Metallocene Dimer Selective Catalysts and Processes to Produce Poly Alpha-Olefin Dimers

Abstract

The present disclosure generally relates to processes to produce alpha-olefin oligomers and poly alpha-olefins. In an embodiment, the present disclosure provides a process to produce a poly alpha-olefin (PAO), the process including:introducing a C6-C32 alpha-olefin and a catalyst system comprising activator and a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under reaction conditions, wherein the alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more; andobtaining a product comprising PAO dimer and optional higher oligomers of alpha-olefin, or a combination thereof, the PAO dimer comprising 96 mol % or more of vinylidene, based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product. In at least one embodiment, a process includes functionalizing and/or hydrogenating a PAO product of the present disclosure. In at least one embodiment, a blend includes a PAO product of the present disclosure.

What is claimed is: 
     
         1 . A process to produce a poly alpha-olefin (PAO), the process comprising:
 introducing a C 6 -C 32  alpha-olefin and a catalyst system comprising activator and a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under reaction conditions, wherein the alpha-olefin is introduced to the reactor at a flow rate of at least 100 g/hr; and   obtaining a product comprising PAO dimer and optional higher oligomers of alpha-olefin, or a combination thereof, the PAO dimer comprising 96 mol % or more of vinylidene, based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product, and the metallocene compound is represented by the formula:   
       
         
           
           
               
               
           
         
       
       wherein:
 each of R 1 , R 2 , and R 3  is independently hydrogen, a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 20  hydrocarbyl group, wherein at least one of R 1 , R 2 , and R 3  is not hydrogen and at least one of R 1 , R 2 , and R 3  is hydrogen; 
 each of R 4 , R 5 , R 6 , and R 7  is independently hydrogen, a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 30  hydrocarbyl group, or one or more of R 4  and R 5 , R 5  and R 6 , or R 6  and R 7 , taken together with the carbon atoms in the indenyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings fused to the indenyl ring; 
 each of R 8 , R 9 , R 10 , R 11 , and R 12  is independently a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 30  hydrocarbyl, silylcarbyl, or germanyl group; 
 M is a group 3, 4 or 5 transition metal; 
 each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C 1 -C 20  substituted or unsubstituted linear, branched linear, or cyclic hydrocarbyl group, or optionally two or more X moieties may together form a fused ring or ring system; and 
 m is an integer equal to 1, 2, or 3. 
 
     
     
         2 . The process of  claim 1 , wherein the metallocene compound is represented by the formula: 
       
         
           
           
               
               
           
         
         wherein:
 each of R 1 , R 2 , and R 3  is independently hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 20  hydrocarbyl or silylcarbyl group; 
 each of R 4  and R 7  is independently a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 30  hydrocarbyl or silylcarbyl group; 
 each of R 8 , R 9 , R 10 , R 11 , and R 12  is independently a hydrogen, or a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 20  hydrocarbyl, silylcarbyl, or germanyl group, or optionally at least three of R 8 , R 9 , R 10 , R 11 , and R 12  are not hydrogen; 
 each of R 13 , R 14 , R 15 , R 16 , R 17 , and R 18  is independently hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 20  hydrocarbyl or silylcarbyl group; 
 M is a group 3, 4 or 5 transition metal; 
 each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C 1 -C 20  substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties may together form a fused ring or ring system; and 
 m is an integer equal to 1, 2, or 3. 
 
       
     
     
         3 . The process of  claim 1 , wherein the reaction conditions comprise a reactor temperature of about 120° C. or greater and a reactor pressure of from 15 psia to 750 psia. 
     
     
         4 . The process of  claim 1 , wherein the reaction conditions comprise a catalyst loading of at least 10,000 g alpha-olefin (gAO) per gram of catalyst (gCat). 
     
     
         5 . The process of  claim 1 , wherein the reaction conditions comprise a flow rate of the catalyst system of at least 6 gCat/hr. 
     
     
         6 . The process of  claim 1 , wherein the reaction conditions comprise a reactor residence time of less than 5 hours. 
     
     
         7 . The process of  claim 1 , wherein the product further comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product:
 up to 4 mol % trisubstituted vinylene,   up to 4 mol % disubstituted vinylene, or   up to 4 mol % trisubstituted vinylene and disubstituted vinylene.   
     
     
         8 . The process of  claim 7 , wherein the product comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product:
 98 mol % or more vinylidene, and   up to 2 mol % trisubstituted vinylene,   up to 2 mol % disubstituted vinylene, or   up to 2 mol % trisubstituted vinylene and disubstituted vinylene.   
     
     
         9 . The process of  claim 8 , wherein the product comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product:
 98 mol % or more vinylidene, and   up to 1 mol % trisubstituted vinylene,   up to 1 mol % disubstituted vinylene, or   up to 1 mol % trisubstituted vinylene and disubstituted vinylene.   
     
     
         10 . The process of  claim 9 , wherein the product comprises, based on total moles (100 mol %) of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product:
 98 mol % or more vinylidene, and   up to 0.5 mol % trisubstituted vinylene,   up to 0.5 mol % disubstituted vinylene, or   up to 0.5 mol % trisubstituted vinylene and disubstituted vinylene.   
     
     
         11 . The process of  claim 1 , wherein each of R 1 , R 2 , and R 3  is independently hydrogen or a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 6  hydrocarbyl group. 
     
     
         12 . The process of  claim 11 , wherein one of R 1 , R 2 , and R 3  is a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 6  hydrocarbyl group, and two of R 1 , R 2 , and R 3  are hydrogen. 
     
     
         13 . The process of  claim 1 , wherein M is Hf. 
     
     
         14 . The process of  claim 1 , wherein the metallocene compound is represented by the formula: 
       
         
           
           
               
               
           
         
       
       or a combination thereof. 
     
     
         15 . The process of  claim 1 , wherein the activator comprises one or more of:
 N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,   N,N-dimethylanilinium tetrakis(perfluoro-naphthyl)borate,   triphenylcarbonium tetrakis(perfluorophenyl)borate,   triphenylcarbonium tetrakis(perfluoronaphthyl)borate,   N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate,   N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate,   alumoxane,   a modified alumoxane, and   an aluminum alkyl.   
     
     
         16 . The process of  claim 1 , wherein the C 6 -C 32  alpha-olefin is selected from the group consisting of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, and combinations thereof. 
     
     
         17 . The process of  claim 1 , wherein the C 6 -C 32  alpha-olefin is selected from the group consisting of 1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and combinations thereof. 
     
     
         18 . The process of  claim 1 , wherein the reaction conditions comprise a reactor temperature of from 130° C. to 180° C., a reactor pressure of from 15 psia to 750 psia, and a catalyst loading of from 25,000 g alpha-olefin (gAO) per 1 g catalyst (gCat) to 90,000 gAO/gCat. 
     
     
         19 . The process of  claim 18 , wherein the reactor conditions comprise a reactor temperature of from 130° C. to 148° C., a reactor pressure of from 30 psia to 100 psia, and a catalyst loading of from 25,000 g alpha-olefin (gAO) per 1 g catalyst (gCat) to 80,000 gAO/gCat. 
     
     
         20 . The process of  claim 1 , further comprising functionalizing the PAO dimer with a reactant to form a functionalized PAO product followed by hydrogenation. 
     
     
         21 . The process of  claim 20 , wherein the reactant is a naphthalene and the functionalized PAO product is a naphthalene PAO dimer adduct. 
     
     
         22 . The process of  claim 20 , wherein the reactant is an anisole and the functionalized PAO product is an anisole PAO dimer adduct. 
     
     
         23 . The process of  claim 1 , further comprising hydrogenating the product. 
     
     
         24 . A lubricant comprising the PAO dimer produced in  claim 1 , a functionalized derivative thereof, a hydrogenated derivative thereof, or a hydrogenated functionalized derivative thereof. 
     
     
         25 . A fuel comprising the PAO dimer produced in  claim 1 , a functionalized derivative thereof, a hydrogenated derivative thereof, or a hydrogenated functionalized derivative thereof. 
     
     
         26 . A driveline or electric vehicle fluid comprising the PAO dimer produced in  claim 1 , a functionalized derivative thereof, a hydrogenated derivative thereof, or a hydrogenated functionalized derivative thereof. 
     
     
         27 . An engine oil comprising the PAO dimer produced in  claim 1 , a functionalized derivative thereof, a hydrogenated derivative thereof, or a hydrogenated functionalized derivative thereof. 
     
     
         28 . A gear oil comprising the PAO dimer produced in  claim 1 , a functionalized derivative thereof, a hydrogenated derivative thereof, or a hydrogenated functionalized derivative thereof. 
     
     
         29 . A compressor oil comprising the PAO dimer produced in  claim 1 , a functionalized derivative thereof, a hydrogenated derivative thereof, or a hydrogenated functionalized derivative thereof. 
     
     
         30 . A process to produce a lubricant comprising a poly alpha-olefin (PAO), the process comprising:
 1) introducing a C 6 -C 32  alpha-olefin and a catalyst system comprising activator and a metallocene compound into a reactor under reaction conditions and obtaining a product comprising PAO dimer and optional higher oligomers of alpha-olefin, or a combination thereof, the PAO dimer comprising 96 mol % or more of vinylidene, based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the product, and the metallocene compound is represented by the formula:   
       
         
           
           
               
               
           
         
       
       wherein:
 each of R 1 , R 2 , and R 3  is independently hydrogen, a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 20  hydrocarbyl group, wherein at least one of R 1 , R 2 , and R 3  is not hydrogen and at least one of R 1 , R 2 , and R 3  is hydrogen; 
 each of R 4 , R 5 , R 6 , and R 7  is independently hydrogen, a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 30  hydrocarbyl group, or one or more of R 4  and R 5 , R 5  and R 6 , or R 6  and R 7 , taken together with the carbon atoms in the indenyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings fused to the indenyl ring; 
 each of R 8 , R 9 , R 10 , R 11 , and R 12  is independently a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 30  hydrocarbyl, silylcarbyl, or germanyl group; 
 M is a group 3, 4 or 5 transition metal; 
 each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C 1 -C 20  substituted or unsubstituted linear, branched linear, or cyclic hydrocarbyl group, or optionally two or more X moieties may together form a fused ring or ring system; and 
 m is an integer equal to 1, 2, or 3; and 
 2) hydrogenating at least a portion of the product from the first oligomerization to form a lubricant. 
 
     
     
         31 . A functionalized PAO comprising the reaction product of: 1) a heteroatom containing group, and 2) a PAO having an Mn of 300 g/mol or less (measured by  1 H NMR), wherein the heteroatom containing group comprises one or more heteroatoms selected from the group consisting of P, O, S, N, Br, Cl, F, I and or B. 
     
     
         32 . A functionalized PAO comprising the reaction product of: 1) a heteroatom containing group, and 2) a PAO having an Mn of 300 g/mol or less (measured by  1 H NMR), wherein the heteroatom containing group comprises one or more sulfonates, amines, aldehydes, esters, alcohols, epoxides, anhydrides, carbonyls, or acids. 
     
     
         33 . The functionalized PAO of  claim 32 , wherein the heteroatom containing group comprises one or more succinic acid, maleic acid, or maleic anhydride, alternately the heteroatom containing group comprises one or more of acids, esters, anhydrides, acid-esters, oxycarbonyls, formyls, formylcarbonyls, hydroxyls, and acetyl halides. 
     
     
         34 . A process for making functionalized PAO comprising:
 1) a first process for making a PAO, said first process having productivity of at least 4500 g/mmol/hr, wherein the first process comprises: contacting, at a temperature of from 35° C. to 150° C., one or more C6 to C32 alpha-olefins and a catalyst system comprising an activator and at least one metallocene compound represented by the formula:   
       
         
           
           
               
               
           
         
       
       wherein:
 each of R 1 , R 2 , and R 3  is independently hydrogen, a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 20  hydrocarbyl group, wherein at least one of R 1 , R 2 , and R 3  is not hydrogen and at least one of R 1 , R 2 , and R 3  is hydrogen; 
 each of R 4 , R 5 , R 6 , and R 7  is independently hydrogen, a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 30  hydrocarbyl group, or one or more of R 4  and R 5 , R 5  and R 6 , or R 6  and R 7 , taken together with the carbon atoms in the indenyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings fused to the indenyl ring; 
 each of R 8 , R 9 , R 10 , R 11 , and R 12  is independently a substituted or unsubstituted linear, branched linear, or cyclic C 1 -C 30  hydrocarbyl, silylcarbyl, or germanyl group; 
 M is a group 3, 4 or 5 transition metal; 
 each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C 1 -C 20  substituted or unsubstituted linear, branched linear, or cyclic hydrocarbyl group, or optionally two or more X moieties may together form a fused ring or ring system; and 
 m is an integer equal to 1, 2, or 3; and 
 2) a second process comprising contacting at least a portion of the PAO produced in the first process with a functionalizing species to form a functionalized PAO. 
 
     
     
         35 . The process of  claim 34 , wherein said functionalizing species is selected from the group consisting of aromatic compounds, benzene, toluene, xylenes, naphthalene, alkylnaphthalene, maleic anhydride, organic amine, organic acid and alcohol. 
     
     
         36 . The process of  claim 35 , further comprising hydrogenating at least a portion of said functionalized PAO to form a hydrogenated PAO, then formulating a lubricating composition comprising the hydrogenated PAO into a gear oil, hydraulic fluid, compressor oil, cooling fluid, engine oil, driveline or electric vehicle fluid. 
     
     
         37 . The process of  claim 34 , further comprising functionalizing at least a portion of said functionalized PAO, then formulating a lubricating composition comprising the functionalized PAO into a gear oil, hydraulic fluid, compressor oil, cooling fluid, engine oil, driveline or electric vehicle fluid. 
     
     
         38 . The process of  claim 34 , further comprising partially hydrogenating said functionalized PAO, then further functionalizing at least a portion of said PAO to form a PAO product, then formulating a lubricating composition comprising the PAO product into a gear oil, hydraulic fluid, compressor oil, cooling fluid, engine oil, driveline or electric vehicle fluid. 
     
     
         39 . The process of  claim 34 , further comprising functionalizing at least a portion of said functionalized PAO to form a second functionalized PAO; hydrogenating said second functionalized PAO to form a PAO product; then formulating a lubricating composition comprising the PAO product into a gear oil, hydraulic fluid, compressor oil, cooling fluid, engine oil, driveline or electric vehicle fluid. 
     
     
         40 . A continuous process to produce a poly alpha-olefin, PAO, comprising:
 contacting a feed containing a C 6 -C 32  alpha-olefin with a catalyst system comprising activator and a metallocene compound in a polymerization reactor, optionally a continuous stirred tank reactor or a continuous tubular reactor, under polymerization conditions, where, optionally, the alpha-olefin is introduced to the reactor at a flow rate of at least 100 g/hr;   obtaining an unsaturated PAO product comprising poly alpha-olefin dimer, wherein the process has a conversion of at least 60%, based upon the weight of the monomer entering the reactor and the PAO produced and a selectivity for dimer of at least 85 wt %, based upon the PAO produced;   wherein the metallocene compound is represented by formula (Z):   
       
         
           
           
               
               
           
         
       
       wherein:
 each R 1 , R 2 , and R 3  is, independently, hydrogen or a substituted or unsubstituted linear, branched (such as branched linear), or cyclic C 1 -C 20 , preferably C 1 -C 8 , hydrocarbyl group, wherein one of R 1 , R 2 , and R 3  is a substituted or unsubstituted linear, branched (such as branched linear), or cyclic C 1 -C 20 , preferably C 1 -C 8 , hydrocarbyl group, and either (i) two of R 1 , R 2 , and R 3  are each a hydrogen, or (ii) one of R 1 , R 2 , and R 3  is a hydrogen or a substituted or unsubstituted linear, branched (such as branched linear), or cyclic C 1 -C 20 , preferably C 1 -C 8 , hydrocarbyl group, and one of R 1 , R 2 , and R 3 , taken together with R 16 , is a bridging group connecting the first and second cyclopentadienyl rings; 
 R 4  and R 5  are each independently a substituted or unsubstituted linear, branched (such as branched linear), or cyclic C 1 -C 30  hydrocarbyl group, or R 4  and R 5 , taken together with the carbon atoms in the first cyclopentadienyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings annelated to the first cyclopentadienyl ring; 
 R 12 , R 13 , R 14 , and R 15  are each independently a hydrogen, or a substituted or unsubstituted linear, branched (such as branched linear), or cyclic C 1 -C 20 , preferably C 1 -C 8 , hydrocarbyl group; and 
 R 16  is a hydrogen, a substituted or unsubstituted linear, branched (such as branched linear), or cyclic C 1 -C 20 , preferably C 1 -C 8 , hydrocarbyl group, substituted silyl or substituted germanyl group, or, taken together with one of R 1 , R 2 , and R 3 , is a bridging group connecting the first and second cyclopentadienyl rings, optionally at least three of R 12 , R 13 , R 14 , R 15 , and R 16  are not hydrogen, optionally two or more of R 12 , R 13 , R 14 , R 15  and R 16  moieties may together form a fused ring or ring system, provided that the fused ring or ring system is not unsaturated when R 1  is bridged to R 16 , and where R 2  is not Me when R 1  or R 3  is bridged to R 16 ; 
 M is a transition metal having an integer valency of v; 
 each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C 1 -C 20  substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties may together form a fused ring or ring system; and 
 m is an integer equal to v-2. 
 
     
     
         41 . The process of  claim 40 , wherein one of R 1 , R 2 , and R 3  is a substituted or unsubstituted linear, branched (such as branched linear), or cyclic C 1 -C 6  hydrocarbyl group, and two of R 1 , R 2 , and R 3  are each a hydrogen. 
     
     
         42 . The process of  claim 40 , wherein one of R 1  and R 3  is a substituted or unsubstituted linear, branched (such as branched linear), or cyclic C 1 -C 6  hydrocarbyl group, R 2  is a hydrogen, and one of R 1  and R 3  is a substituted or unsubstituted linear, branched (such as branched linear), or cyclic C 1 -C 6  hydrocarbyl group, or, taken together with R 16 , is a bridging group connecting the first and second cyclopentadienyl rings. 
     
     
         43 . The process of  claim 42 , wherein the bridging group comprises: 
       
         
           
           
               
               
           
         
       
       where each G4, the same or different at each occurrence, is independently carbon, silicon, or germanium, and R 17 , the same or different at each occurrence, is each independently a C 1 -C 20 , preferably C 1 -C 8 , substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group. 
     
     
         44 . The process of  claim 40 , wherein each X is independently a halogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 6  hydrocarbyl group; M comprises Zr or Hf and m is 2. 
     
     
         45 . The process of  claim 40 , wherein M is Zr, m is 2 and each X is independently a methyl, an ethyl, a propyl, a butyl, a phenyl, a benzyl, a chloride, a bromide, or an iodide. 
     
     
         46 . The process of  claim 40  wherein the a polymerization reactor is a continuous stirred tank reactor or a continuous tubular reactor, the alpha-olefin is introduced to the reactor at a flow rate of at least 100 g/hr, the polymerization residence time is from 2 to 5 hours, and the polymerization temperature is 120° C. or more. 
     
     
         47 . The process of  claim 46  where the vinylidene content of the PAO produced is 95% or more based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO product, the Mn of the PAO product is 350 g/mol or less, the conversion is at least 60%, at least 70%, at least 80%, at least 90%, based upon the weight of the monomer entering the reactor and the PAO produced, the PAO dimer selectivity is at least 60%, based upon the weight of the PAO produced, and the productivity of the continuous process is at least 60,000 g/hour with a catalyst loading of 0.1 gram catalyst per gram of monomer or less.