Solid metallocene catalyst system

Abstract

A solid metallocene-containing catalyst system of an organoaluminoxane, at least one metallocene having at least one olefinically unsaturated substituent and a polyolefin is disclosed. The polyolefin is formed from at least one olefin polymerized in the presence of a combination of a solution of the organoluminoxane in an aromatic liquid, the at least one metallocene, and an aliphatic liquid. The solid metallocene-containing catalyst system may also include one or more the particulate solids.

1 - 30 . (canceled)  
     
     
         31 . A polymer produced using a polymerization process comprising contacting, under polymerization conditions, at least one monomer and a solid prepolymerized catalyst system, wherein the solid prepolymerized catalyst system is produced by 
 (a) combining an aromatic solution comprising an organoaluminoxane dissolved in an aromatic liquid, at least one metallocene having at least one olefinically unsaturated substituent, an aliphatic liquid, and, optionally, a solid particulate support to form a liquid catalyst system;    (b) conducting prepolymerization of at least one olefin in the presence of the liquid catalyst system to produce a prepolymerized solid catalyst; and    (c) separating the resulting solid from the liquid and components dissolved in the liquid.    
     
     
         32 . The polymer of  claim 31 , wherein the liquid catalyst system is formed by combining the aromatic solution with the at least one metallocene and then combining the resulting composition with an aliphatic liquid.  
     
     
         33 . The polymer of  claim 31 , wherein the liquid catalyst system is formed by combining the aromatic solution with the aliphatic liquid and then combining the resulting composition with the at least one metallocene.  
     
     
         34 . The polymer of  claim 31 , wherein the solid particulate support is talc, an inorganic oxide, a resinous particulate, one or more oxides of metals of Groups II, III, IV or V of the Periodic Table, or any combination thereof.  
     
     
         35 . The polymer of  claim 31 , wherein the at least one olefin is ethylene, a mixture of ethylene and 1-butene, or a mixture of ethylene and an alpha olefin having 3 or more carbon atoms.  
     
     
         36 . The polymer of  claim 31 , wherein the at least one olefin is ethylene or a non-aromatic alpha-olefin.  
     
     
         37 . The polymer of  claim 31 , wherein the 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-decene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, 3,4-dimethyl-1-hexene, or any combination thereof.  
     
     
         38 . The polymer of  claim 31 , wherein step (a) is conducted in the presence of a bridged metallocene having olefinic unsaturation in a branch extending outwardly from the bridge, the bridging ligand of said metallocene having the formula  
       
         
           
           
               
               
           
         
         n is 1 or 0;  
         R iv  is Si, Ge, C, or Sn;  
         each R′ is individually selected from hydrogen or hydrocarbyl radicals having 1 to 10 carbons;  
         R″ is selected from hydrocarbyl diradicals containing 1 to 10 carbons;  
         R′″ is selected from hydrogen or hydrocarbyl groups containing 1 to 10 carbons; and  
         Z is the same or different and is independently selected from substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl, or fluorenyl radicals.  
       
     
     
         39 . The polymer  claim 31 , wherein the metallocene is a compound of the formula R x (Z)(Z)MQ k , wherein: 
 each Z is bound to M, and is a cyclopentadienyl-type ligand independently selected from substituted or unsubstituted cyclopentadienyl, indenyl, tetrahydroindenyl, octahydrofluorenyl, or fluorenyl ligands;    R is a structural bridge linking the Z's;    M is a metal selected from IVB, VB, and VIB metals of the periodic table;    each Q is the same or different and is selected from hydrogen, halogens, or organoradicals;    x is 1 or 0; and    k is a number sufficient to fill out the remaining balances of M.    
     
     
         40 . The polymer of  claim 39 , wherein at least one Z has at least one olefinically unsaturated substituent attached.  
     
     
         41 . The polymer of  claim 40 , wherein the metallocene is a bridged metallocene and the olefinically unsaturated substituent is a branch on the bridging unit or on one or both of the cyclopentadienyl-type groups of the bridged ligands.  
     
     
         42 . The polymer of  claim 39 , wherein Q is an organo radical selected from aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radicals.  
     
     
         43 . The polymer of  claim 31 , wherein the metallocene is a bridged metallocene having an olefinically unsaturated substituent of the formula  
       
         
           
           
               
               
           
         
         R″ is a hydrocarbyl diradical having 1 to 20 carbon atoms;  
         n is 1 or 0; and  
         R′ is independently selected from organo radicals having 1 to 10 carbon atoms or hydrogen.  
       
     
     
         44 . The polymer of  claim 31 , wherein the aliphatic liquid is present an amount to produce a volume ratio of the aliphatic liquid to the aromatic solution of organoaluminoxane of at least about 5:1.  
     
     
         45 . The catalyst system as claimed in  claim 31 , wherein the aromatic liquid is selected from benzene, toluene, ethylbenzene, or diethylbenzene.  
     
     
         46 . The polymer of  claim 31 , wherein the aliphatic liquid is selected from pentane, isopentane, hexane, octane, or heptane.  
     
     
         47 . The polymer of  claim 31 , wherein the at least one metallocene is 5-(9-fluorenyl)-5-(cyclopentadienyl)-hexene-1 zirconium dichloride, the organoaluminoxane is methylaluminoxane, the aromatic liquid is toluene, and the aliphatic liquid is hexane.  
     
     
         48 . The polymer of  claim 31 , wherein the polymerization conditions comprise slurry polymerization conditions, gas phase polymerization conditions, or solution polymerization conditions.  
     
     
         49 . The polymer of  claim 48 , wherein the slurry polymerization is conducted in a loop reactor.  
     
     
         50 . The polymer of  claim 49 , wherein the monomer and the solid prepolymerized catalyst system are contacted in the presence of a diluent selected from propane, butane, isobutane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, toluene, xylene, or any combination thereof.