Organometal catalyst compositions
AssigneePhillips Petroleum Company
InventorsMax P. McDaniel, Kathy S. Collins, Anthony P. Eaton, Elizabeth A. Benham, Michael D. Jensen, Joel L. Martin, Gil R. Hawley
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Abstract
This invention provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer. This invention also provides catalyst compositions that are useful for polymerizing at least one monomer to produce a polymer, wherein said catalyst composition comprises a post-contacted organometal compound, a post-contacted organoaluminum compound, and a post-contacted fluorided silica-alumina.
Claims81
A process to produce a catalyst composition, said process comprising contacting at least one organometal compound, and at least one organoaluminum compound, and at least one fluorided silica-alumina to produce said catalyst composition,
- wherein said organometal compound has the following general formula:
- (X1)(X2)(X3)(X4)M1
- wherein M1 is selected from the group consisting of titanium, zirconium, and hafnium;
- wherein (X1) is independently selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls;
- wherein substitutents on said substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls of (X1) are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, silicon, phosphorus, boron, and germanium;
- wherein at least one substituent on (X1) can be a bridging group which connects (X1) and (X2);
- wherein (X3) and (X4) are independently selected from the group consisting of halides, aliphatic groups, substituted aliphatic groups, cyclic groups, substituted cyclic groups, combinations of aliphatic groups and cyclic groups, combinations of substituted aliphatic groups and cyclic groups, combinations of aliphatic groups and substituted cyclic groups, combinations of substituted aliphatic groups and substituted cyclic groups, amido groups, substituted amido groups, phosphido groups, substituted pphosphido groups, alkyloxide groups, substituted alkyloxide groups, aryloxide groups, substituted aryloxide groups, organometallic groups, and substituted organometallic groups;
- wherein (X2) is selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, substituted fluorenyls, halides, aliphatic groups, substituted aliphatic groups, cyclic groups, substituted cyclic groups, combinations of aliphatic groups and cyclic groups, combinations of substituted aliphatic groups and cyclic groups, combinations of aliphatic groups and Substituted cyclic groups, combinations of substituted aliphatic groups and substituted cyclic groups, amido groups, substituted amido groups, phosphido groups, substituted phosphido groups, alkyloxide groups, substituted alkyloxide groups, aryloxide groups, substituted aryloxide groups, organometallic groups, and substituted organometallic groups;
- wherein substitutents on (X2) are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic groups and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, silicon, phosphorus, boron, and germanium;
- wherein at least one substitutuent on (X2) can be a bridging group which connects (X1) and (X2);
- wherein said organoaluminum compound has the general formula:
- Al(X5)n(X6)3−n
- wherein (X5) is a hydrocarbyl having from 1 to about 20 carbon atoms;
- wherein (X6) is a halide, hydride, or alkoxide;
- and
- wherein “n” is a number from 1 to 3 inclusive;
- and
- wherein said fluorided silica-alumina comprises fluoride, silica, and alumina;
- and
- wherein there is a absence of organoborates and aluminoxanes.
A process to produce a catalyst composition comprising:
- (1) contacting a silica-alumina with water containing ammonium bifluoride to produce a fluorided silica-alumina;
- (2) calcining said fluorided silica-alumina at a temperature within a range of 350 to 550° C. to produce a calcined composition having 4 to 20 weight percent fluoride based on the weight of said fluorided silica-alumina;
- (3) combining said calcined composition and bis(n-butylcyclopentadienyl) zirconium dichloride at a temperature within the range of 15° C. to 80° C. to produce a mixture;
- and
- (4) after between 1 minute and 1 hour, combining said mixture and triethylaluminum to produce said catalyst composition.
A process to produce a catalyst composition comprising:
- 1) contacting silica-alumina with a solution of ammonia bifluoride to produce a fluorided silica-alumina to yield about 5 to about 35 weight percent ammonium bifluoride loading;
- 2) calcining said fluorided silica alumina at a temperature in a range of about 300° C. to about 600° C. and a time in the range of about 1 hour to about 10 hours to produce a calcined, fluorided silica-alumina;
- and
- 3) precontacting said calcined, fluorided silica-alumina with bis(n-butylcyclpentadienyl) zirconium dichloride and triethylaluminum for about 1 minute to about 10 hours at a temperature from about 10° C. to about 200° C. before being charged to a polymerization reactor.
A composition according to 19 wherein said composition subsequent to contacting the organometal compound, fluorided silica-alumina, and organoaluminum compound consists essentially of organometal compound and fluorided silica-alumina.
A composition according to 19 wherein said composition subsequent to contacting the organometal compound, fluorided silica-alumina, and organoaluminum compound consists essentially of organometal compound, fluorided silica-alumina, and an organoaluminum compound.
Dependencies are inferred from the claim text.