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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 contact

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 contacting an organometal compound, an organoaluminum compound, and a solid, wherein said solid is selected from the group consisting of titanium tetrafluoride, zirconium tetrafluoride, and a treated solid oxide compound.

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1. A polymerization process comprising contacting at least one monomer and a catalyst composition under polymerization conditions to produce a polymer, wherein the catalyst composition comprises:a contact product of at least one organometal compound, at least one organoaluminum compound, and at leas

1. A polymerization process comprising contacting at least one monomer and a catalyst composition under polymerization conditions to produce a polymer, wherein the catalyst composition comprises:a contact product of at least one organometal compound, at least one organoaluminum compound, and at least one solid, the catalyst composition being substantially free of aluminoxane compounds and fluoro organic borate compounds, wherein: the organometal compound has the following general formula: (X1)(X2)(X3)(X4)M1 wherein: M1 is selected from titanium, zirconium, or hafnium; (X1) is selected from cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls; substituents on the substituted cylopentadienyls, substituted indenyls, and substituted fluorenyls or (X1) are selected front aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, boron groups, germanium groups, or hydrogen; at least one substituent on (X1) can be a bridging group which connects (X1) and (X2); (X3) and (X4) are independently selected from 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, or substituted organometallic groups; (X2) is selected from cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, substituted fluroenyls, 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 or 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, or substituted organometallic groups; substituents on (X2) are selected from the group consisting or aliphatic groups, cyclic groups, combinations of aliphatic groups and cyclic groups, silyl groups, alkyl halid groups, halides organometallic groups, phosphorus groups, nitrogen groups, boron groups, germanium groups, or hydrogen; and at least one substituent on (X2) can be a bridging group which connects (X1) and (X2); the 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; (X6) is a halide, hydride, or alkoxide; and “n” is a number front 1 to 3 inclusive; and the solid is selected from titanium tetrafluoride, zirconium tetrafluoride, or a treated solid oxide compound; wherein the treated solid oxide compound comprises a solid oxide compound having titanium tetrafluoride or zirconium tetrafluoride deposited on the surface of the solid oxide compound; and wherein said solid oxide comprises oxygen and at least one element selected from groups 2-9 and 11-17 of the Periodic Table of Elements, including lanthanides and actinides. 2. The process according to claim 1, wherein the polymerization conditions comprise slurry polymerization conditions.3. The process according to claim 1, wherein the contacting is conducted in a loop reaction zone.4. The process according to claim 1, wherein the contacting is conducted in the presence of a diluent that comprises, in major part, isobutane.5. The process according to claim 1, wherein at least one monomer is ethylene.6. The process according to claim 1, wherein at least one monomer comprises ethylene and an aliphatic 1-olefin having 3 to 20 carbon atoms per molecule.7. A catalyst composition comprising:a contact product of at least one solid, one organometal compound, and at least one organoaluminum compound, the catalyst composition being substantially free of aluminoxane compounds and fluoro organic borate compounds, wherein: the organometal compound has the following general formula: (X1)(X2)(X3)(X4)M1 wherein: M1 is selected from titanium, zirconium, or hafnium; (X1) is selected from cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls; substituents on the substituted cylopentadienyls, substituted indenyls, and substituted fluorenyls of (X1) are selected from aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups, alkyl halide, groups, halides, organometallic groups, phosphorus groups, nitrogen groups, boron groups, germanium groups, or hydrogen; at least one substituent on (X1) can be a bridging group which connects (X1) and (X2); (X3) and (X4) are independently selected from 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, or substituted organometallic groups; (X2) is selected from cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, substituted fluroenyls, 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, or substituted organometallic groups; substituents on (X2) are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic groups and cyclic groups, silyl groups, alkyl halid groups, halides organometallic groups, phosphorus groups, nitrogen groups, boron groups, germanium groups, or hydrogen; and at least one substituent on (X2) can be a bridging group which connects (X1) and (X2); the 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; (X6) is a halide, hydride, or alkoxide; and “n” is a number from 1 to 3 inclusive; and the solid is titanium tetrafluoride, zirconium tetrafluoride, or a treated solid oxide compound; wherein the treated solid oxide compound comprises a solid oxide compound having titanium tetrafluoride or zirconium tetrafluoride deposited on the surface of the solid oxide compound; and wherein said solid oxide comprises oxygen and at least one element selected from, groups 2-9 and 11-17 of the Periodic Table of Elements, including lanthanides and actinides. 8. The catalyst composition according to claim 7, wherein the catalyst composition has an activity greater than 50 grams of polymer per gram of solid per hour under slurry polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 90° C., and an ethylene pressure of 550 psig.9. The catalyst composition according to claim 7, wherein the catalyst composition has an activity greater than 100 grams of polymer per gram of solid per hour under slurry polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 90° C., and an ethylene pressure of 550 psig.10. The catalyst composition according to claim 7, wherein the catalyst composition has a weight ratio of organoaluminum compound to solid in a range from about 3:1 to about 1:100.11. The catalyst composition according to claim 7, wherein the catalyst composition has a weight ratio of organoaluminum compound to solid in a range from 1:1 to 1:50.12. The catalyst composition according to claim 7, wherein the catalyst composition has a weight ratio of solid to organometal compound in a range from about 1000:1 to about 10:1.13. The catalyst composition according to claim 7, wherein the catalyst composition has a weight ratio of solid to organometal compound in a range from 250:1 to 20:1.14. A catalyst composition comprising a contact product of at least, one organometal compound, at least one organoaluminum compound, and at least one solid, wherein the organometal compound is bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dichloride, 1,2-ethanediylbis(η5-1-indenyl)di-n-butoxyhafnium, 1,2-ethanediylbis(η5-1-indenyl)dimethylzirconium, 3,3-pentanediylbis(η5-,4,5,6,7-tetrahydro-1-indenytl)hafnium dichloride, methylphenylsilylbis(η5-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, bis(n-butylcyclopentadienyl)bis(di-t-butylamido)hafnium, bis(n-butylcyclopentadienyl)zirconium dichloride, dimethylsilylbis(1-indenyl)zirconium dichloride, octylphenylsilylbis(1-indenyl)hafnium dichloride, dimethylsilylbis(η5-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, dimethylsilylbis(2-methyl-1-indenyl) zirconium dichloride, 1,2-ethanediylbis(9-fluorenyl)zirconium dichloride, indenyl diethoxy titanium(IV) chloride, (isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(indenyl) zirconium dichloride, methyloctylsilyl bis (9fluorenyl) zirconium dichloride, or bis[1-(N,N,-diisopropylamino)boratabenzene]hydridozirconium trifluoromethylsulfonate;the 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; (X6) is a halide, hydride, or alkoxide; “n” is a number from 1 to 3 inclusive; and the solid is selected from titanium tetrafluoride, zirconium tetrafluoride, or a treated solid oxide compound; wherein the treated solid oxide compound comprises a solid oxide compound having titanium tetrafluoride or zirconium tetrafluoride deposited on the surface of the solid oxide compound; and wherein said solid oxide comprises oxygen and at least one element selected from groups 2-9 and 11-17 of the Periodic Table of Elements, including lanthanides and actinides. 15. The catalyst composition as claimed in claim 14, wherein the organometal compound is selected from bis(n-butylcyclopentadienyi)zirconium dichloride, bis(indenyl)zirconium dichloride, dimethylsilylbis(1-indenyl) zirconium dichloride, or methyloctylsilylbis(9-fluorenyl)zirconium dichloride.16. The catalyst composition as claimed in claim 14, wherein the organoaluminum compound is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, diethylaluminum ethoxide, tributylaluminum, diisobutylaluminum hydride, triisobutylaluminum hydride, triisobutylaluminum, or diethylaluminum chloride.17. The catalyst composition as claimed in claim 14, wherein the organoaluminum compound is triethylaluminum.18. The catalyst composition as claimed in claim 14, wherein the solid oxide compound is selected form alumina, silica, silica-alumina, aluminophosphate, aliminoborate, silica-zirconia, silica-titania, thoria, or mixtures thereof.19. A catalyst composition comprising:a post-contacted organometal compound; a post-contacted organoaluminum compound; and a post-contacted solid, the solid, prior to contacting, being selected from titanium tetrafluoride, zirconium tetrafluoride, or a treated solid oxide compound, the treated solid oxide compound comprising a solid oxide compound having titanium tetrafluoride or zirconium tetrafluoride deposited on the surface of the solid oxide compound, the solid oxide comprising oxygen and at least one element selected from groups 2-9 and 11-17 of the Periodic Table of Elements, including lanthanides and actinides; and the catalyst composition being substantially free of aluminoxane and a fluoro organic borate compound. 20. The catalyst composition as claimed in claim 19, wherein the organometal compound, prior to contacting, has the following general formula:(X1)(X2)(X3)(X4)M1 wherein: M1 is selected from titanium, zirconium, or hafnium; (X1) is selected from cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls; substituents on the substituted cylopentadienyls, substituted indenyls, and substituted fluorenyls of (X1) are selected from aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, boron groups, germanium groups, or hydrogen; at least one substituent on (X1) can be a bridging group which connects (X1) and (X2); (X3) and (X4) are independently selected from 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, or substituted organometallic groups; (X2) is selected from cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, substituted fluroenyls, 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, or substituted organometallic groups; substituents on (X2) are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic groups and cyclic groups, silyl groups, alkyl baud groups, halides organometallic groups, phosphorus groups, nitrogen groups, boron groups, germanium groups, or hydrogen; and at least one substituent on (X2) can be a bridging group which connects (X1) and (X2). 21. The catalyst composition as claimed in claim 19, wherein the organoaluminum compound, prior to contacting, has the following general formula:Al(X5)n(X6)3?n, wherein: (X5) is a hydrocarbyl having from 1 to about 20 carbon atoms; (X6) is a halide, hydride, or alkoxide; and “n” is a number from 1 to 3 inclusive. 22. The catalyst composition as claimed in claim 19, wherein the organometal compound, prior to contacting, is selected from bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dichloride, 1,2-ethanediylbis(η5-1-indenyl)di-n-butoxyhafnium, 1,2-ethanediylbis(η5-1-indenyl)dimethylzirconium, 3,3-pentanediylbis(η5-,4,5,6,7-tetrahydro-1-identyl)hafnium dichloride, methylphenylsilylbis(η5-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, bis(n-butylcyclopentadienyl)bis(di-t-butylamido)hafnium, bis(n-butylcyclopentadienyl)zirconium dichloride, dimethylsilylbis(1-indenyl)zirconium dichloride, octylphenylsilylbis(1-indenyl)hafnium dichloride, dimethylsilylbis(η5-4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, dimethylsilylbis(2-methyl-1-indenyl) zirconium dichloride, 1,2-ethanediylbis(9-fluorenyl)zirconium dichloride, indenyl diethoxy titanium(IV) chloride, (isopropylamidodimethylsilyl)cyclopentadienyltitanium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(indenyl) zirconium dichloride, methyloctylsilyl bis (9fluorenyl) zirconium dichloride, or bis[1-(N,N,-diisopropylamino)boratabenzene]hydridozirconium trifluoromethylsulfonate.23. The catalyst composition as claimed in claim 19, wherein the organometal compound, prior to contacting, is selected from bis(n-butylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, dimethylsilylbis(1-indenyl)zirconium dichloride, or methyloctylsilylbis (9-fluorenyl)zirconium dichloride.24. The catalyst composition as claimed in claim 19, wherein the organoaluminum compound, prior to contacting, is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, diethylaluminum ethoxide, tributylaluminum, diisobutylaluminum hydride, triisobutylaluminum hydride, triisobutylaluminum, or diethylaluminum chloride.25. The catalyst composition as claimed in claim 19, wherein the organoaluminum compound, prior to contacting, is triethylaluminum.26. The catalyst composition as claimed in claim 19, wherein the solid oxide compound, prior to contacting, is selected form alumina, silica, silica-alumina, aluminophosphate, aliminoborate, silica-zirconia, silica-titania, thoria, or mixtures thereof.27. A polymerization process comprising contacting at least one monomer and the catalyst composition of claim 19 under polymerization conditions to produce a polymer.28. A process according to claim 27, wherein the polymerization conditions comprise slurry polymerization conditions.29. A process according to claim 27, wherein the contacting is conducted in a loop reaction zone.30. A process according to claim 27, wherein the contacting is conducted in the presence of a diluent that comprises, in a major part, isobutane.31. A process according to claim 27, wherein at least one monomer is ethylene.32. A process according to claim 27, wherein at least one monomer comprises ethylene and an aliphatic 1-olefin having 3 to 20 carbon atoms per molecule.33. The catalyst composition according to claim 27, wherein the catalyst composition has an activity greater than 50 grams or polymer per grain of solid per hour under slurry polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 90° C., and an ethylene pressure of 550 psig.34. The catalyst composition according to claim 27, wherein the catalyst composition has an activity greater than 100 grams of polymer per gram of solid per hour under slurry polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 90° C., and an ethylene pressure of 550 psig.35. A polymerization process comprising contacting at least one monomer and a catalyst composition under polymerization conditions to produce a polymer,the catalyst composition being produced by a process comprising contacting at least one organometal compound, at least one organoaluminum compound, and at least one solid to produce a catalyst substantially free of aluminoxane compounds and fluoro organic borate compounds, wherein: the organometal compound has the following general formula: (X1)(X2)(X3)(X4)M1 wherein: M1 is selected from titanium, zirconium, or hafnium; (X1) is selected from cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyl substituted indenyls, and substituted fluorenyls; substituents on the substituted cylopentadienyls, substituted indenyls, and substituted fluorenyls of (X1) are selected from aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, silyl groups, alkyl halide groups, halides, organometallic groups, phosphorus groups, nitrogen groups, boron groups, germanium groups, or hydrogen; at least one substituent on (X1) can be a bridging group which connects (X1) and (X2); (X3) and (X4) are independently selected from 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, or substituted organometallic groups; (X2) is selected from cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, substituted fluroenyls, 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, or substituted organometallic groups; substituents on (X2) are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic groups and cyclic groups, silyl groups, alkyl halid groups, halides organometallic groups, phosphorus groups, nitrogen groups, boron groups, germanium groups, or hydrogen; and at least one substituent on (X2) can be a bridging group which connects (X1) and (X2); the 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; (X6) is a halide, hydride, or alkoxide; and “n” is a number from 1 to 3 inclusive; and the solid is selected from titanium tetrafluoride, zirconium tetrafluoride, or a treated solid oxide compound; wherein the treated solid oxide compound comprises a solid oxide compound having titanium tetrafluoride or zirconium tetrafluoride deposited on the surface of the solid oxide compound; and wherein said solid oxide comprises oxygen and at least one element selected from groups 2-9 and 11-17 of the Periodic Table of Elements, including lanthanides and actinides. 36. A process according to claim 35, wherein the polymerization conditions comprise slurry polymerization conditions.37. A process according to claim 35, wherein the contacting is conducted in a loop reaction zone.38. A process according to claim 35, wherein the contacting is conducted in the presence of a diluent that comprises, in a major part, isobutane.39. A process according to claim 35, wherein at least one monomer is ethylene.40. A process according to claim 35, wherein at least one monomer comprises ethylene and an aliphatic 1-olefin having 3 to 20 carbon atoms per molecule.41. The catalyst composition according to claim 35, wherein the catalyst composition has an activity greater than 50 grams of polymer per gram of solid per hour under slurry polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 90° C., and an ethylene pressure of 550 psig.42. The catalyst composition according to claim 35, wherein the catalyst composition has an activity greater than 100 grams of polymer per gram of solid per hour under slurry polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 90° C., and an ethylene pressure of 550 psig.