Compositions that can produce polymers

Abstract

This invention provides a compositions that are useful for polymerizing at least one monomer into at least one polymer.

1 - 25 . (canceled) 
     
     
         26 . A polymerization process, the process comprising:
 contacting a catalyst composition with at least one monomer in a polymerization zone 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 treated solid oxide compound,   wherein the at least one organometal compound has the following general formula:
   (X 1 )(X 2 )(X 3 )(X 4 )M 1    
 wherein M 1  is titanium, zirconium, or hafnium; 
 wherein (X 1 ) is a cyclopentadienyl, an indenyl, a fluorenyl, a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl, and wherein each substituent on the substituted cyclopentadienyl, the substituted indenyl, or the substituted fluorenyl, independently is an aliphatic group, a cyclic group, a combination of aliphatic and cyclic groups, an organometallic group, or hydrogen; 
 wherein (X 3 ) and (X 4 ) independently are a halide, an aliphatic group, a cyclic group, a combination of aliphatic and cyclic groups, or an organometallic group; 
 wherein (X 2 ) is a halide, an aliphatic group, a cyclic group, a combination of aliphatic and cyclic groups, an organometallic group, a cyclopentadienyl, an indenyl, a fluorenyl, a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl, and wherein each substituent on the substituted cyclopentadienyl, the substituted indenyl, or the substituted fluorenyl, independently is an aliphatic group, a cyclic group, a combination of aliphatic and cyclic groups, an organometallic group, or hydrogen; and 
 wherein (X 1 ) and (X 2 ) optionally are connected by a bridging group; 
   wherein the at least one organoaluminum compound has the following general formula:
   Al(X 5 ) n (X 6 ) 3−n    
 wherein (X 5 ) is a hydrocarbyl having from 1 to 20 carbon atoms; 
 wherein (X 6 ) is a halide, a hydride, or an alkoxide; 
 wherein “n” is a number from 1 to 3, inclusive; 
   wherein the at least one treated solid oxide compound comprises a calcined contact product of at least one solid oxide compound and at least one electron-withdrawing anion source compound;   wherein the at least one treated solid oxide compound has a surface area greater than 100 M 2 /g;   wherein when the at least one solid oxide compound is alumina and the at least one electron-withdrawing anion source compound is a fluoride compound, the alumina is calcined alumina;   wherein there is a substantial absence of aluminoxanes and borate compounds; and   wherein the catalyst composition has a catalyst activity greater than 100 grams of polyethylene per gram of treated solid oxide compound 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.   
     
     
         27 . The process of  claim 26 , wherein (X 1 ) and (X 2 ) independently are a cyclopentadienyl, an indenyl, a fluorenyl, a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl, and wherein each substituent on the substituted cyclopentadienyl, the substituted indenyl, or the substituted fluorenyl, independently is hydrogen, methyl, ethyl, propyl, butyl, tert-butyl, isobutyl, amyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, dodecyl, 2-ethylhexyl, pentenyl, butenyl, or phenyl. 
     
     
         28 . The process of  claim 26 , wherein (X 3 ) and (X 4 ) independently are a halide or a hydrocarbyl group having from 1 to 10 carbon atoms. 
     
     
         29 . The process of  claim 26 , wherein the bridging group connecting (X 1 ) and (X 2 ) is an aliphatic group, a cyclic group, a combination of aliphatic and cyclic groups, or an organometallic group. 
     
     
         30 . The process of  claim 26 , wherein the bridging group connecting (X 1 ) and (X 2 ) comprises a silicon or germanium atom. 
     
     
         31 . The process of  claim 26 , wherein (X 5 ) is an alkyl group having from 1 to 10 carbon atoms, and “n” is equal to 3. 
     
     
         32 . The process of  claim 26 , wherein the at least one solid oxide compound is Al 2 O 3 , B 2 O 3 , BeO, Bi 2 O 3 , CdO, Co 3 O 4 , Cr 2 O 3 , CuO, Fe 2 O 3 , Ga 2 O 3 , La 2 O 3 , Mn 2 O 3 , MoO 3 , NiO, P 2 O 5 , Sb 2 O 5 , SiO 2 , SnO 2 , SrO, ThO 2 , TiO 2 , V 2 O 5 , WO 3 , Y 2 O 3 , ZnO, ZrO 2 , silica-alumina, silica-zirconia, silica-titania, alumino-phosphate, or any mixture thereof. 
     
     
         33 . The process of  claim 26 , wherein the at least one solid oxide compound is alumina, zirconia, titania, silica-alumina, silica-zirconia, silica-titania, alumino-phosphate, or any mixture thereof. 
     
     
         34 . The process of  claim 26 , wherein the at least one electron-withdrawing anion source compound comprises an electron-withdrawing anion selected from a halide, sulfate, or triflate. 
     
     
         35 . The process of  claim 26 , wherein the contact product of the at least one solid oxide compound and the at least one electron-withdrawing anion source compound is calcined for about 1 hour to about 10 hours at a temperature in a range from about 400° C. to about 800° C. 
     
     
         36 . The process of  claim 26 , wherein the at least one treated solid oxide compound has a pore volume greater than about 1 cc/g. 
     
     
         37 . The process of  claim 26 , wherein the catalyst activity of the catalyst composition is greater than 1000 grams of polyethylene per gram of treated solid oxide compound 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. 
     
     
         38 . The process of  claim 26 , wherein the at least one monomer comprises an unsaturated hydrocarbon having from 2 to 20 carbon atoms. 
     
     
         39 . The process of  claim 26 , wherein the at least one monomer is ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, or mixtures thereof. 
     
     
         40 . The process of  claim 26 , wherein the at least one monomer comprises ethylene and 1-hexene. 
     
     
         41 . The process of  claim 26 , wherein the polymerization process is a slurry polymerization process, a gas phase polymerization process, or a solution polymerization process. 
     
     
         42 . The process of  claim 26 , wherein the polymerization process is conducted in a loop slurry reactor. 
     
     
         43 . A polymerization process, the process comprising:
 contacting a catalyst composition with at least one monomer in a polymerization zone 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 treated solid oxide compound,   wherein the at least one organometal compound has the following general formula:
   (X 1 )(X 2 )(X 3 )(X 4 )M 1    
 wherein M 1  is titanium, zirconium, or hafnium; 
 wherein (X 1 ) is a cyclopentadienyl, an indenyl, a fluorenyl, a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl, and wherein each substituent on the substituted cyclopentadienyl, the substituted indenyl, or the substituted fluorenyl, independently is an aliphatic group, a cyclic group, a combination of aliphatic and cyclic groups, an organometallic group, or hydrogen; 
 wherein (X 3 ) and (X 4 ) independently are a halide or a hydrocarbyl group having from 1 to 10 carbon atoms; 
 wherein (X 2 ) is a cyclopentadienyl, an indenyl, a fluorenyl, a substituted cyclopentadienyl, a substituted indenyl, or a substituted fluorenyl, and wherein each substituent on the substituted cyclopentadienyl, the substituted indenyl, or the substituted fluorenyl, independently is an aliphatic group, a cyclic group, a combination of aliphatic and cyclic groups, an organometallic group, or hydrogen; and 
 wherein (X 1 ) and (X 2 ) optionally are connected by a bridging group, and wherein the bridging group is an aliphatic group, a cyclic group, a combination of aliphatic and cyclic groups, or an organometallic group; 
   wherein the at least one organoaluminum compound has the following general formula:
   Al(X 5 ) 3    
 wherein (X 5 ) is an alkyl group having from 1 to 10 carbon atoms; 
   wherein the at least one treated solid oxide compound comprises a calcined contact product of at least one solid oxide compound and at least one electron-withdrawing anion source compound;   wherein the at least one treated solid oxide compound has a surface area greater than 100 M 2 /g, a pore volume greater than about 1 cc/g, and a particle size in a range from about 50 to about 200 microns;   wherein the at least one solid oxide compound is Al 2 O 3 , B 2 O 3 , BeO, Bi 2 O 3 , CdO, CO 3 O 4 , Cr 2 O 3 , CuO, Fe 2 O 3 , Ga 2 O 3 , La 2 O 3 , Mn 2 O 3 , MoO 3 , NiO, P 2 O 5 , Sb 2 O 5 , SiO 2 , SnO 2 , SrO, ThO 2 , TiO 2 , V 2 O 5 , WO 3 , Y 2 O 3 , ZnO, ZrO 2 , silica-alumina, silica-zirconia, silica-titania, alumino-phosphate, or any mixture thereof;   wherein when the at least one solid oxide compound is alumina and the at least one electron-withdrawing anion source compound is a fluoride compound, the alumina is calcined alumina;   wherein there is a substantial absence of aluminoxanes and borate compounds;   wherein the catalyst composition has a catalyst activity greater than 100 grams of polyethylene per gram of treated solid oxide compound 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; and   wherein the at least one monomer is ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 3-ethyl-1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, or mixtures thereof.   
     
     
         44 . The process of  claim 43 , wherein:
 (X 3 ) and (X 4 ) independently are fluoro, chloro, or methyl;   the at least one treated solid oxide compound comprises fluorided alumina, chlorided alumina, sulfated alumina, fluorided silica-alumina, or chlorided silica-alumina;   the catalyst activity of the catalyst composition is greater than 1000 grams of polyethylene per gram of treated solid oxide compound 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; and   the polymerization process is a slurry polymerization process, a gas phase polymerization process, or a solution polymerization process.   
     
     
         45 . The process of  claim 43 , wherein the catalyst composition consists essentially of a contact product of the at least one organometal compound, the at least one organoaluminum compound, and the at least one treated solid oxide compound.