least one mono-1-olefin having 2 to 8 carbon atoms per molecule with a catalyst having chromium present in both the hexavalent state and a lower valence state, said catalyst being produced by a process comprising forming a silica-containing support containing hexavalent chromium, thereafter as a separate step anhydrously impregnating said support with a chromium component in an anhydrous solvent wherein the chromium has a valence of less than 6 , and thereafter removing said solvent by gentle heating at a temperature of no more than about 100° C. and recovering said catalyst as the finished product of the process and wherein a weight ratio of said hexavalent chromium to said chromium having a valence of less than 6 is within the range of about 0.1:1 to 10:1.
Claim 3
Dependent Claim
17 words
A method according to claim 1 wherein said mono-1-olefin is selected from ethylene, propylene, 1-butene, and 1-hexene.
Claim 4
Dependent Claim
27 words
A method according to claim 2 comprising in addition recovering a polymer from said polymerization process, wherein said polymer has a melt index of at least 0.1.
Claim 5
Dependent Claim
11 words
A method according to claim 1 wherein said mono-1-olefin comprises ethylene.
Claim 6
Dependent Claim
75 words
A method according to claim 1 wherein said chromium component having a valence of less than 6 is a zerovalent chromium compound, wherein a weight ratio of said hexavalent chromium to said chromium having a valence of less than 6 is within the range of about 0.5:1 to about 3:1 and wherein a total amount of chromium present is within the range of 0.01 to 10 weight percent based on the weight of said support.
Claim 7
Dependent Claim
14 words
A method according to claim 1 wherein said silica-containing support is a silica-titania cogel.
Claim 8
Dependent Claim
25 words
A method according to claim 1 wherein said chromium component having a valence of less than 6 is selected from dibenzene chromium and dicumene chromium.
Claim 9
Dependent Claim
44 words
A method according to claim 1 wherein said anhydrous impregnation is carried out using n-hexane as a solvent and wherein said solvent is removed by heating at said temperature of no more than about 100° C. under a vacuum or in an inert atmosphere.
Claim 10
Dependent Claim
41 words
A method according to claim 1 wherein said silica-containing support containing a hexavalent chromium compound is formed by incorporating a chromium compound having a valence of lower than 6 with said silica-containing support and thereafter calcining in the presence of oxygen.
Claim 11
Dependent Claim
19 words
A method according to claim 1 wherein said anhydrous impregnation is carried out in the substantial absence of oxygen.
Claim 12
Dependent Claim
130 words
A polymerization process comprising contacting at least one mono-1-olefin having 2 to 8 carbon atoms per molecule with a catalyst having chromium present in both the hexavalent state and a lower valence state, said catalyst being produced by a process consisting essentially of forming a dried silica-containing support containing a chromium compound wherein the chromium has a valence of less than 6, thereafter as a separate step anhydrously impregnating said support with a hexavalent chromium compound as a solution in an anhydrous solvent and thereafter removing said solvent by gentle heating at a temperature of not more than about 100° C. and wherein a weight ratio of said hexavalent chromium to said chromium having a valence of less than 6 is within the range of from about 0.1:1 to 10:1.
Claim 13
Dependent Claim
130 words
A polymerization process comprising contacting at least one mono-1-olefin having 2 to 8 carbon atoms per molecule with a catalyst having chromium present in both the hexavalent state and a lower valence state, said catalyst being produced by a process consisting essentially of forming a dried silica-containing support containing a chromium compound wherein the chromium has a valence of less than 6, thereafter as a separate step anhydrously impregnating said support with a hexavalent chromium compound as a solution in an anhydrous solvent and thereafter removing said solvent by gentle heating at a temperature of not more than about 100° C. and wherein a weight ratio of said hexavalent chromium to said chromium having a valence of less than 6 is within the range of from about 0.1:1 to 10:1.
Claim 14
Dependent Claim
17 words
A method according to claim 11 wherein said mono-1-olefin is selected from ethylene, propylene, 1-butene, and 1-hexene.
Claim 15
Dependent Claim
26 words
A method according to claim 12 comprising in addition recovering polymer from said polymerization process, wherein said polymer has a melt index of at least 0.1.
Claim 16
Dependent Claim
11 words
A method according to claim 11 wherein said mono-1-olefin comprises ethylene.
Claim 17
Dependent Claim
75 words
A method according to claim 11 wherein said chromium compound having a valence of less than 6 is a zerovalent chromium compound, wherein a weight ratio of said hexavalent chromium to said chromium having a valence of less than 6 is within the range of about 0.5:1 to about 3:1 and wherein a total amount of chromium present is within the range of 0.01 to 10 weight percent based on the weight of said support.
Claim 18
Dependent Claim
25 words
A method according to claim 11 wherein said chromium compound having a valence of less than 6 is selected from dicumene chromium and dibenzene chromium.
Claim 19
Dependent Claim
15 words
A method according to claim 1 wherein said hexavalent chromium compound is tertiary butyl chromate.
Claim 20
Dependent Claim
14 words
A method according to claim 11 wherein said hexavalent chromium compound is chromium trioxide.
Claim 21
Dependent Claim
38 words
A method according to claim 1 wherein said chromium compound having a valence of less than 6 is combined with said support by anhydrous impregnation and wherein said anhydrous impregnations are carried out utilizing n-hexane as a solvent.
Claim 22
Dependent Claim
18 words
A method according to claim 11 wherein said impregnation is carried out in the substantial absence of oxygen.
Claim 23
Dependent Claim
41 words
A method according to claim 1 wherein said hexavalent chromium compound is tertiary butyl chromate, said chromium compound having a valence of less than 6 is selected from dibenzene chromium and dicumene chromium and wherein said support is a silica-titania cogel.
References Cited (Backward Citations)
US3157712A
Cited
US3349067A
Cited
US3231483A
Cited
US3378536A
Cited
US3624063A
Cited
US3900457A
Cited
US3887494A
Cited
US4186260A
Cited
US3976632A
Cited
US4001196A
Cited
US4188471A
Cited
US4151122A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-01-17 | 1986-07-19 | 1987-01-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-01-17 | 1990-07-19 | 1991-01-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-01-17 | 1994-07-19 | 1995-01-18 | $7700.00 | Window Closed / Lapsed |