IPC분류정보
국가/구분 |
United States(US) Patent
등록
|
국제특허분류(IPC7판) |
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출원번호 |
US-0832287
(2007-08-01)
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등록번호 |
US-8513478
(2013-08-20)
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발명자
/ 주소 |
- Wu, Margaret M.
- Hagemeister, Mark P.
- Yang, Norman
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출원인 / 주소 |
- ExxonMobil Chemical Patents Inc.
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대리인 / 주소 |
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인용정보 |
피인용 횟수 :
4 인용 특허 :
78 |
초록
▼
Liquid poly-alpha-olefins having a KV100 of 2 to 6000 cSt, 20 weight percent dimer or less and a viscosity index of 60 or more are obtained by contacting in a reaction zone, in the presence of from 0 to 60 psi hydrogen, C3 to C20 alpha-olefin monomers with a non-coordinating anion activator, a singl
Liquid poly-alpha-olefins having a KV100 of 2 to 6000 cSt, 20 weight percent dimer or less and a viscosity index of 60 or more are obtained by contacting in a reaction zone, in the presence of from 0 to 60 psi hydrogen, C3 to C20 alpha-olefin monomers with a non-coordinating anion activator, a single bridged meso-metallocene transition metal compound having less than about 35 wt % racemic isomer, and a co-activator. The molar ratio of activator to meso-metallocene is from 10:1 to 0.1:1, and the alpha-olefin monomers in the feed components are present in at least 20 wt % or more based upon the weight of the meso-metallocene, non-coordinating anion activator, co-activator, monomers, and solvent or diluent. The productivity of the process is at least 50,000 g of total product per gram of transition metal compound and no more than 5% monomer is converted from olefin to alkane.
대표청구항
▼
1. A process to produce a liquid poly-alpha-olefin comprising: a) contacting in a reaction zone, in the presence of below 20 psi hydrogen, one or more C3 to C20 alpha-olefin monomers with a non-coordinating anion activator, a single bridged meso-metallocene transition metal compound having less than
1. A process to produce a liquid poly-alpha-olefin comprising: a) contacting in a reaction zone, in the presence of below 20 psi hydrogen, one or more C3 to C20 alpha-olefin monomers with a non-coordinating anion activator, a single bridged meso-metallocene transition metal compound having less than about 35 wt % racemic isomer, and a co-activator selected from the group consisting of alkyl aluminum compounds and alkyl alumoxanes, provided that when the alkyl alumoxane is present it is present in a molar ratio of less than 0.1:1 of alkylalumoxane to meso-metallocene, and provided that when the alkyl aluminum compound is present it is present at a molar ratio of alkyl aluminum to meso-metallocene of from 2:1 to 10,000 to 1, where the molar ratio of activator to meso-metallocene is from 10:1 to 0.1:1, andprovided that ethylene is not present at more than 30 volume % of the monomers entering the reaction zone,provided that the alpha-olefin monomers in the feed components are present in at least 20 weight % or more based upon the weight of the meso-metallocene, non-coordinating anion activator, co-activator, monomers, and solvent or diluent, and where:i) the productivity of the process is at least 50,000 g of total product per gram of transition metal compound (where the total product is defined to be the total amount of product exiting the reactor, minus unreacted monomers and solvents);ii) no more than 5% monomer is converted from olefin to alkane;iii) the yield of product is greater than 95%; andb) obtaining a liquid polyalphaolefin product having a pour point of less than 25° C., a KV100 of 3 to 1000 cSt, 10 weight % dimer or less and a viscosity index of 60 or more. 2. The process of claim 1, wherein the meso-metallocene is defined as (Cp-A′-Cp*)MX1X2 wherein: M is the metal center, and is a Group 4 metal;Cp and Cp* are the same or different cyclopentadienyl rings that are each bonded to M, and substituted with from zero to four substituent groups S″ being, independently, a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl or germylcarbyl, or Cp and Cp* are the same or different cyclopentadienyl rings in which any two adjacent S″ groups are optionally joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent;A′ is a bridging group;X1 and X2 are, independently, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbyl radicals; or both X are joined and bound to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms; or both together can be an olefin, diolefin or aryne ligand; or when Lewis-acid activators, such as methylalumoxane, which are capable of donating an X ligand as described above to the transition metal component are used, both X may, independently, be a halogen, alkoxide, aryloxide, amide, phosphide or other univalent anionic ligand or both X can also be joined to form a anionic chelating ligand. 3. The process of claim 2, wherein M is titanium, zirconium or hafnium. 4. The process of claim 1, wherein the KV100 is 150 cSt to 1000 cSt or more. 5. The process of claim 1, wherein the KV100 is 300 cSt to 1000 cSt or more. 6. The process of claim 1, wherein the KV100 is 600 cSt to 1000 cSt or more. 7. The process of claim 1, wherein the pour point is −10° C. or less. 8. The process of claim 1, wherein more than 95 wt % of the total product has greater than 18 carbon atoms. 9. The process of any of claim 1, wherein the process is continuous or semi-continuous. 10. The process of claim 1, wherein the meso-metallocene is meso-dimethylsilylbis(2-methylindeny) zirconium dihalide or mesoethylenebis(indenyl)zirconium dihalide. 11. The process of claim 1, wherein the meso-metallocene is meso-dimethylsilylbis(2-methylindeny)zirconium dialkyl or mesoethylenebis(indenyl)zirconium dialkyl. 12. The process of claim 1, wherein the co-activator is represented by the formula: R′3Al, where each R′ is, independently, selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, iso-butyl, n-butyl, t-butyl, n-pentyl, iso-pentyl, neopentyl, n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and their iso-analogs. 13. The process of claim 1, wherein the non-coordinating anion activator is N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dialkylphenylanilinium tetrakis(pentafluorophenyl)borate, trityl tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)boron, tri-alkylammonium tetrakis(pentafluorophenyl)borate, tetra-alkylammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronapthyl)borate, N,N-dialkylphenylanilinium tetrakis(perfluoronapthyl)borate, trityl tetrakis(perfluoronapthyl)borate, tris(perfluoronapthyl)boron, tri-alkylammonium tetrakis(perfluoronapthyl)borate, or tetra-alkylammonium tetrakis(perfluoronapthyl)borate. 14. The process of claim 1, wherein the monomers are one or more of are selected from the group consisting of propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1-uneicosene, 1-docosene, 1-tricosene, 1-tetracosene, 1-pentacosene, 1-hexacosene, 4-methyl-1-pentene, 4-phenyl-1-butene, and 5-phenyl-1-pentene. 15. The process of claim 1 wherein less than 20 wt % rac isomer is present. 16. The process of claim 1 wherein the poly-alpha-olefin contains less than 300 ppm of a Group 4 metal. 17. The process of claim 1 wherein the poly-alpha-olefin contains less than 100 ppm of a Group 13 metal. 18. The process of claim 1 wherein the poly-alpha-olefin contains less than 300 ppm of aluminum. 19. The process of claim 1 wherein the poly-alpha-olefin has an Mw/Mn of between 1.5 and 3.5. 20. The process of claim 1 wherein the poly-alpha-olefin has an Mw/Mn of between 1.5 and 2.5. 21. The process of claim 1 wherein the poly-alpha-olefin has a melting point of 0° C. or less or has no measurable melting point. 22. The process of claim 1 wherein the poly-alpha-olefin has less than 20 J/g of heat release. 23. The process of claim 1 wherein the poly-alpha-olefin has a Viscosity Index of 100 or more. 24. The process of claim 1 wherein the poly-alpha-olefin has a vinylidene disubstituted olefin content of more than 65 mol %.
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