Organometal compound catalyst

Abstract

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 a post-contacted organometal compound, a post-contacted organoaluminum compound, and a post-contacted treated solid oxide compound.

1 - 22 . (canceled)  
     
     
         23 . A polymer produced using a polymerization process comprising contacting, under polymerization conditions, at least one monomer and a catalyst composition which is substantially free of aluminoxanes; 
 wherein the catalyst composition comprises a post-contacted organometal compound, a post-contacted organoaluminum compound, and a post-contacted treated solid oxide compound;    wherein the treated solid oxide compound comprises at least one halogen, zirconium, and a solid oxide compound;    wherein the halogen is selected from chlorine, bromine, or fluorine; and    wherein the solid oxide compound is selected from alumina, aluminophosphate, aluminosilicate, or mixtures thereof;    the polymer having a HLMI/MI of at least about 50.    
     
     
         24 . The polymer of  claim 23 , wherein the treated solid oxide compound is contacted with at least one additional metal.  
     
     
         25 . The polymer of  claim 24 , wherein the one additional metal is selected from zinc, silver, copper, antimony, gallium, tin, nickel, tungsten, or mixtures thereof.  
     
     
         26 . The polymer of  claim 23 , wherein the polymerization conditions comprise slurry polymerization conditions.  
     
     
         27 . The polymer of  claim 26 , wherein the polymerization takes place in a loop reaction zone.  
     
     
         28 . The polymer of  claim 27 , wherein the polymerization is conducted in the presence of a diluent that comprises, in major part, isobutane.  
     
     
         29 . The polymer of  claim 23 , wherein the catalyst composition has an activity greater than 500 g/g/hr under slurry polymerization conditions, using isobutane as a diluent, with a polymerization temperature of 90° C., and an ethylene pressure of 550 psig.  
     
     
         30 . The polymer of  claim 23 , wherein at least one monomer is ethylene.  
     
     
         31 . The polymer of  claim 23 , wherein the polymer comprises ethylene and at least one aliphatic 1-olefin having 3 to 20 carbon atoms per molecule.  
     
     
         32 . The polymer of  claim 31 , wherein the aliphatic 1-olefin having 3 to 20 carbon atoms per molecule is selected from propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, or 1-octene, or mixture thereof.  
     
     
         33 . The polymer of  claim 23 , wherein at least one monomer is selected from 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, 1,3-butadiene, isoprene, piperylene, 2,3-dimethyl-1,3-butadiene, 1,4-pentadiene, 1,7-hexadiene or mixture thereof.  
     
     
         34 . The polymer of  claim 23 , wherein the organometal compound is selected from bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dichloride, 1,2-ethanediylbis(η 5 -1-indenyl)di-n-butoxyhafnium, 1,2-ethanediylbis(η 5 -1-indenyl)dimethylzirconium, 3,3-pentanediylbis(η 5 -4,5,6,7-tetrahydro-1-indenyl)hafnium dichloride, methylphenylsilylbis(η 5 -4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, bis(n-butylcyclopentadienyl)di-t-butylamido hafnium, bis(n-butylcyclopentadienyl) zirconium dichloride, dimethylsilylbis(1-indenyl)zirconium dichloride, nonyl(phenyl)silylbis(1-indenyl)hafnium dichloride, dimethylsilylbis(η 5 -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, (isopropylamido-dimethylsilyl)cyclopentadienyl titanium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, methyloctylsilylbis(9-fluorenyl)zirconium dichloride, or bis-(1-(N,N-diisopropylamino)boratabenzene)hydridozirconium trifluoromethyl-sulfonate.  
     
     
         35 . The polymer of  claim 34 , wherein the organometal compound is selected from bis(n-butylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, dimethylsilylbis(1-indenyl)zirconium dichloride, or methyloctylsilylbis(9-fluorenyl)zirconium dichloride.  
     
     
         36 . The polymer of  claim 23 , wherein the weight ratio of the post-contacted organoaluminum compound to the post-contacted treated solid oxide compound in the catalyst composition ranges from about 5:1 to about 1:1000.  
     
     
         37 . The polymer of  claim 23 , wherein the weight ratio of the post-contacted treated solid oxide compound to the post-contacted organometal compound in the catalyst composition ranges from about 10,000:1 to about 1:1.  
     
     
         38 . The polymer of  claim 23 , wherein the solid oxide compound is calcined at a temperature in a range of about 200° C. to 900° C., for about 1 minute to about 100 hours, before or after the solid oxide compound is contacted with a zirconium-containing compound.  
     
     
         39 . The polymer of  claim 23 , wherein the halogen is added to the solid oxide compound during or after calcining.  
     
     
         40 . A polymer produced using a polymerization process comprising contacting, under polymerization conditions, at least one monomer and a catalyst composition, the polymer having a HLMI/MI of at least about 50; 
 wherein the catalyst composition is produced by a process comprising contacting at least one organometal compound, at least one organoaluminum compound, and at least one treated solid oxide compound to produce the catalyst composition, wherein the organometal compound has the following general formula:      (X 1 )(X 2 )(X 3 )(X 4 )M 1      wherein M 1  is selected from titanium, zirconium, or hafnium;    wherein X 1  is selected from cyclopentadienyls, indenyls, fluorenyls, substituted cyclopentadienyls, substituted indenyls, or substituted fluorenyls;    wherein substituents on the substituted cylopentadienyls, substituted indenyls, and substituted fluorenyls of X 1  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, or germanium groups;    wherein at least one substituent on X 1  is optionally a bridging group which connects X 1  and X 2 ;    wherein X 3  and X 4  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, substitute alkyloxide groups, aryloxide groups, substituted aryloxide groups, organometallic groups, or substituted organometallic groups;    wherein X 2  is selected from 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, or substituted organometallic groups;    wherein substituents on X 2  are selected from 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, or germanium groups;    wherein at least one substituent on X 2  is optionally a bridging group which connects X 1  and X 2 ;    wherein the 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 about 20 carbon atoms;    wherein X 6  is a halide, hydride, or alkoxide; and    wherein n is a number from 1 to 3 inclusive;    wherein the treated solid oxide compound comprises at least one halogen, zirconium, and a solid oxide compound;    wherein the halogen is at least one selected from chlorine, bromine, or fluorine;    wherein the solid oxide compound is selected from alumina, aluminophosphate, alminosilicate, or mixtures thereof; and    wherein there is a substantial absence of aluminoxanes.    
     
     
         41 . An article that comprises the polymer produced according to  claim 23 .  
     
     
         42 . An article that comprises the polymer produced according to  claim 40 .  
     
     
         43 . The article of  claim 41 , wherein the article is selected from household containers, utensils, film products, drums, fuel tanks, pipes, geomembranes or liners.