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US5183868A
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Olefin polymerization over pi-olefin complex of chromium supported on aluminophosphate
Assignee: Phillips Petroleum Co
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Filing: 1990-07-23
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Granted: 1993-02-02
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Expires: 2010-07-23
Abstract
Abstract Olefins are polymerized using, as a catalyst, a pi-olefin complex of a transition metal supported on aluminophosphate. The most effective complexes are cycloheptatrienyl-(1,3-cycloheptadiene)chromium(-1) compounds and alkyl-substituted derivatives thereof. A metal alkyl co-catalyst, such as triethylborane or triethylaluminum, can also be present. The catalyst is best suited for forming ethylene polymers and copolymers. Both the polymerization process using the described catalyst, and the catalyst system, per se, constitute different aspects of the invention.
Inventors
- 👤 Kim W. Nordquest
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 17:10
CPC Classifications
C; C08; C08F; C08F10/00
Claims Analysis
Total Claims: 16
Claim 1
Independent Claim
46 words
A polymerization process which comprises contacting at least one mono-1-olefin having 2 to 8 carbon atoms per molecule with a catalyst system comprising a pi-olefin complex of chromium (-1) supported on an activated aluminophosphate support wherein said pi-olefin is cycloheptatrienyl-(1,3-cycloheptadiene), or an alkyl substituted derivative thereof.
Claim 2
Dependent Claim
46 words
A polymerization process which comprises contacting at least one mono-1-olefin having 2 to 8 carbon atoms per molecule with a catalyst system comprising a pi-olefin complex of chromium (-1) supported on an activated aluminophosphate support wherein said pi-olefin is cycloheptatrienyl-(1,3-cycloheptadiene), or an alkyl substituted derivative thereof.
Claim 3
Dependent Claim
26 words
A polymerization process as defined in claim 1 wherein the mole ratio of phosphorus to aluminum in said activated aluminophosphate is from about 0.6:1 to 0.9:1.
Claim 4
Dependent Claim
23 words
A polymerization process as defined in claim 2 wherein the mole ratio of phosphorus to aluminum in said activated aluminophosphate is about 0.6:1.
Claim 5
Dependent Claim
21 words
A polymerization process as defined in claim 2 wherein said aluminophosphate support is prepared by activating the aluminophosphate at 600° F.
Claim 6
Dependent Claim
39 words
A polymerization process as defined in claim 1 wherein the polymerization of olefin is conducted at a temperature of from about 20° C. to about 110° C., and a pressure of from about 100 psi to about 600 psi.
Claim 7
Dependent Claim
14 words
A polymerization process as defined in claim 1 wherein the olefin polymerized comprises ethylene.
Claim 8
Dependent Claim
58 words
A polymerization process which comprises contacting at least one mon-1-olefin having 2 to 8 carbon atoms per molecule with a catalyst system comprising a pi-olefin complex chromium (-1) supported on an activated aluminophosphate support wherein said pi-olefin in said complex is selected from the group consisting of 1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 1-methyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 2-ethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-butyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-n-hexyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-diethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 5,7,7-trimethyl-(1,3,5-cycloheptatrienyl)-(1,3cycloheptadiene), 2,3,7,7-tetramethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), and mixtures thereof.
Claim 9
Dependent Claim
58 words
A polymerization process which comprises contacting at least one mon-1-olefin having 2 to 8 carbon atoms per molecule with a catalyst system comprising a pi-olefin complex chromium (-1) supported on an activated aluminophosphate support wherein said pi-olefin in said complex is selected from the group consisting of 1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 1-methyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 2-ethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-butyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-n-hexyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-diethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 5,7,7-trimethyl-(1,3,5-cycloheptatrienyl)-(1,3cycloheptadiene), 2,3,7,7-tetramethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), and mixtures thereof.
Claim 10
Dependent Claim
12 words
The process according to claim 7 wherein said compound is (1,3,5-cyloheptatrienyl)-(1,3-cycloheptadiene)-chromium (-1).
Claim 11
Dependent Claim
37 words
The process according to claim 8 wherein the polymerization is carried out at a temperature of from about 80° C. to about 100° C., and at a pressure of from about 300 psi to about 500 psi.
Claim 12
Dependent Claim
24 words
The process according to claim 9 wherein the mole ratio of phosphorus to aluminum in said aluminophosphate is from about 0.6:1 to about 0.9:1.
Claim 13
Dependent Claim
25 words
A polymerization process ad defined in claim 1 wherein said polymerization is carried out in the presence of a cocatalyst which is a trihydrocarbylborane compound.
Claim 14
Dependent Claim
44 words
A catalyst system comprising: an aluminophosphate solid support; and carried on said support, a pi-olefin negative valence chromium complex in which the pi-olefin in said complex is selected from the group consisting of (1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 1-methyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 2-ethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-butyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-n-hexyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-diethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 5,7,7-trimethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 2,3,7,7-tetramethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), and mixtures thereof.
Claim 15
Dependent Claim
44 words
A catalyst system comprising: an aluminophosphate solid support; and carried on said support, a pi-olefin negative valence chromium complex in which the pi-olefin in said complex is selected from the group consisting of (1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 1-methyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 2-ethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-butyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-n-hexyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 7-diethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 5,7,7-trimethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), 2,3,7,7-tetramethyl-(1,3,5-cycloheptatrienyl)-(1,3-cycloheptadiene), and mixtures thereof.
Claim 16
Dependent Claim
18 words
A catalyst system as defined in claim 12 wherein said pi-olefin negative valence chromium complex is cycloheptatrienyl-(1,3-cycloheptadiene)chromium (-1).
References Cited (Backward Citations)
US4105844A
Cited
US4424139A
Cited
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