Selective olefin dimerization with supported metal complexes activated by alkylaluminum compounds or ionic liquids

Abstract

Methods for dimerizing alpha-olefins utilizing immobilized buffered catalysts wherein the catalytic component is of the form: where X is a halogen, n=2 or 3, M=Ti, V, Cr, Mn, Fe, Co and Ni and R1, R2, R3 and R4 are selected from the group consisting of hydrogen, alkyl, aryl, alkenyl, alkinyl, alkyloxy, substituted aryl, and X are provided. A method for dimerizing alpha-olefins utilizing the immobilized buffered catalysts and a co-catalyst is also provided.

What is claimed is: 
     
         1 - 9 . (canceled) 
     
     
         10 . A process for the dimerization of olefins comprising the steps of:
 modifying a support material containing OH groups with air alkylaluminum compound to form a modified support material;   mixing an organometallic complex of the formula   
       
         
           
           
               
               
           
         
       
       where X is a halogen, n=2 or 3, M=Ti, V, Cr, Mn, Co and Ni and R1, R2, R3 and R4 are selected from the group consisting of hydrogen, and X with one or more co-catalysts selected from the group of MAO and B(C 6 Fi) 3  and with the modified support material to form a combined catalyst; and
 mixing the combined catalyst with one or more alpha-olefins. 
 
     
     
         11 . The process of  claim 10  wherein the alkylaluminum compound is chloroethylaluminum. 
     
     
         12 . The process of  claim 10  wherein the support is silica, zeolite, partially hydrolyzed trimethylaluminum, or a mixture thereof. 
     
     
         13 . The process of  claim 10  wherein the one more alpha-olefins is selected from the group alkenes having between three and ten carbon atoms. 
     
     
         14 . The process of  claim 10  wherein the olefin dimerization is conducted in a fixed bed reactor. 
     
     
         15 . (canceled) 
     
     
         16 . A process for the dimerization of olefins comprising the steps of:
 modifying a support material containing —H groups with an alkylaluminum compound to form a modified support material;   mixing an ionic liquid having a melting point below about 100° C. with a buffer to form a buffered ionic liquid;   mixing the buffered ionic liquid with an organometallic complex of the formula   
       
         
           
           
               
               
           
         
       
       where X is a halogen, n=2 or 3, M=Fe and R1, R2, R3 and R4 are selected from hydrogen and X, and at least one of R1 and R2=X, to form a buffered ionic liquid/catalyst complex;
 mixing the buffered ionic liquid/catalyst complex with the modified support material to form an immobilized buffered catalyst; and 
 mixing the immobilized buffered catalyst with one or more alpha-olefins. 
 
     
     
         17 . The process of  claim 16  wherein M=Fe, X=Cl, n=3 and up to three of R1, R2, R3 and R4=hydrogen. 
     
     
         18 . The process of  claim 16  wherein the one or more alpha-olefins is selected from the group alkenes having between five and ten carbon atoms. 
     
     
         19 . The process of  claim 16  wherein the ionic liquid comprises a salt selected from the group consisting of AlCl 3 AlRCl 2  and AlR 2 Cl, where R is an alkyl chain. 
     
     
         20 . The process of  claim 16  wherein the ionic liquid comprises a cation selected from the group consisting of ammonium, imidazolium, sulfonium and phosphonium salts. 
     
     
         21 . The process of  claim 16  wherein the alkylaluminum compound is a chloroethylaluminum. 
     
     
         22 . The process of  claim 16  wherein the support is silica, zeolite, partially hydrolyzed trimethylaluminum, or a mixture thereof. 
     
     
         23 . The process of  claim 16  wherein the step of mixing the immobilized buffered catalyst with one or more alpha-olefins is conducted in a fixed bed reactor. 
     
     
         24 . The process of  claim 16  wherein the alpha-olefin dimerization reaction comprises 1,2- or 2,1-insertion. 
     
     
         25 . The process of  claim 16  further comprising drying the immobilized buffered catalyst to form a powder prior to the mixing the immobilized buffered catalyst with one or more alpha-olefins. 
     
     
         26 . A process for the dimerization of olefins comprising the steps of:
 modifying a support material containing OH groups with an alkylaluminum compound to form a modified support material;   mixing an organometallic complex of the formula   
       
         
           
           
               
               
           
         
       
       where X is a halogen, n=3, M=Fe and R1, R2, R3 and R4 are selected from the group consisting of hydrogen and X, and at least one of R1 and R2=X, with one or more co-catalysts selected from the group of MAO and B(C 6 F 5 ) 3  and with the modified support material to form a combined catalyst; and
 mixing the combined catalyst with one or more alpha-olefins. 
 
     
     
         27 . The process of  claim 26  wherein the alkylaluminum compound is a chloroethylaluminum. 
     
     
         28 . The process of  claim 26  wherein the support is silica, zeolite, partially hydrolyzed trimethylaluminum, or a mixture thereof. 
     
     
         29 . The process of  claim 26  wherein the one or more alpha-olefins is selected from the group alkenes having between three and ten carbon atoms. 
     
     
         30 . The process of  claim 26  wherein the olefin dimerization is conducted in a fixed bed reactor.