Organometal catalyst compositions
AssigneePhillips Petroleum Company
InventorsMax P. McDaniel, Kathy S. Collins, James L. Smith, Elizabeth A. Benham, Marvin M. Johnson, Anthony P. Eaton, Michael D. Jensen, Joel L. Martin, Gil R. Hawley
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Abstract
This invention provides catalyst composition for polymerizing at least one monomer to produce a polymer, wherein said catalyst composition comprises as organometal compound, as organoaluminum compound, and a fluorided solid oxide compound.
Claims32
A process to produce a catalyst composition, said process comprising contacting respectively organometal compound, at least one organoaluminum compound, and a fluorided 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 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 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 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 solid oxide compound comprises fluoride and a solid oxide compound;
- wherein said solid oxide compound is selected from the group consisting of silica-titania and silica-zirconia;
- and
- wherein there is an absence of organoborates and aluminoxanes.
A process comprising:
- 1) contacting a solid oxide compound with water containing ammonium bifluoride to produce a fluorided solid oxide compound;
- wherein said solid oxide compound is selected from the group consisting of silica-titania and silica-zirconia;
- 2) calcining said fluorided solid oxide compound at a temperature within a range of 350 to 600° C. to produce a calcined composition having 4 to 20 weight percent fluoride based on the weight of said fluorided solid oxide compound before calcining;
- 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.
Dependencies are inferred from the claim text.