Organometal compound catalyst
AssigneePhillips Petroleum Company
InventorsMax P. McDaniel, Kathy S. Collins, Gil R. Hawley, Michael D. Jensen, Elizabeth A. Benham, Anthony P. Eaton, Joel L. Martin, Christopher E. Wittner
Life of this patent
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Abstract
This invention is directed to an organometal compound catalyst that is useful for polymerizing at least one monomer to produce a polymer. The catalyst is produced by combining a titanium, zirconium or hafnium organometal compound, preferably a metallocene, at least one organoaluminum compound, and a treated solid oxide. The treated solid oxide compound contains at least one halogen, zirconium and a solid oxide compound.
Claims43
A process to produce a catalyst composition, said process comprising contacting at least one organometal compound, at least one organoaluminum compound, and at least one treated solid oxide compound 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 selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls;
- wherein substituents on said substituted cylopentadienyls, 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, boron groups, and germanium groups;
- wherein at least one substituent on X1 is optionally 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 phosphido 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 substituents 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, boron groups, and germanium groups;
- wherein at least one substituent on X2 is optionally a bridging group which connects X1 and X2;
- wherein said organoaluminum compound has the following 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;
- wherein said treated solid oxide compound comprises at least one halogen, zirconium, and a solid oxide compound;
- wherein said halogen is at least one selected from the group consisting of chlorine, bromine, and fluorine;
- wherein said solid oxide compound is selected from the group consisting of alumina, aluminophosphate, alminosilicate, and mixtures thereof;
- wherein there is a substantial absence of aluminoxanes.
A process to produce a catalyst composition being substantially free of aluminoxanes, said process comprising:
- (1) contacting alumina with a solution containing a zirconium tetraalkoxide, (Zr(OR)4), where R is an aliphatic radical containing one to twelve carbons, to produce a zirconium-containing alumina having from 1 to 10 weight percent zirconium based on the weight of the zirconium-containing alumina before calcining;
- (2) calcining the zirconium-containing alumina at a temperature within a range of 350 to 600° C. for 3 to 20 hours to produce a calcined composition;
- (3) contacting the calcined composition with carbon tetrachloride in an amount equal to 0.05 to 1 times the weight of the alumina before calcining for 10 minutes to 30 minutes to produce a chlorided, zirconium-containing alumina;
- (4) combining the chlorided, zirconium-containing alumina and bis(n-butylcyclopentadienyl) zirconium dichloride at a temperature within a range of 15° C. to 80° C. for about 1 minute to 1 hour to produce a mixture;
- and
- (5) combining the mixture with triethylaluminum to produce the catalyst composition.
A catalyst composition which is substantially free of aluminoxanes comprising a post-contacted organometal compound, a post-contacted organoaluminum compound, and a post-contacted treated solid oxide compound;
- wherein said treated solid oxide compound comprises at least one halogen, zirconium, and a solid oxide compound;
- wherein said halogen is selected from the group consisting of chlorine, bromine, and fluorine;
- wherein the solid oxide compound is selected from the group consisting of alumina, aluminophosphate, aluminosilicate, and mixtures thereof.
Dependencies are inferred from the claim text.