Functionalized catalyst supports and supported catalyst systems

Abstract

Functionalized catalyst supports useful in formation of supported catalyst systems for the polymerization of olefins are disclosed. Methods for preparing functionalized catalyst supports and supported catalyst compositions therefrom as well as polymerization processes utilizing such supported catalysts are also disclosed. The functionalized catalyst support comprises a particulated support material having chemically bonded thereto a plurality of non-ionic, Lewis acid, aluminum-containing groups containing at least one fluoro-substituted hydrocarbyl ligand containing from 1 to 20 carbons bonded to the aluminum, said support being capable of activating a Group 3-10 metal complex for the addition polymerization of one or more addition polymerizable monomers.

What is claimed is:  
     
         27 . A supported catalyst comprising: 
 a functionalized catalyst support comprising a particulated support material having chemically bonded thereto a plurality of non-ionic, Lewis acid, aluminum-coating groups containing at least one fluoro-substituted hydrocarbyl ligand containing from 1 to 20 carbons bonded to the aluminum, said composition being capable of activating a Group 3-10 metal complex for the addition polymerization of one or more addition polymerizable monomers; and    a Group 3-10 metal complex containing a substituent which reacts with the functionalized catalyst support to thereby form a composition which is catalytically active for the polymerization of olefins.    
     
     
         28 . A supported catalyst according to claim  27 , wherein the Group 3-10 metal complex contains at least one π-bonded anionic ligand group which is a conjugated or non-conjugated, cyclic or non-cyclic dienyl group, an allyl group, an aryl group, or a substituted derivative thereof.  
     
     
         29 . A supported catalyst according to claim  28 , wherein the 7r-bonded anionic ligand group is a cyclopentadienyl group or a derivative thereof.  
     
     
         36 . A method for preparing a supported catalyst composition comprising 
 (I) preparing a functionalized catalyst support comprising: 
 (a) slurrying a particulated support in a hydrocarbon diluent;  
 (b) adding a compound of the formula, Ar f   z″ Al 2 Ql 6-z″  in sufficient quantity to fully react with surface groups as defined by titration with Et 3 Al, to form a treated support, where  
   Ar f  is a fluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms;    z″ is a number from 0 to 6, and    Q 1  independently each occurrence is selected from the groups consisting of hydrocarbyl-, hydrocarbyloxy-, and dihydrocarbylamido-group, of from 1 to 20 atoms other than hydrogen; 
 (c) washing the treated support with a hydrocarbon liquid, and  
 (d) optionally drying the functionalized catalyst support; and  
   adding to the functionalized catalyst support a Group 3-10 metal complex containing a substituent which reacts with the functionalized catalyst support to thereby form a composition which is catalytically active for the polymerization of olefins.    
     
     
         37 . A polymerization process comprising contacting one or more addition polymerizable monomers under gas phase or slurry polymerization conditions with a catalyst composition according to any of claim  27 ,  28 , or  29 .  
     
     
         38 . A process according to claim  37 , wherein propylene is polymerized to form polypropylene.  
     
     
         39 . A process according to claim  37 , wherein ethylene is polymerized, optionally with one or more α-olefin monomers and/or α,Ω-dienes, to form an ethylene polymer.  
     
     
         40 . A polymerization process comprising contacting one or more addition polymerizable monomers under gas phase or slurry polymerization conditions with a catalyst composition prepared according to claim  36 .  
     
     
         41 . A process according to claim  40  wherein propylene is polymerized to form polypropylene, preferably isotactic polypropylene.  
     
     
         42 . A process according to claim  40 , wherein ethylene is polymerized, optionally with one or more α-olefin monomers and/or α,Ω-dienes, to form an ethylene polymer.  
     
     
         55 . The supported catalyst according to claim  27 , wherein the functionalized catalyst support has a chemical structure of the formula:  
       So[Me m1 (K 1   k1 )(D d )]s  
       wherein: 
 So is a particulated solid support material;  
 Me is aluminum;  
 m1 is a number from 1-20;  
 K 1  independently each occurrence is a ligand group bonded to Me having from 1 to 30 atoms other than hydrogen, with the proviso that in at least one occurrence, K 1  is a fluoro-substituted hydrocarbyl group of from 1 to 20 carbons, and optionally two or more K 1  groups may be bonded together thereby forming a bridging group linking two or more Me atoms or forming a fused ring system;  
 k1 is a number from 1 to 5 selected to provide charge neutrality to the complex;  
 D is a bridging moiety chemically bonded to So by means of which the group, [Me m1 (K 1   k1 )(D d )], is attached to the particulated solid support;  
 d is a positive number from 0 to 5, preferably 1 to 3, more preferably 1, and less than or equal to m, said d equaling the average number of chemical bonds to the substrate per group, [Me m1 (K 1   k1 )(D d )];  
 s is a number greater than or equal to 2 and is equal to the number of [Me m1 (K 1   k1 )(D d )] groups attached to the substrate, So.  
 
     
     
         56 . The supported catalyst according to  claim 55 , wherein the support material is silica, the fluorosubstituted hydrocarbyl group is a fluoroaryl group, and s is chosen to provide a concentration of [Me m1 (K 1   k1 )(D d )] groups on the support from 1×10 −5  μmole/gram to 2 mmole/gram.  
     
     
         57 . The supported catalyst according to  claim 55 , wherein K 1  is pentafluorophenyl and k1 equals 2.  
     
     
         58 . The supported catalyst according to  27  wherein the catalyst comprises a reaction product of: 
 (a) a solid inorganic oxide support material and  
 the ligand exchange product derived from the contacting of the non-ionic Lewis acid which is a trifluoroarylaluminum- or trifluoroarylboron-compound with one or more trihydrocarbylaluminum-, dihydrocarbylaluminumhydrocarbyloxide-, or dihydrocarbylaluminum(dihydrocarbyl)amido-compounds having up to 20 atoms other than hydrogen in each hydrocarbyl-, hydrocarbyloxy- or dihydrocarbylamido group, or a mixture thereof.  
 
     
     
         59 . The method according to claim  36 , where the support has been pretreated with Q 1   3 Al, where Q 1  is independently selected from the group consisting of hydrocarbyl-, hydrocarbyloxy-, or dihydrocarbylamido-groups, of from 1 to 20 atoms other than hydrogen, and the amount of Q 1   3 Al is chosen to pacify 1-99% of any reactive surface species as determined by titration with Et 3 Al.  
     
     
         60 . The method according to  claim 59 , wherein the amount of Q 1   3 Al is chosen to pacify 50-90% of any reactive surface species of the support, as determined by titration with Et 3 Al.  
     
     
         61 . The method according to claim  36 , wherein the support has been pretreated with Q 1   3 Al in a quantity from 0.1 to 1.5 mmol Al/gram support wherein Q 1  is independently selected from the group consisting of hydrocarbyl-, hydrocarbyloxy-, or dihydrocarbylamido-groups, of from 1 to 20 atoms other than hydrogen.  
     
     
         62 . The method according to any one of claim  36 ,  59 ,  60 , or  61  wherein the support is an inorganic oxide.