This invention discloses an improved process which employs mixed alpha-olefins as feed over activated metallocene catalyst systems to provide essentially random liquid polymers particularly useful in lubricant components or as functional fluids.
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1. A process comprising contacting a metallocene compound, an activator, optionally a co-activator, and a feed having an average carbon number of at least 4.1 and comprising at least two different alpha-olefin monomers selected from C3 to C30 alpha-olefins under conditions suitable to obtain an esse
1. A process comprising contacting a metallocene compound, an activator, optionally a co-activator, and a feed having an average carbon number of at least 4.1 and comprising at least two different alpha-olefin monomers selected from C3 to C30 alpha-olefins under conditions suitable to obtain an essentially random liquid polymer comprising said at least two feed alpha-olefins, with the proviso that any one of ethylene and propylene, if present in said feed, is present in the amount of less than 50 wt % individually, and hydrogen, if present in the reaction atmosphere, has a partial pressure of less than 5 psi, wherein said random liquid polymer is characterized by a χ value (degree of randomness) ranging from 0.7 to 1.4, wherein said metallocene compound is characterized by the formula 1: wherein M is selected from Zr, Hf, Ti; each X is independently selected from the group consisting of halide and hydrogen, branched or unbranched C1 to C20 hydrocarbyls, L1 and L2 are independently selected from tetrahydroindenyl, fluorenyl, and their alkyl substituted analogs, and A can be present or absent and when present is selected from R1R2Si, R1R2C, (R1R2C)2, (R1R2Si)2; wherein R1 and R2 are independently selected from hydrogen, branched or unbranched C1 to C20 hydrocarbyl radicals, phenyl, and substituted phenyl, and when A is bridged, the catalyst represented can be racemic or meso form. 2. The process of claim 1, wherein said at least two different alpha-olefin monomers are selected from the group consisting of linear alpha-olefins, alpha-olefins characterized by alkyl or aryl substitution at least two carbons away from the double bond, and mixtures thereof. 3. The process of claim 1, wherein said at least two different alpha-olefins are selected from the group consisting of C4-C8 linear alpha-olefins, C12-C24 linear alpha-olefins, 4-methyl-1-pentene, 5-methyl-1-hexene, 4-ethyl-1-hexene, 4-phenyl-1-pentene, and 5-phenyl-1-pentene. 4. The process of claim 1, wherein said at least two different alpha-olefins are provided directly, without separation of individual alpha-olefins, from an alpha-olefin-producing process selected from an ethylene growth process, an olefin metathesis process, a wax-cracking process, a syn gas synthesis process, and mixtures thereof. 5. The process according to claim 1, wherein the composition of said random liquid polymer is characterized by an incorporation of each alpha-olefin monomer within said product of within at least 20 wt % of the distribution of said alpha-olefin monomer within said feed. 6. The process according to claim 1, wherein the composition of the random liquid polymer is characterized by the ratio of the incorporated monomer mole % to the feed monomer mole % ranging from 0.5 to 5. 7. The process according to claim 1, wherein said random liquid polymer is characterized by a stereo-arrangement of each monomer that is isotactic, atactic, syndiotactic or a combination of these tacticities. 8. The process according to claim 1, wherein said activator is selected from among Lewis acid activators and ionic activators. 9. The process according to claim 1, wherein said contacting further comprises contacting a promoter or co-activator selected from the group consisting of alkylaluminum compounds having the formula R3Al and alkylboron compounds having the formula R3B, where each R is independently selected from C1 to C20 alkyl group or H. 10. The process according to claim 1, wherein said contacting further comprises contacting in the presence of H2. 11. The process according to claim 1, wherein said contacting is further characterized by contacting in the absence of H2. 12. The process according to claim 1, wherein said random liquid polymer is characterized by a bromine number of greater than 2 and said process further comprises contacting said product with hydrogen to obtain a second polymer product characterized by a bromine number of less than 2. 13. The process according to claim 1, wherein said feed comprises at least two alpha-olefins selected from C3 to C24 alpha-olefins. 14. The process according to claim 1, wherein said feed comprises at least two different alpha-olefins selected from C4 to C18 alpha-olefins. 15. The process according to claim 1, wherein said feed comprises at least three different alpha-olefins. 16. The process according to claim 1, wherein said feed comprises at least four different alpha-olefins. 17. The process according to claim 1, wherein said feed comprises less than 80 wt % of alpha-olefins selected from C8 to C12 alpha-olefins, based on the combined weight of alpha-olefins in said feed. 18. The process according to claim 1, wherein no alpha-olefin is present in said feed in an amount greater than 33 wt %, based on the combined weight of alpha-olefins in said feed. 19. The process according to claim 1, wherein the feed is selected from at least one alpha-olefin selected from 1-butene and 1-hexene and at least one alpha-olefin selected from C12-C18 alpha-olefins, and wherein the combined amount of 1-decene and 1-octene is less than 40 wt %. 20. The process according to claim 1, wherein said feed is characterized by an average carbon number of between 4.1 and 14. 21. The process according to claim 1, wherein said feed is characterized by an average carbon number between 5.5 and 11 and further characterized by the presence of C8 to C12 alpha-olefins in the combined amount of less than 50 wt %, based on the combined weight of alpha-olefins in said feed. 22. The process according to claim 1, wherein said feed is characterized by an average carbon number between 5.5 and 11 and further characterized by the presence of C8 to C12 alpha-olefins in the combined amount of less than 10 wt %, based on the combined weight of alpha-olefins in said feed. 23. The process according to claim 1, wherein said feed is obtained and used for said contacting without separation or isolation of alpha-olefins from an ethylene growth process. 24. The process of claim 1, wherein said product is further characterized by at least one of the parameters selected from: (a) Mn=200-50,000; (b) Mw=200-80,000; (c) MWD=1 to 5; (d) Pour Point less than 10° C.; (e) KV at 40° C. of 4 to 80,000 cSt; (f) KV at 100° C. of 1.5 to 5,000 cSt; (g) a Viscosity Index (VI) greater than or equal to 100. 25. The process according to claim 1, wherein said product is further characterized by a Viscosity Index (VI) of at least 120. 26. The process according to claim 1, wherein said feed comprises from 1 wt % to 95 wt % C4 to C8 alpha-olefins, based on the combined weight of alpha-olefins in said feed. 27. The process according to claim 1, wherein said feed comprises from 5 wt % to 85 wt % C4 to C8 alpha-olefins, based on the combined weight of alpha-olefins in said feed. 28. The process according to claim 1, wherein said feed comprises from 5 wt % to 85 wt % C4 to C8 alpha-olefins, 15 wt % to 95 wt % C12-C18 alpha-olefins, and less than 80 wt % C8-C10 alpha-olefins, based on the combined weight of alpha-olefins in said feed. 29. The process according to claim 1, wherein said feed comprises from 5 wt % to 85 wt % 1-hexene, based on the combined weight of alpha-olefins in said feed. 30. The process according to claim 1, wherein said feed comprises from 5 wt % to 85 wt % 1-hexene, and less than 80 wt % of any one of 1-octene and 1-decene, based on the combined weight of alpha-olefins in said feed. 31. The process according to claim 1, wherein said feed comprises from 5 wt % to 85 wt % 1-hexene, and less than 55 wt % of any one of 1-octene and 1-decene, based on the combined weight of alpha-olefins in said feed. 32. The process according to claim 1, wherein said feed comprises from 5 wt % to 85 wt % 1-hexene, and less than 25 wt % of any one of 1-octene and 1-decene, based on the combined weight of alpha-olefins in said feed. 33. The process according to claim 1, wherein said feed comprises from 60 wt % to 75 wt % of alpha-olefins selected from 1-hexene, 1-heptene and/or 1-octene and mixtures thereof and 25 wt % to 40 wt % of alpha-olefins selected from 1-dodecene, 1-tetradecene, and mixture thereof, based on the combined weight of alpha-olefins in said feed, and said product is characterized by a viscosity index of from 140 to 375, a KV at 100° C. of from 10 to 1000 cSt, and a pour point of less than −10° C. 34. A process comprising contacting a metallocene compound, an activator, and a feed having an average carbon number of between 5.5 and 14, said feed comprising at least two different alpha-olefin monomers selected from C4 to C24 alpha-olefins, under conditions suitable to obtain a polymer comprising said at least two alpha-olefins, wherein hydrogen, if present in the reaction atmosphere, has a partial pressure of less than 5 psi, and said metallocene compound is characterized by the formula 1: wherein M is selected from Zr, Hf, Ti; each X is independently selected from the group consisting of halide and branched or unbranched C1 to C20 hydrocarbyls, L1 and L2 are independently selected from tetrahydroindenyl, fluorenyl, and their alkyl substituted analogs, and A can be present or absent and when present is selected from R1R2Si, R1R2C, (R1R2C)2, (R1R2Si)2; wherein R1 and R2 are independently selected from hydrogen, branched or unbranched C1 to C20 hydrocarbyl radicals, phenyl, and substituted phenyl, and when A is bridged, the catalyst represented can be in the racemic or meso form, and wherein said activator is selected from among Lewis acid activators and ionic activators, and obtaining thereby a polymer characterized by: (a) Mn=200-50,000;(b) Mw=200-80,000;(c) MWD=1 to 5;(d) a pour point less than 10° C.;(e) a KV at 100° C.=1.5 to 5,000;(h) a VI greater than or equal to 100;(i) having no distinct melting point above 0° C.;(j) by having the ratio of the amount of any alpha-olefin monomer incorporated in said polymer to the amount of said any alpha-olefin in said feed being from 0.5 to 3; and(k) a χ value (degree of randomness) ranging from 0.7 to 1.4. 35. The process of claim 34, wherein ethylene and/or propylene, if present in said feed, are present in the combined amount of less than 50 wt %, based on the combined weight of alpha-olefins in said feed. 36. The process of 34, wherein 1-octene and/or 1-decene, if present in said feed, are present in the amount of 66 wt % or less individually, based on the combined weight of alpha-olefins in said feed. 37. The process of claim 34, wherein 1-octene and/or 1-decene and/or 1-dodecene, if present in said feed, are present in the amount of less than 70 wt % individually, based on the combined weight of alpha-olefins in said feed. 38. The process of claim 34, wherein 1-octene and/or 1-decene and/or 1-dodecene, if present in said feed, are present in the amount of less than 55 wt % individually, based on the combined weight of alpha-olefins in said feed. 39. The process of claim 34, wherein 1-octene and/or 1-decene and/or 1-dodecene, if present in said feed, are present in the amount of less than 25 wt % individually, based on the combined weight of alpha-olefins in said feed. 40. The process of claim 34, wherein the average carbon number of said feed is from 5.7 to less than 12. 41. The process according to claim 1, wherein said activators are selected from methylaluminoxane, alkylanilinium tetrakis(perfluorophenyl)borate, tris(pentafluorophenyl)boron, their analogs and derivatives, and mixtures thereof. 42. The process according to claim 1, wherein said activator is N,N-dimethylanilinium tetrakis(perfluorophenyl)borate. 43. The process according to claim 1, wherein said co-activators are present and at least one is a co-activator selected from triethyl aluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and tri-n-dodecylaluminum. 44. The process according to claim 1, wherein said catalyst has a productivity of less than 1,000 gram of product per gram of metallocene component. 45. The process according to claim 1, wherein said feed comprises from 5 wt % to 85 wt % 1-hexene, and less than 25 wt % of any one of 1-octene, 1-decene, and 1-dodecene, based on the combined weight of alpha-olefins in said feed. 46. The process of claim 1, wherein said feed further comprises at least 20 wt % 1-hexene, based on the combined weight of alpha-olefins in said feed. 47. The process according to claim 1, wherein said feed comprises from 20 wt % to 75 wt % of alpha-olefins selected from 1-hexene, 1-heptene and 1-octene and mixtures thereof, and 25 wt % to 75 wt % of alpha-olefins selected from 1-dodecene, 1-tetradecene, and mixture thereof, based on the combined weight of alpha-olefins in said feed and said product is characterized by a viscosity index of from 140 to 375, a KV at 100° C. of from 10 to 1000 cSt, and a pour point of less than −10° C. 48. The process of claim 34, wherein said feed comprises from 5 wt % to 85 wt % 1-hexene, and less than 55 wt % of any one of 1-octene and 1-decene and less than 80% of any one of 1-tetradecene and 1-hexadecene, based on the combined weight of alpha-olefins in said feed. 49. The process according to claim 34, further comprising treating said polymer with hydrogen and hydrogenation catalyst to give fully saturated polymer with low bromine number of less than 2.
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이 특허에 인용된 특허 (81)
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