Polymerization process utilizing an organometal compound, organoaluminum compound and a solid mixed oxide compound

Abstract

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

That which is claimed is:  
     
         1 . A process to produce a composition of matter, said process comprising contacting an organometal compound, a solid Lewis acid compound, and an organoaluminum compound to produce said composition, 
 wherein said composition consists essentially of a post-contacted organometal compound, a post-contacted solid Lewis acid compound, and optionally, a post-contacted organoaluminum compound, and    wherein said composition can polymerize ethylene into a polymer with an activity greater than a composition that uses the same organometal compound, and the same organoaluminum compound, but uses untreated Ketjen grade B alumina instead of said solid Lewis acid, and    wherein said organometal compound has the following general formula    (X 1 )(X 2 )(X 3 )(X 4 )M 1      wherein M 1  is selected from the group consisting of titanium, zirconium, and hafnium, and    wherein (X 1 ) is independently selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls, and    wherein said substituents on said substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls, are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, and hydrogen; and    wherein (X 3 ) and (X 4 ) are independently selected from the group consisting of halides, aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, and    wherein (X 2 ) is selected from the group consisting of Group OMC-I or Group-OMC-II, and    wherein said organoaluminun compound has the following general formula.    A1(X 5 ) n (X 6 ) 3-n      wherein (X 5 ) is a hydrocarbyl having from 1-20 carbon atoms, and    wherein (X 6 ) is a halide, hydride, or alkoxide, and    wherein “n” is a number from 1 to 3 inclusive.    
     
     
         2 . A process to produce a composition of matter, said process comprising contacting an organometal compound, a solid mixed oxide compound, and an organoaluminum compound to produce said composition, 
 wherein said composition consists essentially of a post-contacted organometal compound, a post-contacted solid mixed oxide compound, and optionally, a post-contacted organoaluminum compound, and    wherein said composition can polymerize ethylene into a polymer with an activity greater than 100 (gP/(gS·hr)), and    wherein said organometal compound has the following general formula    (X 1 )(X 2 )(X 3 )(X 4 )M 1      wherein M 1  is selected from the group consisting of titanium, zirconium, and hafnium, and    wherein (X 1 ) is independently selected from the group consisting of cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls, and    wherein said substituents on said substituted cyclopentadienyls, substituted indenyls, and substituted fluorenyls, are selected from the group consisting of aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, and hydrogen; and    wherein (X 3 ) and (X 4 ) are independently selected from the group consisting of halides, aliphatic groups, cyclic groups, combinations of aliphatic and cyclic groups, and organometallic groups, and    wherein (X 2 ) is selected from the group consisting of Group OMC-I or Group OMC-II, and    wherein said organoaluminun compound has the following general formula.    A1(X 5 ) n (X 6 ) 3-n      wherein (X 5 ) is a hydrocarbyl having from 1-20 carbon atoms, and    wherein (X 6 ) is a halide, hydride, or alkoxide, and    wherein “n” is a number from 1 to 3 inclusive, and    wherein said solid mixed oxide compounds comprise oxygen and at least two elements selected from the group consisting of groups 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 of the periodic table, including lanthanides and actinides.    
     
     
         3 . A process according to  claim 2  wherein said activity is greater than 150.  
     
     
         4 . A process according to  claim 3  wherein said activity is greater than 200.  
     
     
         5 . A process according to  claim 4  wherein said activity is greater than 250.  
     
     
         6 . A process according to  claim 4  wherein said activity is greater than 300.  
     
     
         7 . A composition produced by the process of  claim 2 .  
     
     
         8 . A process of using the composition of  claim 7  to polymerize monomers into polymers.  
     
     
         9 . A manufacture that comprises polymers produced according to  claim 8 .  
     
     
         10 . A machine that comprises manufactures according to  claim 9 .  
     
     
         11 . A process according to  claim 8  wherein said polymers are produced under slurry polymerization conditions.  
     
     
         12 . A process according to  claim 11  wherein said polymerization is conducted in a loop reactor.  
     
     
         13 . A process according to  claim 12  wherein said polymerization is conducted in the presence of a diluent that comprises, in major part, isobutane.  
     
     
         14 . A manufacture that comprises polymers produced according to  claim 13 .  
     
     
         15 . A machine that comprises manufactures according to  claim 14 .  
     
     
         16 . A composition produced by the process of  claim 6 .  
     
     
         17 . A process of using the composition of  claim 16  to polymerize monomers into polymers.  
     
     
         18 . A manufacture that comprises polymers produced according to  claim 17 .  
     
     
         19 . A machine that comprises manufactures according to  claim 18 .  
     
     
         20 . A process according to  claim 17  wherein said polymers are produced under slurry polymerization conditions.  
     
     
         21 . A process according to  claim 20  wherein said polymerization is conducted in a loop reactor.  
     
     
         22 . A process according to  claim 21  wherein said polymerization is conducted in the presence of a diluent that comprises, in major part, isobutane.  
     
     
         23 . A manufacture that comprises polymers produced according to  claim 22 .  
     
     
         24 . A machine that comprises manufactures according to  claim 23 .  
     
     
         25 . A process to produce a composition of matter, said process comprising contacting an organometal compound, a solid mixed oxide compound, and an organoaluminum compound to produce said composition, 
 wherein said composition consists essentially of a post-contacted organometal compound, a post-contacted solid mixed oxide compound, and optionally, a post-contacted organoaluminum, compound, and    wherein said composition can polymerize ethylene into a polymer with an activity greater than 300 (gP/(gS·hr)), and    wherein said organometal compound is selected from the group consisting of 
 bis(cyclopentadienyl) hafnium dichloride;  
 bis(cyclopentadienyl) zirconium dichloride;  
 [ethyl(indenyl) 2 ] hafnium dichloride;  
 [ethyl(indenyl) 2 ] zirconium dichloride;  
 [ethyl(tetrahydroindenyl) 2 ] hafnium dichloride;  
 [ethyl(tetrahydroindenyl) 2 ] zirconium dichloride;  
 bis(n-butylcyclopentadienyl) hafnium dichloride;  
 bis(n-butylcyclopentadienyl) zirconium dichloride;  
 ((dimethyl)(diindenyl) silane) zirconium dichloride;  
 ((dimethyl)(diindenyl) silane) hafnium dichloride;  
 ((dimethyl)(ditetrahydroindenyl) silane) zirconium dichloride;  
 ((dimethyl)(di(2-methyl indenyl)) silane) zirconium dichloride;  
 bis(fluorenyl) zirconium dichloride, and  
   wherein said organoaluminum compound is selected from the group consisting of 
 trimethylaluminum;  
 triethylaluminum;  
 tripropylaluminum;  
 diethylaluminum ethoxide;  
 tributylaluminum;  
 triisobutylaluminum hydride;  
 triisobutylaluminum;  
 diethylaluminum chloride, and  
   wherein said solid mixed oxide compounds are selected from the group consisting of mixtures of two or more oxides 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 and ZrO 2 .