Processes to Produce Polyalpha-Olefin Compositions

Abstract

A process to produce polyalpha-olefins includes contacting a feed stream of at least one alpha-olefin monomer having 4 to 25 carbon atoms with a metallocene catalyst compound and an activator, and optionally an alkyl-aluminum compound, under polymerizations conditions in a reactor. The alpha-olefin monomer is present at 10% volume or more in the reactor and the feed stream includes less than 600 ppm of heteroatom containing compounds. The process further includes obtaining a polyalpha-olefin with at least 50 mole % C5 to C24 alpha-olefin monomer and kinematic viscosity at 100° C. of 5000 cSt or less.

1 .- 120 . (canceled) 
     
     
         121 . A process to produce a polyalpha-olefin comprising:
 contacting a feed stream comprising at least one alpha-olefin monomer having 5 to 24 carbon atoms with a metallocene catalyst compound and an activator, and optionally an alkyl-aluminum compound, under polymerization conditions wherein the alpha-olefin monomer having 5 to 24 carbon atoms is present at 10 volume % or more (based upon the total volume of the catalyst, monomers, and any diluents or solvents present) in the reactor and where the feed stream comprises less than 600 ppm of heteroatom containing compounds; and   obtaining a polyalpha-olefin comprising at least 50 mole % of a C5 to C24 alpha-olefin monomer where the polyalpha-olefin has Kinematic viscosity at 100° C. of 5000 cSt or less.   
     
     
         122 . The process of  claim 121  wherein the metallocene catalyst compound is a racemic, bridged metallocene catalyst compound. 
     
     
         123 . The process of  claim 121  wherein the metallocene comprises one or more of dimethylsilylbis(cyclopentadienyl)zirconium dichloride; isopropylidenebis(cyclopentadienyl)zirconium dichloride; rac-ethylenebis(1-indenyl)zirconium dichloride; rac-dimethylsilylbis(tetrahydroindenyl)zirconium dichloride; diphenylmethylidene(cylcopentadienyl)(9-fluorenyl)zirconium dichloride; bis(indenyl)zirconium dichloride; cyclopentadienyl(indenyl)zirconium dichloride; bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride; bis(1,3-dimethylcyclopentadienyl)zirconium dichloride; bis(tetramethylcyclopentadienyl)zirconium dichloride; or bis(pentamethylcyclopentadienyl)zirconium dichloride. 
     
     
         124 . The process of  claim 121  where the metallocene is selected from the group consisting of rac-dimethylsilylbis(tetrahydroindenyl)ZrX 2 , meso-ethylidenebis(indenyl)ZrX 2 , (R n Cp) 2 ZrX 2  or (R m Ind) 2 ZrX 2 ), ethylidenebis(R n Cp) 2 ZrX 2 , dimethylsilylbis(R n Cp) 2 ZrX 2 , ethylidenebis(R n Ind) 2 ZrX 2 , dimethylsilylbis(R n Ind) 2 ZrX 2 ,
 wherein X is a halogen, a substituted or unsubstituted phenyl group, or a C1 to C20 alkyl, Cp is a cyclopentadienyl ring, R is a C1 to C20 alkyl group, n is a number denoting the degree of substitution of Cp and is a number from 0 to 5, Ind is an indenyl ring, m is a number denoting the degree of substitution of Ind and is a number from 0 to 7. 
 
     
     
         125 . The process of  claim 121  further comprising:
 optionally treating the polyalpha-olefin to reduce heteroatom containing compounds to less than 600 ppm; 
 optionally separating the polyalpha-olefins from solvents or diluents; 
 contacting the polyalpha-olefin with hydrogen and a hydrogenation catalyst; and 
 obtaining a polyalpha-olefin having a bromine number less than 1.8. 
 
     
     
         126 . The process of  claim 125  wherein the polyalpha-olefin is treated to remove heteroatom containing compounds prior to contacting with the hydrogen and or the hydrogenation catalyst and wherein the treated polyalpha-olefin comprises 10 ppm of heteroatom containing compounds or less. 
     
     
         127 . The process of  claim 121  wherein the activator comprises methylalumoxane and or modified methylalumoxane. 
     
     
         128 . The process of  claim 121  wherein the activator comprises one or more of N,N-dimethylanilinium tetra(pentafluorophenyl)borate, N,N-dialkylphenylanilinium tetra(pentafluorophenyl)borate (where the alkyl is a C1 to C18 alkyl group), trityl tetra(pentafluorophenyl)borate, tris(pentafluorophenyl)boron, tri-alkylammonium tetra(pentafluorophenyl)borate (where the alkyl is a C1 to C18 alkyl group), tetra-alkylammonium tetra(pentafluorophenyl)borate (where the alkyl is a C1 to C18 alkyl group). 
     
     
         129 . The process of  claim 121  wherein the process is a continuous process comprising:
 continuously introducing a feed stream comprising at least 10 mole % of the one or more C5 to C24 alpha-olefins into a reactor, 
 continuously introducing the metallocene compound and the activator into the reactor, 
 optionally continuously introducing co-activator into the reactor, and 
 continuously withdrawing the polyalpha-olefin from the reactor. 
 
     
     
         130 . The process of  claim 129  further comprising maintaining a concentration of hydrogen in the reactor of 1000 ppm or less by weight. 
     
     
         131 . The process of  claim 129  wherein the process further comprises:
 optionally, continuously treating the polyalpha-olefin to reduce heteroatom containing compounds to less than 600 ppm; 
 continuously contacting the polyalpha-olefin with hydrogen and a hydrogenation catalyst; and 
 continuously obtaining a polyalpha-olefin having a bromine number less than 1.8. 
 
     
     
         132 . The process of  claim 121  wherein two monomers having 5 to 18 carbon atoms are present in the polyalpha-olefin. 
     
     
         133 . The process of  claim 121  wherein the temperature is from 70° C. to 150° C. 
     
     
         134 . The process of  claim 133  wherein the pressure is from 1 to 50 atmospheres. 
     
     
         135 . The process of  claim 134  wherein the feed stream, metallocene and activator are contacted for a residence time of 1 minute to 1 hour. 
     
     
         136 . The process of  claim 121  wherein solvent or diluent selected from the group consisting of butanes, pentanes, hexanes, heptanes, octanes, nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, benzene, toluene, o-xylenes, m-xylenes, p-xylenes, ethylbenzene, isopropylbenzene, and n-butylbenzene is present. 
     
     
         137 . The process of  claim 121  wherein the metallocene and activator are combined prior to entering the reactor with an alkylaluminum compound represented by the formula: R 3 Al, wherein each R is independently a C1 to C20 alkyl group and can be n-alkyl or iso-alkyl group. 
     
     
         138 . The process of  claim 137  wherein the R groups are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-butyl, pentyl, isopentyl, n-pentyl, hexyl, isohexyl, n-hexyl, heptyl, octyl, isocotyl, n-octyl, nonyl, isononyl, n-nonyl, decyl, isodecyl, n-cecyl, undecyl, isoundecyl, n-undecyl, dodecyl, isododecyl, and n-dodecyl. 
     
     
         139 . The process of  claim 121  wherein ethylene is present in the monomer feed at from 0.5 to 10 mole %. 
     
     
         140 . The process of  claim 121  where the feed olefins are contacted with molecular sieve, activated alumina, silica gel, oxygen removing catalyst, and or purifying clays to reduce the heteroatom-containing compounds in the feed to below 10 ppm. 
     
     
         141 . The process of  claim 121  wherein the polyalpha-olefin is contacted with hydrogen and a hydrogenation catalyst at a temperature from 100 to 300° C., for a time period from 5 minutes to 24 hours, and at a hydrogen pressure of from 100 to 2000 psi. 
     
     
         142 . The process of  claim 141  wherein the hydrogenation catalyst is selected from the group consisting of one or more of Ni, Pd, Pt, Co, Rh, Fe, Ru, Os, Cr, Mo, and W, supported on silica, alumina, clay, titania, zirconia, or mixed metal oxide supports. 
     
     
         143 . A process to reduce the mole % of mm triad groups in a hydrogenated polyalpha-olefin comprising contacting a polyalpha-olefin with a hydrogenation catalyst and hydrogen and recovering the hydrogentated polyalpha-olefin having from 1 to 80% less mm triad groups than the polyalpha-olefin prior to contact with the hydrogen and hydrogenation catalyst;
 wherein the polyalpha-olefin comprises more than 50 mole % of one or more C5 to C24 alpha-olefin monomers where the polyalpha-olefin has Z mole % or more of units represented by the formula:   
       
         
           
           
               
               
           
         
         where j, k and m are each, independently, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, n is an integer from 1 to 350, and 
         where Z=8.420*Log(V)−4.048, where V is the kinematic viscosity of the polyalpha-olefin measured at 100° C. in cSt. 
       
     
     
         144 . The process of  claim 143  wherein the hydrogenated polyalpha-olefin has from 25 to 70 mole % mm triads. 
     
     
         145 . The process of  claim 144  wherein the hydrogenated polyalpha-olefin has a bromine number of less than 0.5.