WO2008077911A1 - Ligands and catalyst systems for the oligomerization of olefinic monomers - Google Patents
Ligands and catalyst systems for the oligomerization of olefinic monomers Download PDFInfo
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- WO2008077911A1 WO2008077911A1 PCT/EP2007/064398 EP2007064398W WO2008077911A1 WO 2008077911 A1 WO2008077911 A1 WO 2008077911A1 EP 2007064398 W EP2007064398 W EP 2007064398W WO 2008077911 A1 WO2008077911 A1 WO 2008077911A1
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- WIPO (PCT)
- Prior art keywords
- groups
- substituted
- group
- methoxyphenyl
- ligand
- Prior art date
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- 239000003446 ligand Substances 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000000178 monomer Substances 0.000 title claims abstract description 38
- 238000006384 oligomerization reaction Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 72
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 69
- 230000008569 process Effects 0.000 claims abstract description 65
- 125000001424 substituent group Chemical group 0.000 claims abstract description 48
- 125000003118 aryl group Chemical group 0.000 claims abstract description 41
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 36
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 7
- -1 o- anisyl group Chemical group 0.000 claims description 99
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 63
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 56
- 239000005977 Ethylene Substances 0.000 claims description 56
- 239000011651 chromium Substances 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 36
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 33
- 229910052804 chromium Inorganic materials 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052721 tungsten Inorganic materials 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 4
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 91
- 239000000203 mixture Substances 0.000 description 85
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 84
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 84
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 83
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 77
- 239000000047 product Substances 0.000 description 68
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 27
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 23
- 239000007787 solid Substances 0.000 description 23
- 239000002904 solvent Substances 0.000 description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 11
- 150000004820 halides Chemical group 0.000 description 11
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical group [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 125000005842 heteroatom Chemical group 0.000 description 10
- 238000004679 31P NMR spectroscopy Methods 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000370 acceptor Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 125000004437 phosphorous atom Chemical group 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000013638 trimer Substances 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005119 centrifugation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000004104 aryloxy group Chemical group 0.000 description 6
- 239000012018 catalyst precursor Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 229940086542 triethylamine Drugs 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 5
- 239000003426 co-catalyst Substances 0.000 description 5
- 239000000306 component Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 125000002950 monocyclic group Chemical group 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 150000002899 organoaluminium compounds Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 4
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 3
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- UWLFCNHEPBTLHT-UHFFFAOYSA-N neopentyllithium Chemical compound [Li]CC(C)(C)C UWLFCNHEPBTLHT-UHFFFAOYSA-N 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 125000006413 ring segment Chemical group 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 2
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LTEQMZWBSYACLV-UHFFFAOYSA-N Hexylbenzene Chemical compound CCCCCCC1=CC=CC=C1 LTEQMZWBSYACLV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000005922 Phosphane Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 229910052787 antimony Chemical group 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 2
- 229910000066 arsane Inorganic materials 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- CTNFGBKAHAEKFE-UHFFFAOYSA-N bis(2-methylpropyl)alumanyloxy-bis(2-methylpropyl)alumane Chemical compound CC(C)C[Al](CC(C)C)O[Al](CC(C)C)CC(C)C CTNFGBKAHAEKFE-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 229960000359 chromic chloride Drugs 0.000 description 2
- 239000011636 chromium(III) chloride Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- NFJPEKRRHIYYES-UHFFFAOYSA-N methylidenecyclopentane Chemical compound C=C1CCCC1 NFJPEKRRHIYYES-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229910000064 phosphane Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010454 slate Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical compound [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 1
- WVSBQYMJNMJHIM-UHFFFAOYSA-N (benzene)chromium tricarbonyl Chemical compound [Cr].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1 WVSBQYMJNMJHIM-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- 101100406879 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) par-2 gene Proteins 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- WBKDDMYJLXVBNI-UHFFFAOYSA-K chromium(3+);2-ethylhexanoate Chemical compound [Cr+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O WBKDDMYJLXVBNI-UHFFFAOYSA-K 0.000 description 1
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 description 1
- PPUZYFWVBLIDMP-UHFFFAOYSA-K chromium(3+);triiodide Chemical compound I[Cr](I)I PPUZYFWVBLIDMP-UHFFFAOYSA-K 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- UZDWIWGMKWZEPE-UHFFFAOYSA-K chromium(iii) bromide Chemical compound [Cr+3].[Br-].[Br-].[Br-] UZDWIWGMKWZEPE-UHFFFAOYSA-K 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 125000004092 methylthiomethyl group Chemical group [H]C([H])([H])SC([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000006574 non-aromatic ring group Chemical group 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910000067 stibane Inorganic materials 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004014 thioethyl group Chemical group [H]SC([H])([H])C([H])([H])* 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0264—Phosphorus acid amides
- B01J31/0265—Phosphazenes, oligomers thereof or the corresponding phosphazenium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5355—Phosphoranes containing the structure P=N-
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
Definitions
- the present invention relates to ligands and to catalyst systems comprising said ligands.
- the present invention further relates to a process for the oligomerization of olefinic monomers using said catalyst systems .
- the efficient catalytic trimerization or tetramerization of olefinic monomers is an area of great interest for the production of olefinic trimers and tetramers of varying degrees of commercial value.
- 1-hexene is a valuable comonomer for linear low-density polyethylene (LLDPE) and 1-octene is valuable as a chemical intermediate in the production of plasticizer alcohols, fatty acids, detergent alcohol and lubrication oil additives as well as a valuable comonomer in the production of polymers such as polyethylene.
- 1-Hexene and 1-octene can be produced by a conventional transition metal oligomerization process, although the trimerization and tetramerization routes are preferred.
- US-A-5968866 discloses an ethylene oligomerization/trimerization process which uses a catalyst comprising a chromium complex which contains a coordinating asymmetric tridentate phosphane, arsane or stibane ligand and an aluminoxane to produce alpha- olefins which are enriched in 1-hexene.
- US5523507 discloses a catalyst based on a chromium source, a 2 , 5-dimethylpyrrole ligand and an alkyl aluminium activator for use in the trimerization of ethylene to 1-hexene.
- WO 02/04119 discloses a catalyst for the trimerization of olefins comprising a source of chromium, molybdenum or tungsten, a ligand containing at least one phosphorus, arsenic or antimony atom bound to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, but excluding the case where all such polar substituents are phosphane, arsane or stibane groups, and optionally an activator.
- the ligand used in most of the examples is (2-methoxyphenyl) 2PN (Me) P (2-methoxyphenyl) 2 •
- WO 2005/039758 discloses a trimerization catalyst composition and a process for the trimerization of olefinic monomers using said catalyst composition.
- Catalytic systems for the tetramerization of ethylene to 1-octene have recently been described. A number of these catalysts are based on chromium.
- WO 2004/056478 and WO 2004/056479 disclose catalyst compositions and processes for the tetramerization of olefins.
- the catalyst compositions disclosed in WO 2004/056478 comprise a transition metal and a heteroatomic ligand having the general formula (R) n A-B-C (R) m where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, oxygen, bismuth, sulphur, selenium, and nitrogen, and B is a linking group between A and C, and R is independently selected from any homo or heterohydrocarbyl group of which at least one R group is substituted with a polar substituent and n and m are determined by the respective valence and oxidation state of A and/or C.
- the catalyst compositions disclosed in WO 2004/056479 comprise a transition metal and a heteroatomic ligand having the general formula (R') n A-B-
- R' is independently selected from any homo or heterohydrocarbyl group.
- Example 16 of WO 2004/056478 discloses an ethylene tetramerization reaction using Cr (III) acetylacetonoate, (phenyl) 2PN (isopropyl) P (2-methoxyphenyl) 2 in a ratio of 1:2 mol/mol, and MAO, with an Al : Cr atomic ratio of 136:1, at 45 0 C and 45 barg.
- the reaction produced a product composition with over 24 wt% of the products having greater than 11 carbon atoms, based on the weight of all products (9.00 wt% C ⁇ 1 + liquids and
- WO 2004/056480 discloses the tandem tetramerization and polymerisation of ethylene. Specifically, WO 2004/056480 discloses a process for polymerising olefins to produce branched polyolefins in the presence of a distinct polymerization catalyst and a distinct tetramerization catalyst, wherein the tetramerization catalyst produces 1-octene in a selectivity greater than 30% and the 1-octene produced is at least partially incorporated into the polyolefin chain.
- the tetramerization catalysts disclosed in the Sasol documents mentioned above have good selectivity for 1-octene within the Cs fraction, again, a relatively high level of by-product formation is observed.
- the by-product consists of Cg compositions; however, only about 70 to 80 %wt . of the Cg by-product composition is 1-hexene, with the remaining Cg by-product comprising compounds such as methylcyclopentane and methylenecyclopentane .
- the presence of these remaining Cg by-product compositions which have very little commercial use or value, is highly undesirable from both an economic point of view as well as from a product separation point of view.
- the ligands and catalyst systems of the present invention provide excellent results in the trimerization and tetramerization of olefinic monomers.
- the selective production of 1-hexene and 1-octene from ethylene is achieved while reducing the level of byproduct formation, especially C ] _ Q by-products, solids (i.e. heavy waxes and/or polyethylene) and Cg compositions/isomers other than 1-hexene.
- a ligand having the general formula (I) : (R 1 ) 2 P-P(R 1 ) m (R 2 ) n N (R 3 ) (I) wherein R 3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; the R 1 groups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions,- and the R 2 groups are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions; with the proviso that m is 0 or 1, n is 1 or 2 and the total of m + n is 2.
- R 3 is selected from hydrogen, a hydrocarbyl group,
- R 3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof;
- the R 1 groups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions;
- the R 2 groups are independently selected from hydrocarbyl, substituted hydrocarbyl , heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions; with the proviso that m is 0 or 1, n is 1 or 2 and the total of m + n is 2.
- a ligand system prepared by reacting: (i) a compound of formula (V) :
- a catalyst system comprising: a) a source of chromium, molybdenum or tungsten; b) a ligand or a ligand system as described herein; and c) a cocatalyst .
- simultaneous trimerization and tetramerization of olefinic monomers wherein the process comprises contacting at least one olefinic monomer with the catalyst system herein at a pressure in the range of from below atmospheric to 100 barg and at a temperature in the range of from 0 0 C to 200 0 C.
- trimerization means the catalytic trimerization of an olefinic monomer to give a product composition enriched in the compound derived from the reaction of three of said olefinic monomers.
- trimerization includes the cases wherein all the olefinic monomers in the feed stream are identical as well as the cases wherein the feed stream contains two or more different olefinic monomers.
- trimerization when used in relation to the trimerization of ethylene means the trimerization of ethylene to form a Cg alkene, especially 1-hexene. - S -
- trimerization selectivity when used in relation to the trimerization of ethylene means the amount of Cg fraction formed within the product composition.
- 1-hexene selectivity when used in relation to the trimerization of ethylene means the amount of 1-hexene formed within the Cg fraction of the product composition.
- the overall yield of 1-hexene in the trimerization of ethylene is the product of the "trimerization selectivity" multiplied by the "1-hexene selectivity" .
- tetramerization means the catalytic tetramerization of an olefinic monomer to give a product composition enriched in the compound derived from the reaction of four of said olefinic monomers.
- the term tetramerization includes the cases wherein all the olefinic monomers in the feed stream are identical as well as the cases wherein the feed stream contains two or more different olefinic monomers.
- tetramerization when used in relation to the tetramerization of ethylene means the tetramerization of ethylene to form a Cg alkene, especially 1-octene.
- tetramerization selectivity when used in relation to the tetramerization of ethylene means the amount of Cg fraction formed within the product composition .
- hydrocarbyl refers to a group only containing carbon and hydrogen atoms .
- the hydrocarbyl group may be a saturated or unsaturated, linear or branched alkyl, a non-aromatic ring or an aromatic ring. Unless otherwise stated, the preferred hydrocarbyl groups for use herein are those containing from 1 to 20 carbon atoms.
- substituted hydrocarbyl refers to hydrocarbyl groups which contain one or more inert heteroatom containing functional groups.
- inert heteroatom containing functional groups is meant that the functional groups do not interfere to any substantial degree with the trimerization and tetramerization process .
- heterohydrocarbyl refers to a hydrocarbyl group wherein one or more of the carbon atoms is replaced by a heteroatom, such as Si, S, N or 0.
- the carbon atom of the hydrocarbyl group which is replaced by a heteroatom can be either an internal carbon atom of the hydrocarbyl group or the carbon atom through which the heterohydrocarbyl group is attached, e.g. the atom which is attached to the nitrogen atom in the case of the bridging group, e.g. -N(OMe)-.
- substituted heterohydrocarbyl refers to heterohydrocarbyl groups which contain one or more inert heteroatom containing functional groups.
- aromatic refers to a monocyclic or polycyclic, aromatic or heteroaromatic ring having from 5 to 14 ring atoms, optionally containing from 1 to 3 heteroatoms selected from N, 0 and S.
- the aromatic groups are monocyclic or polycyclic aromatic rings, such as cyclopentadienyl (which can also include ferrocenyl groups), phenyl, biphenyl, naphthyl or anthracenyl .
- the preferred aromatic groups are monocyclic or polycyclic aromatic rings having from 5 to 10 ring atoms, more preferred aromatic groups are monocyclic aromatic rings containing from 5 to 6 carbon atoms, such as phenyl and cyclopentadienyl, and a most preferred aromatic group is a phenyl group.
- substituted aromatic as used herein means that the aromatic group may be substituted with one or more substituents .
- the ligands of the present invention have the general formulae (I) and (II) below:
- R 1 , R 2 , R 3 , and R 4 are as defined above.
- R 3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof.
- R 3 is selected from hydrogen or the groups consisting of alkyl, substituted alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, alkenyl, substituted alkenyl, cycloalkyl, substituted cycloalkyl, alkoxycarbonyl , carbonyloxy, alkoxy, aminocarbonyl , carbonylamino, dialkylamino, silyl groups or derivatives thereof, and alkyl or aryl groups substituted with any of these substituents or halogen or a nitro group.
- R 3 is an alkyl, substituted alkyl (including heterocyclic substituted alkyl with at least one heteroatom, such as N or 0, and alkyl groups substituted with a heteroatom or heteroatomic group), cycloalkyl, substituted cycloalkyl, substituted cyclic aryl, substituted aryl, aryloxy or substituted aryloxy group.
- R 3 groups include C ] _-C]_5 alkyl groups, substituted C ] _-C ] _ 5 alkyl groups, C2-C 1 5 alkenyl groups, substituted C2-C15 alkenyl groups, C3-C15 cycloalkyl groups, substituted C3-C 1 5 cycloalkyl groups, C 5 -C15 aromatic groups, substituted C5-C 15 aromatic groups, C ] _-Cj_5 alkoxy groups and substituted C]_-C]_ 5 alkoxy groups.
- R 3 groups are the C ] _-C ⁇ 5 alkyl groups, which include both linear and branched alkyl groups; suitable examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl , alkyl branched pentyl groups, hexyl , alkyl branched hexyl groups, heptyl , alkyl branched heptyl groups, octyl and alkyl branched octyl groups .
- the substituents on the R 1 and/or R 2 groups can contain carbon atoms and/or heteroatoms .
- the substituents may be either polar or non-polar.
- Suitable substituents include hydrocarbyl groups which may be straight -chain or branched, saturated or unsaturated, aromatic or non- aromatic.
- the hydrocarbyl substituents may optionally contain heteroatoms such as Si, S, N or 0.
- Suitable aromatic hydrocarbyl substituents include monocyclic and polycyclic aromatic groups, preferably having from 5 to 10 carbon atoms in the ring, such as phenyl and C 1 -C 4 alkyl phenyl groups.
- Suitable non-aromatic hydrocarbyl substituents include linear or branched alkyl or cycloalkyl groups, preferably having from 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
- R 1 and/or R 2 groups include halides such as chloride, bromide and iodide, thiol, -OH, A 1 - ⁇ -, -S-A 1 , -CO-A 1 , -NH 2 , -NHA 1 , -
- NA 1 A 2 , -CO-NA 1 A 2 , -NO 2 , 0, in which A 1 and A 2 , independently, are non-aromatic groups preferably having from 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl and isopropyl .
- preferred substituents are hydrocarbyl groups.
- Particularly preferred hydrocarbyl substituents are C 1 -C 4 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, most preferably methyl.
- n is 1 and n is i. In another embodiment m is 0 and n is 2. Typically, in the ligands of the present invention, component (b) , m is 0 and n is 2.
- the R 1 groups of the ligand are independently selected from optionally substituted aromatic groups, each bearing a polar substituent on at least one of the ortho-positions.
- bearing a polar substituent on at least one of the ortho-positions means that, in the same ligand, the R 1 group is substituted with a polar substituent on one or both of its ortho positions.
- optionally substituted in relation to the
- R 1 groups of the ligand of the present invention which are independently selected from optionally substituted aromatic groups, each bearing a polar substituent on at least one of the ortho-positions, means that, in addition to the polar substituent on at least one of the ortho- positions, the same R 1 group may contain one or more other substituents .
- Polar is defined by IUPAC as an entity with a permanent electric dipole moment. Therefore, as used herein, the term “polar substituents” means a substituent which incorporates a permanent electric dipole moment .
- Suitable polar substituents for use herein include but are not necessarily limited to, optionally branched c l ⁇ c 20 alkoxy groups, i.e. the R 1 and/or R 2 groups are substituted with a hydrocarbyl group connected through an oxygen bridging atom; optionally substituted C 5 -C 14 aryloxy groups, i.e. the R 1 and/or R 2 groups are substituted with an optionally substituted aromatic group connected through an oxygen bridging atom; optionally branched C]_-C2o alkoxy (C]_-C2o) alkyl groups, i.e.
- the R 1 and/or R 2 groups are substituted with a C1-C20 hydrocarbyl group bearing a C 1 -C 2 0 alkoxy group,- hydroxyl ; amino; (di-)C]_-Cg alkylamino; nitro; C ⁇ -Cg alkylsulphonyl ; C]_-Cg alkylthio (C ⁇ -Cg ) alkyl groups,- sulphate; heterocyclic groups, especially with at least one N and/or 0 ring atom; and tosyl groups.
- Suitable polar substituents include methoxy, ethoxy, isopropoxy, phenoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, eicosanoxy, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsulphonyl, tosyl, methoxymethyl, methylthiomethyl , 1 , 3-oxazolyl , hydroxyl, amino, methoxymethyl, phosphino, arsino, stibino, sulphate, nitro and the like.
- the polar substituents in the R 1 groups are independently selected from optionally branched C ] _-
- the polar substituents are independently selected from optionally branched C1-C20 alkoxy groups, especially optionally branched C ] _-Cg alkoxy groups such as, for example, methoxy, ethoxy or isopropoxy of which methoxy is a particularly preferred polar substituent; alternatively, longer optionally branched C]_-C2 Q alkoxy groups such as optionally branched Cg-C2o alkoxy groups, for example decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy or eicosanoxy groups, of which eicosanoxy is preferred, may be preferred as the polar substituents in order
- the RA group is independently selected from substituted or unsubstituted aromatic groups bearing an optionally branched C]_-C2o alkoxy group on at least one of the ortho-positions, such as an o- anisyl group.
- R 1 groups of the ligands having the formulae (I) and (II) are the same and bear the same number and type of polar substituent (s) . It is particularly preferred that each of said RA groups bears a polar substituent on only one of the two available ortho-positions .
- R ⁇ groups of the ligands having the formulae (I) and (II) are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions. It is preferred that each of said R 2 groups are independently selected from substituted or unsubstituted aromatic groups, including substituted or unsubstituted heteroaromatic groups, which do not contain a polar substituent at any of the ortho-positions.
- Said R 2 groups may be independently selected from a group comprising optionally substituted benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl , dimethylhydrazyl , methyl, ethyl, ethenyl, propyl, butyl, tert-butyl, propenyl , propynyl , cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl groups .
- said R 2 groups may be independently selected from a group comprising optionally substituted phenyl, tolyl, biphenyl, naphthyl, thiophenyl and ethyl groups.
- said R 2 groups are independently selected from optionally substituted phenyl groups which do not contain a polar substituent at any of the ortho-positions, or alternatively, do not contain any polar substituents at all .
- Any polar substituent present in said R 2 groups may be electron donating.
- Said R 2 groups may optionally contain non-polar substituent.
- IUPAC defines non-polar as an entity without a permanent electric dipole moment.
- Suitable non-polar substituents may be a methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl , hexyl , cyclopentyl, 2-methylcyclohexyl , cyclohexyl, cylopentadienyl, phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, ethenyl, propenyl and benzyl group, or the like.
- the non-polar substituent is not electron donating.
- said R 2 group is an unsubstituted phenyl group.
- n is 2 then the two R 2 groups may optionally be linked together to form a cyclic structure incorporating the phosphorus atom.
- one or both of the phosphorus atoms of the ligands of the present invention may be independently oxidised by S, Se, N or 0.
- Typically, neither of the phosphorus atoms of the second ligand are oxidised by S, Se, N or 0.
- the ligands according to general formulae (I) and (II) can be prepared by a process which comprises reacting: (i) a compound of formula (III) :
- Suitable HX acceptors include neopentyl lithium, n- butyl lithium, sec-butyl lithium, lithium hydride, sodium hydride, potassium hydride, triethylamine, trimethylamine, tripropylamine and the like.
- the ligands according to general formulae (I) and (II) can alternatively be prepared by a process which comprises reacting: (i) a compound of formula (V) : X-P(Rl) 2 (V); wherein X is a halide and R 1 is as defined above for general formulae (I) and (II) ; and (ii) a compound of formula (VI) :
- a ligand system prepared by a process which comprises reacting: (i) a compound of formula (III) :
- a ligand system prepared by a process which comprises reacting: (i) a compound of formula (V) :
- the ligands and ligand systems of the present invention can be used in a catalyst system which comprises : (a) a source of chromium, molybdenum or tungsten;
- the source of chromium, molybdenum or tungsten, component (a) , for the catalyst system of the present invention can include simple inorganic and organic salts of chromium, molybdenum or tungsten.
- simple inorganic and organic salts are halides, acetylacetonates , carboxylates , oxides, nitrates, sulfates and the like.
- Further sources of chromium, molybdenum or tungsten can also include co-ordination and organometallic complexes, for example chromium trichloride tris-tetrahydrofuran complex, (benzene) tricarbonylchromium, chromium hexacarbonyl , and the like.
- the source of chromium, molybdenum or tungsten, component (a) , for the catalyst system are selected from simple inorganic and organic salts of chromium, molybdenum or tungsten.
- the source of chromium, molybdenum or tungsten, component (a) , for the catalyst system is a simple inorganic or organic salt of chromium, molybdenum or tungsten, which is soluble in a solvent such as those disclosed in WO 02/04119.
- the source of chromium, molybdenum or tungsten can also include a mixture of any combination of simple inorganic salts, simple organic salts, co-ordination complexes and organometallic complexes.
- component (a) is a source of chromium, particularly chromium (III) .
- Preferred sources of chromium for use herein are simple inorganic and organic salts of chromium and coordination or organometallic complexes of chromium. More preferred sources of chromium for use herein are the simple inorganic and organic salts of chromium, such as salts of carboxylic acids, preferably salts of alkanoic acids containing 1 to 30 carbon atoms, salts of aliphatic- ⁇ -diketones and salts of ⁇ -ketoesters (e.g.
- chromium (III) 2-ethylhexanoate, chromium (III) octanoate and chromium (III) acetylacetonate) and halide salts of chromium, such as chromium trichloride, chromium trichloride tris-tetrahydrofuran complex, chromium tribromide, chromium trifluoride, and chromium tri- iodide .
- chromium (III) acetylacetonate also called chromium tris(2,4- pentanedionate) , Cr(acac)3, chromium trichloride, CrCl3, and chromium trichloride tris-tetrahydrofuran complex, CrCl 3 (THF) 3 .
- the cocatalyst, component (c) may in principle be any compound or mixture of compounds that generates an active catalyst system with the source of chromium, molybdenum or tungsten, component (a) , and the ligand, component (b) .
- Compounds which are suitable for use as a cocatalyst include organoaluminium compounds, organoboron compounds, organic salts, such as methyllithium and methylmagnesium bromide and inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate , sodium hexafluoroantimonate and the like.
- Particularly preferred cocatalysts are organoaluminium compounds .
- Suitable organoaluminium compounds for use herein are those having the formula AlR 4 3 , wherein each R 4 group is independently selected from C ⁇ -C 3 O alkyl (preferably C]_-C]_2 alkyl) , oxygen containing moieties or halides, and compounds such as LiAlH 4 and the like.
- Non- limiting examples of suitable organoaluminium compounds include trimethylaluminium (TMA) , triethylaluminium (TEA) , tri-n-butyl aluminium, tri-isobutylaluminium (TIBA) , tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride, dimethylaluminium chloride, diethylaluminium chloride and aluminoxanes (also called alumoxanes) .
- TMA trimethylaluminium
- TEA triethylaluminium
- TIBA tri-isobutylaluminium
- tri-n-octylaluminium tri-n-octylaluminium
- methylaluminium dichloride ethylaluminium dichloride
- dimethylaluminium chloride diethylaluminium chloride
- aluminoxane cocatalysts may comprise any aluminoxane compound or a mixture of aluminoxane compounds .
- Aluminoxanes may be prepared by the controlled addition of water to an alkylaluminium compound, such as those mentioned above, or are available commercially.
- suitable aluminoxanes include methyl aluminoxane (MAO) , modified methyl aluminoxane (MMAO) , tetraisobutyl dialuminoxane (TIBAO) , tetra-n-butyl dialuminoxane and tetra-n-octyl dialuminoxane.
- aluminoxane as used within this specification includes commercially available aluminoxanes, which are derived from the corresponding trialkylaluminium by addition of water and which may contain from 2 to 15 %wt . , typically about 5 %wt . , but optionally about 10 %wt . , of aluminium.
- the quantity of cocatalyst in the catalyst system the present invention is typically enough to provide a ratio in the range from 0.1 to 20,000, preferably from 1 to 2000, more preferably 1 to 1000, most preferably 1 to 500, aluminium or boron atoms per atom of chromium, molybdenum or tungsten.
- the catalyst system of the present invention may independently comprise more than one ligand as defined above .
- the amount of chromium, molybdenum or tungsten, namely component (a) , and the amount of ligand, component (b) can be present in the system in a molar ratio in the range of from 100:1 to 1:100, preferably from 10:1 to 1:10. More preferably, the chromium, molybdenum or tungsten, component (a) , and the ligand, component (b) , are present in a molar ratio in the range of from 3:1 to 1:3. Most preferably the amount of component (a) and the amount of component (b) are present in a molar ratio of from 1:0.9 to 1:1.1.
- the three catalyst components of the catalyst system, (a) , (b) and (c) may be added together simultaneously or sequentially in any order so as to provide an active catalyst.
- the three catalyst components of the catalyst system, (a) , (b) and (c) may be contacted in the presence of any suitable solvent.
- suitable solvents are known to those skilled in the art, suitable solvents may include any inert solvent that does not react with the co-catalyst component, such as saturated aliphatic, unsaturated aliphatic, aromatic, halogenated hydrocarbons and ionic liquids.
- Typical solvents include, but are not limited to, benzene, toluene, xylene, ethylbenzene, cumene, propane, butane, pentane, heptane, decane, dodecane, tetradecane, methylcyclohexane, methylcycopentane, cyclohexane, 1- hexene , 1-octene and the like.
- suitable solvents are those disclosed in WO 02/04119, such as hydrocarbon solvents and polar solvents such as diethyl ether, tetrahydrofuran, acetonitrile and the like.
- the catalyst system is formed by adding the co-catalyst component, (c) , to a catalyst precursor composition comprising components (a) and (b) .
- the catalyst system of the present invention may be prepared either in the presence (i.e. "in-situ") or absence of the olefinic monomer.
- the three catalyst components of the catalyst system, (a) , (b) and (c) may be combined fully in the absence of the olefinic monomer, or the olefinic monomer may be included prior to contacting the components of the catalyst system, simultaneously with the components of the catalyst system or at any point in the process of contacting the components of the catalyst .
- the three components of the catalyst system, (a) , (b) and (c) may be combined at a temperature in the range of from -100 to 200 0 C, preferably 0 to 150 0 C, more preferably 20 to 100 0 C.
- the catalyst system of the present invention may be unsupported or supported on a support material .
- suitable support materials can be found in WO 02/04119, WO 2004/056478 and WO 2004/056479.
- the olefinic monomers suitable for use in the trimerization and tetramerization process of the present invention can be any olefinic monomers, which can be converted into a trimer or tetramer.
- Suitable olefinic monomers include, but are not necessarily limited to, ethylene, propylene, optionally branched C4-C24, preferably C4-C20/ ⁇ -olefins, optionally branched C4-C24, preferably C4-C20/ internal olefins, optionally branched C 4 " C 2 4 ' Preferably C 4 -C2C vinylidene olefins, optionally branched C4-C 24 / preferably C 4 -C2O' cyclic olefins and optionally branched C 4 -C 24 , preferably C 4 -C 2 0/ dienes, as well as optionally branched C 4 -C24, preferably C 4 -C20/ functionalized olefins.
- Suitable olefinic monomers include, but are not necessarily limited to, linear ⁇ -olefins, such as ethylene, 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 and 1-eicosene; branched ⁇ - olefins such as 4-methylpent-l-ene and 2 -ethyl-1-hexene; linear and branched internal-olefins such as 2-butene; styrene; cyclohexene; norbornene and the like.
- linear ⁇ -olefins such as
- Mixtures of olefinic monomers can also be used in the process of the present invention.
- Preferred olefinic monomers for use in the trimerization and tetramerization process of the present invention are propylene and ethylene. Especially preferred is ethylene.
- the catalyst system and process of the present invention are particularly useful for the simultaneous trimerization and tetramerization of ethylene to 1-hexene and 1-octene.
- the simultaneous trimerization and tetramerization reaction can be performed in solution phase, slurry phase, gas phase or bulk phase.
- a diluent or solvent which is substantially inert under trimerization and tetramerization conditions may be employed.
- Suitable diluents or solvents are aliphatic and aromatic hydrocarbons, halogenated hydrocarbons and olefins which are substantially inert under trimerization and tetramerization conditions may be employed, such as those disclosed in WO 02/04119, WO2004/056478 and WO2004/056479.
- the trimerization and tetramerization process of the present invention may be performed in any one of a number of suitable reactors, which are well known to one skilled in the art. Typically the trimerization and tetramerization process of the present invention is carried out in a batch, semi-batch or continuous mode. The simultaneous trimerization and tetramerization process of the present invention may be carried out under the following range of reaction conditions. Typically, the temperature will be in the range from about 0 0 C to about 200 °C, preferably from about 10 °C to about 150 0 C, more preferably from about 40 °C to about 150 0 C, even more preferably from about 70 0 C to about 150 0 C.
- the process of present invention may also conveniently be performed at temperature range of from about 20 0 C to about 120 0 C. However, it may be commercially desirable to perform the process of the present invention at an elevated temperature, therefore, the process of the present invention is highly suitable to be applied at a temperature in the range of from about 70 0 C to about 100 0 C.
- the pressure range under which the process of the present invention may be performed is typically in the range of from below atmospheric pressure to about 100 barg. Preferably, the pressure will be in the range from about 0.1 to about 80 barg, more preferably from about 0.5 to about 70 barg, especially in the range of from about 1 to about 60 barg. Temperatures and pressures outside those stated above may also be employed, however, the reaction product will either have an excess of heavy and/or solid by-products or an insignificant amount of the trimer or tetramer.
- the process of the present invention can be used as a tuneable process for the trimerization and tetramerization of olefinic monomers.
- tuneable it is meant that by varying the reaction conditions of the process of the present invention, the amount of trimers and tetramers in the product composition produced by the process of the present invention may be varied. This may be useful for a tuneable, continuous or semi-continuous, process for the trimerization and tetramerization of olefinic monomers, wherein the product composition can be changed (e.g.
- this may be especially useful for a tuneable, continuous or semi- continuous, process for the trimerization and tetramerization of ethylene, wherein the product composition can be changed (e.g. from producing a higher proportion of 1-hexene to a higher proportion of 1- octene, or vice-versa) by changing the reactor conditions without having to interrupt the olefinic monomer feed or the trimerization and tetramerization product flow.
- the process comprises contacting at least one olefinic monomer under trimerization and tetramerization reaction conditions with a catalyst system of the present invention, wherein the process is a continuous or semi-continuous process and the reaction conditions are varied during the process. Variation of the reaction conditions can be performed to make continual adjustments to a process to ensure a consistent product slate or can be performed to a process to change the product slate produced.
- a preferred version of this embodiment is a process for the trimerization and tetramerization of ethylene, wherein the process comprises contacting ethylene with a catalyst system of the present invention, wherein the process is a continuous or semi-continuous process and the reaction conditions are varied during the process.
- Separation of the products, reactant and catalyst can be performed by any technique known to one skilled in the art, such as distillation, filtration, centrifugation, liquid/liquid separation, extraction, etc .
- the use of the process of the present invention for the catalytic trimerization and tetramerization of ethylene to 1-hexene and 1-octene provides a process with very high selectivity for 1- hexene and 1-octene over all the other products formed in the Cg and Cg fractions respectively and with reduced formation of by-products compared with equivalent trimerization and tetramerization processes.
- the overall yield of 1-hexene and 1-octene in the process for the trimerization and tetramerization of ethylene of the present invention depends upon the reaction conditions employed.
- the trimerization and tetramerization selectivity (i.e. the amount of trimers and tetramers of the olefinic monomers in the overall product composition) of the process of the present invention is at least 65 %wt , preferably at least 70 %wt , more preferably at least 75 %wt , of the overall product composition.
- the trimerization and tetramerization selectivity for the trimerization and tetramerization of ethylene (i.e. the amount of Cg and Cg fraction in the overall product composition) using the process of the present invention is at least 60 %wt , preferably at least 70 %wt , more preferably at least 80 %wt , of the overall product composition .
- the amount of 1-hexene produced by the trimerization and tetramerization of ethylene using the process of the present invention is typically in the range of from 10 %wt to 90 %wt, preferably from 11 %wt to 85 %wt, more preferably from 12 %wt to 80 %wt, of the overall product composition.
- the amount of 1-octene produced by the trimerization and tetramerization of ethylene using the process of the present invention is typically in the range of from 10 %wt to 90 %wt, preferably from 11 %wt to 85 %wt, more preferably from 12 %wt to 80 %wt, of the overall product composition.
- the 1-hexene selectivity (i.e. the amount of 1- hexene present in the Cg fraction of the product composition) in the trimerization and tetramerization of ethylene using the process of the present invention is preferably at least 85 %wt , more preferably at least 90 %wt , most preferably at least 92 %wt of the Cg fraction of the product composition.
- the 1-octene selectivity (i.e. the amount of 1- octene present in the C ⁇ fraction of the product composition) in the trimerization and tetramerization of ethylene using the process of the present invention is preferably at least 85%wt, more preferably at least 90 %wt , most preferably at least 92 %wt of the C ⁇ fraction of the product composition.
- the amount of solids produced in the trimerization and tetramerization of ethylene using the process of the present invention is typically at most about 5 %wt .
- Lower levels of solid olefin waxes and polyethylene produced in the trimerization and tetramerization of ethylene are desirable in commercial operations as this can reduce the amount of fouling of the reactor equipment, reduce the amount of waste by-products and reduce the amount of operational "downtime" due to maintenance and cleaning of the reactor equipment .
- the amount of C]_Q produced in the trimerization and tetramerization of ethylene using the process of the present invention is typically at most about 10 %wt .
- the amount of Ci_ 2 ⁇ c 1 4 produced in the trimerization and tetramerization of ethylene using the process of the present invention is typically at most about 10 %wt .
- the olefinic product composition of the trimerization and tetramerization of ethylene using the process of the present invention typically comprises a combined total content of 1-hexene and 1-octene of at least 70 %wt of the overall product composition, wherein the 1-hexene content is at least 10 %wt of the overall product composition, the 1-hexene selectivity is at least 90 %wt of the Cg fraction of the product composition, the 1- octene content is at least 10 %wt of the overall product composition, the 1-octene selectivity is at least 90 %wt of the Cs fraction of the product composition, and the amount of solids produced is at most about 5 %wt of the overall product composition.
- the olefinic product composition of the trimerization and tetramerization of ethylene using the process of the present invention comprises a total content of compounds other than 1-hexene and 1-octene of at most 40 %wt of the overall product composition, preferably at most 30 %wt and more preferably at most 20 %wt, wherein the 1-hexene content is at least 10 %wt of the overall product composition, the 1-hexene selectivity is at least 90 %wt of the Cg fraction of the product composition, the 1- octene content is at least 10 %wt of the overall product composition, the 1-octene selectivity is at least 90 %wt of the Cg fraction of the product composition, and the amount of solids produced is at most about 5 %wt of the overall product composition.
- GC Gas Chromatography
- trimerization selectivity when used in relation to the trimerization of ethylene to 1-hexene means the amount of Cg -fraction formed within the product composition, as determined by GC.
- tetramerization selectivity when used in relation to the tetramerization of ethylene to 1-octene means the amount of C ⁇ -fraction formed within the product composition, as determined by GC.
- 1-hexene selectivity when used in relation to the trimerization of ethylene to 1-hexene means the amount of 1-hexene formed within the Cg- fraction of the product composition, as determined by GC.
- the overall yield of 1-hexene in the trimerization of ethylene is the product of the "trimerization selectivity” multiplied by the "1-hexene selectivity” .
- the term “1-octene selectivity" when used in relation to the tetramerization of ethylene to 1-octene means the amount of 1-octene formed within the C ⁇ - fraction of the product composition, as determined by GC.
- the overall yield of 1-octene in the tetramerization of ethylene is the product of the "tetramerization selectivity" multiplied by the "1-octene selectivity”.
- the amount of "solids”, mainly consisting of heavy wax and polyethylene, has been determined by weighing, after its isolation from the reactor wall and appendages, followed by washing with toluene on a glass filter (P3) and by vacuum drying .
- the amount of "total product” is the sum of the amount of largely olefinic product derived from GC analysis and the amount of solids.
- the NMR data was obtained at room temperature with a Varian 300 MHz or 400 MHz apparatus.
- the catalyst compositions of the present invention were prepared from catalyst precursor compositions containing ligands B, C, D, E, F and G and a chromium source, these components are described below. Chromium source
- Chromium tris (2 , 4-pentanedionate) also called chromium tris (acetylacetonate) , i.e. Cr(acac)3, was used as the chromium source in the simultaneous tri- and tetramerization reactions of ethylene.
- Ligand composition E Chromium tris (2 , 4-pentanedionate) , also called chromium tris (acetylacetonate) , i.e. Cr(acac)3, was used as the chromium source in the simultaneous tri- and tetramerization reactions of ethylene.
- the reaction product between (2- methoxyphenyl) 2PNH (methyl) and (phenyl) 2PCl (ligand component E) was prepared by the following method. Under a nitrogen atmosphere 1.015 g (3.62 mmol) (2- methoxyphenyl) 2 PC1 in was added to 10 ml methylamine (2M in THF) in 50 ml pentane . The resulting mixture was stirred overnight at room temperature. The precipitate was removed by centrifugation. The solvents were removed from the resulting solution under vacuum. Washing with pentane yielded 0.85g (3.09mmol; (84%)) (2- methoxyphenyl) 2 PNH (methyl) as a white solid. 31 P-NMR (in C 6 D 6 ) signal at ⁇ 31.6.
- Pd[II] compound Upon complexation of a Pd[II] compound,
- the (2-methoxyphenyl) 2PN (CH3 ) P (2-methoxyphenyl) 2 ligand was prepared by first forming a solution of 1.59 g (5 mmol) (2-methoxyphenyl) 2PNEt 2 in 20 ml diethyl ether. To this solution 10 ml of a 1 M HCl solution in diethyl ether (10 mmol HCl) was added under an inert atmosphere at room temperature. The suspension thus formed was stirred overnight. The diethyl ether was removed from the product under vacuum and 20 ml of dry toluene was added.
- the (phenyl) 2PN (isopropyl) P (phenyl) 2 ligand was prepared by the following method. At 0 0 C, under a nitrogen atmosphere, 15 ml triethylamine was added to 6.3 g (phenyl) 2PCI in 80 ml of dry dichloromethane . To the resulting mixture, 0.844 g isopropylamine was added and allowed to stir overnight at room temperature. The solvents were removed from the resulting solution in- vacuo and 50 ml of dry toluene was added. The mixture was then filtered over a small layer of silica.
- the (phenyl) 2PN (isopropyl) P (2 -methoxyphenyl) 2 ligand was prepared by the following method.
- Ligand composition F The reaction product of (2 -methoxyphenyl ) ? PNH (methyl) and
- the reaction product of (2- methoxyphenyl) 2 PNH ( isopropyl) and (2-methoxyphenyl) 2 PCl (ligand composition G) was prepared as follows. Under a nitrogen atmosphere, 3 ml triethylamine was added to 1.5 ml isopropylamine (17.6 mmol) in 5 ml dry toluene. To the resulting mixture, 2.2 g (7.84 mmol) (2- methoxyphenyl) 2 PC1 in 20 ml toluene was slowly added and allowed to stir overnight at room temperature. The precipitate was removed by centrifugation. The solvents were removed from the resulting solution in vacuo.
- 31 P - NMR in C 6 D 6 ) ⁇ 0 . 0 and - 3 5 . 4
- Table 1 were placed in a glass bottle, to which dry toluene (typically 4 g) was added to obtain the catalyst precursor solution. Finally the bottle was sealed with a septum cap.
- dry toluene typically 4 g
- catalyst precursor solutions (the chromium tris (acetylacetonate) solutions are introduced as catalyst precursor solution which is to be activated by the pre-dosed MAO in- situ in the autoclave) , or part of these solutions, were used in the simultaneous tri- and tetramerization reaction of ethylene.
- the reactor was scavenged by introducing 250 ml toluene, MAO (0.6 g solution) and subsequent stirring at 70 0 C under nitrogen pressure of 0.4-0.5 MPa for 30 min.
- the reactor contents were discharged via a tap in the base of the autoclave.
- the reactor was evacuated to about 0.4 kPa and loaded with approximately 250 ml toluene (or heptane) , heated to 40 0 C and pressurised with ethylene to 15 barg or as indicated in Table 1.
- a MAO-solution typically an intake of 3.12 g, 6 mmol Al
- toluene typically an intake of 3.12 g, 6 mmol Al
- an Al/Cr atomic ratio of 200 typically, the total volume injected was about 25 ml: the MAO-solution diluted with toluene to 8 ml was injected and the injector system was rinsed twice with 8 ml toluene
- the stirring at 800 rpm was continued for 30 minutes.
- the Cr-catalyst precursor system (typically 30 ⁇ mol on Cr intake), prepared as described above, was introduced into the stirred reactor using an injection system with the aid of toluene (the total volume injected was about 25 ml: the catalyst solution diluted with toluene to 8 ml was injected and the injector system was rinsed twice with 8 ml toluene) .
- the initial loading of the reactor was about 300 ml of largely toluene.
- comparative ligand C having a predominant P-N-P structure, an isopropyl group on N and two phenyl groups on each P, also shows a higher 1-octene selectivity than comparative ligand D, but at the expense of increased solids formation at elevated temperatures (> 70 0 C) .
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Abstract
The present invention relates to a ligand having the general formula (I) : (R1) 2P-P(R1)m(R2)n=N(R3) (I) wherein R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; the R1 groups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions; and the R2 groups are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions, with the proviso that m is 0 or 1, n is 1 or 2 and the total of m + n is 2. The present invention also relates to catalyst systems and a process for the simultaneous trimerization and tetramerization of olefinic monomers using said ligands.
Description
LIGANDS AND CATALYST SYSTEMS FOR THE OLIGOMERIZATION OF
OLEFINIC MONOMERS
Field of the Invention
The present invention relates to ligands and to catalyst systems comprising said ligands. The present invention further relates to a process for the oligomerization of olefinic monomers using said catalyst systems . Background of the Invention
The efficient catalytic trimerization or tetramerization of olefinic monomers, such as the trimerization and tetramerization of ethylene to 1-hexene and 1-octene, is an area of great interest for the production of olefinic trimers and tetramers of varying degrees of commercial value. In particular, 1-hexene is a valuable comonomer for linear low-density polyethylene (LLDPE) and 1-octene is valuable as a chemical intermediate in the production of plasticizer alcohols, fatty acids, detergent alcohol and lubrication oil additives as well as a valuable comonomer in the production of polymers such as polyethylene. 1-Hexene and 1-octene can be produced by a conventional transition metal oligomerization process, although the trimerization and tetramerization routes are preferred.
Several different catalytic systems have been disclosed in the art for the trimerization of ethylene to 1-hexene. A number of these catalysts are based on chromium .
US-A-5198563 (Phillips) discloses chromium-based catalysts containing monodentate amine ligands useful for trimerizing olefins.
US-A-5968866 (Phillips) discloses an ethylene oligomerization/trimerization process which uses a catalyst comprising a chromium complex which contains a coordinating asymmetric tridentate phosphane, arsane or stibane ligand and an aluminoxane to produce alpha- olefins which are enriched in 1-hexene. US5523507 (Phillips) discloses a catalyst based on a chromium source, a 2 , 5-dimethylpyrrole ligand and an alkyl aluminium activator for use in the trimerization of ethylene to 1-hexene.
Chem. Commun., 2002, 8, 858-859 (BP), discloses chromium complexes of ligands of the type A^PN (Me) PAr2
(Ar = ortho-methoxy-substituted aryl group) as catalysts for the trimerization of ethylene.
WO 02/04119 (BP) discloses a catalyst for the trimerization of olefins comprising a source of chromium, molybdenum or tungsten, a ligand containing at least one phosphorus, arsenic or antimony atom bound to at least one hydrocarbyl or heterohydrocarbyl group having a polar substituent, but excluding the case where all such polar substituents are phosphane, arsane or stibane groups, and optionally an activator. The ligand used in most of the examples is (2-methoxyphenyl) 2PN (Me) P (2-methoxyphenyl) 2 •
Although the catalysts disclosed in the BP documents mentioned above have good selectivity for 1-hexene within the Cg fraction, a relatively high level of by-product formation (e.g. C^Q by-products) is typically observed.
WO 2005/039758 (Shell) discloses a trimerization catalyst composition and a process for the trimerization of olefinic monomers using said catalyst composition.
Catalytic systems for the tetramerization of ethylene to 1-octene have recently been described. A number of these catalysts are based on chromium.
WO 2004/056478 and WO 2004/056479 (Sasol) disclose catalyst compositions and processes for the tetramerization of olefins. The catalyst compositions disclosed in WO 2004/056478 comprise a transition metal and a heteroatomic ligand having the general formula (R) nA-B-C (R) m where A and C are independently selected from a group which comprises phosphorus, arsenic, antimony, oxygen, bismuth, sulphur, selenium, and nitrogen, and B is a linking group between A and C, and R is independently selected from any homo or heterohydrocarbyl group of which at least one R group is substituted with a polar substituent and n and m are determined by the respective valence and oxidation state of A and/or C. The catalyst compositions disclosed in WO 2004/056479 comprise a transition metal and a heteroatomic ligand having the general formula (R')nA-B-
C(R' ) m where A, B, C, n and m are as defined above, and
R' is independently selected from any homo or heterohydrocarbyl group.
Example 16 of WO 2004/056478 discloses an ethylene tetramerization reaction using Cr (III) acetylacetonoate, (phenyl) 2PN (isopropyl) P (2-methoxyphenyl) 2 in a ratio of 1:2 mol/mol, and MAO, with an Al : Cr atomic ratio of 136:1, at 45 0C and 45 barg. However, the reaction
produced a product composition with over 24 wt% of the products having greater than 11 carbon atoms, based on the weight of all products (9.00 wt% C^1+ liquids and
15.11 wt% solids) . WO 2004/056480 (Sasol) discloses the tandem tetramerization and polymerisation of ethylene. Specifically, WO 2004/056480 discloses a process for polymerising olefins to produce branched polyolefins in the presence of a distinct polymerization catalyst and a distinct tetramerization catalyst, wherein the tetramerization catalyst produces 1-octene in a selectivity greater than 30% and the 1-octene produced is at least partially incorporated into the polyolefin chain. Although the tetramerization catalysts disclosed in the Sasol documents mentioned above have good selectivity for 1-octene within the Cs fraction, again, a relatively high level of by-product formation is observed. Typically, the by-product consists of Cg compositions; however, only about 70 to 80 %wt . of the Cg by-product composition is 1-hexene, with the remaining Cg by-product comprising compounds such as methylcyclopentane and methylenecyclopentane . The presence of these remaining Cg by-product compositions, which have very little commercial use or value, is highly undesirable from both an economic point of view as well as from a product separation point of view.
It has now been surprisingly found that the ligands and catalyst systems of the present invention provide excellent results in the trimerization and
tetramerization of olefinic monomers. In particular the selective production of 1-hexene and 1-octene from ethylene is achieved while reducing the level of byproduct formation, especially C]_Q by-products, solids (i.e. heavy waxes and/or polyethylene) and Cg compositions/isomers other than 1-hexene. Summary of the Invention
According to the present invention there is provided a ligand having the general formula (I) : (R1)2P-P(R1)m(R2)n=N(R3) (I) wherein R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; the R1 groups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions,- and the R2 groups are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions; with the proviso that m is 0 or 1, n is 1 or 2 and the total of m + n is 2. According to another aspect of the present invention there is provided a ligand having the general formula
(ID :
P(R1)m(R2)n-P(Rl)2=N(R3) (II) wherein R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a
heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof; the R1 groups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho-positions; and the R2 groups are independently selected from hydrocarbyl, substituted hydrocarbyl , heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions; with the proviso that m is 0 or 1, n is 1 or 2 and the total of m + n is 2.
According to a further aspect of the present invention there is a provided a process for preparing a ligand having the general formulae (I) or (II) which comprises reacting: (i) a compound of formula (III) :
X-P(R1)m(R2)n (III) wherein X is a halide, and R1, R2, m and n are as defined above for ligands having general formulae (I) and (II); and (ii) a compound of formula (IV) :
(R1J2P-N(R3JH (IV) wherein R1 and R3 are as defined above for ligands of general formulae (I) and (II); in the presence of an HX-acceptor.
According to a further aspect of the present invention there is provided a process for preparing a ligand having the general formula (I) or (II) which comprises reacting:
(i) a compound of formula (V) :
X-P(R1J2 (V) wherein X is halide, and R1 is as defined above for ligands of general formulae (I) and (II) ; and (ii) a compound of formula (VI) :
(Ri)1n(R2JnP-N(RS)H (VI) wherein R1, R2, R3, m and n are as defined above for ligands of general formulae (I) and (II) ,- in the presence of an HX-acceptor. According to yet a further aspect of the present invention there is provided a ligand system prepared by reacting :
(i) a compound of formula (III) :
X-P(R1)m(R2)n (III) wherein X is a halide, and R1, R2, m and n are as defined above for ligands (I) and (II) ; and (ii) a compound of formula (IV) :
(R1)2P-N(R3)H (IV) wherein R1 and R3 are as defined above for ligands (I) and (II) ; in the presence of an HX-acceptor.
According to yet a further aspect of the present invention there is provided a ligand system prepared by reacting: (i) a compound of formula (V) :
X-P(R1J2 (V) wherein X is halide, and R1 is as defined above for ligands having the general formulae (I) and (II) ; and (ii) a compound of formula (VI) :
(R1)m(R2)nP-N(R3)H (VI) wherein R1, R2, R3, m and n are as defined above for ligands having the general formulae (I) and (II); in the presence of an HX-acceptor. According to the present invention there is provided a catalyst system comprising: a) a source of chromium, molybdenum or tungsten; b) a ligand or a ligand system as described herein; and c) a cocatalyst .
According to another aspect of the present invention, there is provided simultaneous trimerization and tetramerization of olefinic monomers, wherein the process comprises contacting at least one olefinic monomer with the catalyst system herein at a pressure in the range of from below atmospheric to 100 barg and at a temperature in the range of from 0 0C to 200 0C. Detailed Description of the Invention
As used herein, the term "trimerization" means the catalytic trimerization of an olefinic monomer to give a product composition enriched in the compound derived from the reaction of three of said olefinic monomers. The term trimerization includes the cases wherein all the olefinic monomers in the feed stream are identical as well as the cases wherein the feed stream contains two or more different olefinic monomers.
In particularly, the term "trimerization" when used in relation to the trimerization of ethylene means the trimerization of ethylene to form a Cg alkene, especially 1-hexene.
- S -
The term "trimerization selectivity" when used in relation to the trimerization of ethylene means the amount of Cg fraction formed within the product composition. The term "1-hexene selectivity" when used in relation to the trimerization of ethylene means the amount of 1-hexene formed within the Cg fraction of the product composition. The overall yield of 1-hexene in the trimerization of ethylene is the product of the "trimerization selectivity" multiplied by the "1-hexene selectivity" .
The term "tetramerization" means the catalytic tetramerization of an olefinic monomer to give a product composition enriched in the compound derived from the reaction of four of said olefinic monomers. The term tetramerization includes the cases wherein all the olefinic monomers in the feed stream are identical as well as the cases wherein the feed stream contains two or more different olefinic monomers. In particularly, the term "tetramerization" when used in relation to the tetramerization of ethylene means the tetramerization of ethylene to form a Cg alkene, especially 1-octene.
The term "tetramerization selectivity" when used in relation to the tetramerization of ethylene means the amount of Cg fraction formed within the product composition .
The term "1-octene selectivity" when used in relation to the tetramerization of ethylene means the amount of 1-octene formed within the Cg fraction of the
product composition. The overall yield of 1-octene in the tetramerization of ethylene is the product of the "tetramerization selectivity" multiplied by the "1-octene selectivity" . The term "hydrocarbyl" as used herein refers to a group only containing carbon and hydrogen atoms . The hydrocarbyl group may be a saturated or unsaturated, linear or branched alkyl, a non-aromatic ring or an aromatic ring. Unless otherwise stated, the preferred hydrocarbyl groups for use herein are those containing from 1 to 20 carbon atoms.
The term "substituted hydrocarbyl" as used herein refers to hydrocarbyl groups which contain one or more inert heteroatom containing functional groups. By "inert heteroatom containing functional groups" is meant that the functional groups do not interfere to any substantial degree with the trimerization and tetramerization process .
The term "heterohydrocarbyl" as used herein refers to a hydrocarbyl group wherein one or more of the carbon atoms is replaced by a heteroatom, such as Si, S, N or 0. The carbon atom of the hydrocarbyl group which is replaced by a heteroatom can be either an internal carbon atom of the hydrocarbyl group or the carbon atom through which the heterohydrocarbyl group is attached, e.g. the atom which is attached to the nitrogen atom in the case of the bridging group, e.g. -N(OMe)-. The term "substituted heterohydrocarbyl" as used herein refers to heterohydrocarbyl groups which contain one or more inert heteroatom containing functional groups.
The term "aromatic" as used herein, refers to a monocyclic or polycyclic, aromatic or heteroaromatic ring having from 5 to 14 ring atoms, optionally containing from 1 to 3 heteroatoms selected from N, 0 and S. Preferably, the aromatic groups are monocyclic or polycyclic aromatic rings, such as cyclopentadienyl (which can also include ferrocenyl groups), phenyl, biphenyl, naphthyl or anthracenyl . Unless otherwise stated, the preferred aromatic groups are monocyclic or polycyclic aromatic rings having from 5 to 10 ring atoms, more preferred aromatic groups are monocyclic aromatic rings containing from 5 to 6 carbon atoms, such as phenyl and cyclopentadienyl, and a most preferred aromatic group is a phenyl group. The term "substituted aromatic" as used herein means that the aromatic group may be substituted with one or more substituents .
By the term "ortho-position" when used in relation to substituents on aromatic R^ and/or R2 groups, it is meant that the substituent is in the ortho position relative to the atom bonded to the phosphorus atom.
The ligands of the present invention have the general formulae (I) and (II) below:
(R1) 2P-P(R1) m (R2)n=N(R3) (D P(R1)m(R2)n-P(R1)2=N(R3) (II) wherein R1, R2, R3, and R4 are as defined above.
R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof. Typically, R3 is selected from hydrogen or the groups consisting of alkyl, substituted
alkyl, aryl, substituted aryl, aryloxy, substituted aryloxy, alkenyl, substituted alkenyl, cycloalkyl, substituted cycloalkyl, alkoxycarbonyl , carbonyloxy, alkoxy, aminocarbonyl , carbonylamino, dialkylamino, silyl groups or derivatives thereof, and alkyl or aryl groups substituted with any of these substituents or halogen or a nitro group. More preferably R3 is an alkyl, substituted alkyl (including heterocyclic substituted alkyl with at least one heteroatom, such as N or 0, and alkyl groups substituted with a heteroatom or heteroatomic group), cycloalkyl, substituted cycloalkyl, substituted cyclic aryl, substituted aryl, aryloxy or substituted aryloxy group. Examples of suitable R3 groups include C]_-C]_5 alkyl groups, substituted C]_-C]_5 alkyl groups, C2-C15 alkenyl groups, substituted C2-C15 alkenyl groups, C3-C15 cycloalkyl groups, substituted C3-C15 cycloalkyl groups, C5-C15 aromatic groups, substituted C5-C15 aromatic groups, C]_-Cj_5 alkoxy groups and substituted C]_-C]_5 alkoxy groups. Most preferred R3 groups are the C]_-C^5 alkyl groups, which include both linear and branched alkyl groups; suitable examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl , alkyl branched pentyl groups, hexyl , alkyl branched hexyl groups, heptyl , alkyl branched heptyl groups, octyl and alkyl branched octyl groups .
Examples of suitable =N(R3) groups include =N (methyl), =N (ethyl), =N(propyl), =N (isopropyl) , =N (butyl), =N (tert-butyl) , =N (pentyl), =N (hexyl), =N(2- ethylhexyl) , =N (cyclohexyl) , =N (1-cyclohexylethyl) , =N(2-
methylcyclohexyl) , =N(benzyl), =N(phenyl), =N(2-octyl), =N(4-methoxyphenyl) , =N (4-tert-butylphenyl) , =N ((CH2) 3 -N- morpholine) , =N(Si (CH3) 3) , =N (CH2CH2CH2Si (OMe) 3 )), =N(decyl) and =N(allyl) . The substituents on the R1 and/or R2 groups can contain carbon atoms and/or heteroatoms . The substituents may be either polar or non-polar. Suitable substituents include hydrocarbyl groups which may be straight -chain or branched, saturated or unsaturated, aromatic or non- aromatic. The hydrocarbyl substituents may optionally contain heteroatoms such as Si, S, N or 0. Suitable aromatic hydrocarbyl substituents include monocyclic and polycyclic aromatic groups, preferably having from 5 to 10 carbon atoms in the ring, such as phenyl and C1-C4 alkyl phenyl groups. Suitable non-aromatic hydrocarbyl substituents include linear or branched alkyl or cycloalkyl groups, preferably having from 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
Other suitable substituents on the R1 and/or R2 groups include halides such as chloride, bromide and iodide, thiol, -OH, A1-©-, -S-A1, -CO-A1, -NH2, -NHA1, -
NA1A2, -CO-NA1A2, -NO2, =0, in which A1 and A2, independently, are non-aromatic groups preferably having from 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl and isopropyl .
When the R1 and/or R2 groups of the ligand are substituted, preferred substituents are hydrocarbyl groups. Particularly preferred hydrocarbyl substituents
are C1-C4 alkyl groups, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, most preferably methyl.
In one embodiment of the present invention, m is 1 and n is i. In another embodiment m is 0 and n is 2. Typically, in the ligands of the present invention, component (b) , m is 0 and n is 2.
The R1 groups of the ligand are independently selected from optionally substituted aromatic groups, each bearing a polar substituent on at least one of the ortho-positions. For the avoidance of doubt, the phrase "bearing a polar substituent on at least one of the ortho-positions" means that, in the same ligand, the R1 group is substituted with a polar substituent on one or both of its ortho positions. The term "optionally substituted" in relation to the
R1 groups of the ligand of the present invention, which are independently selected from optionally substituted aromatic groups, each bearing a polar substituent on at least one of the ortho-positions, means that, in addition to the polar substituent on at least one of the ortho- positions, the same R1 group may contain one or more other substituents .
Polar is defined by IUPAC as an entity with a permanent electric dipole moment. Therefore, as used herein, the term "polar substituents" means a substituent which incorporates a permanent electric dipole moment .
Suitable polar substituents for use herein include but are not necessarily limited to, optionally branched c l~c 20 alkoxy groups, i.e. the R1 and/or R2 groups are substituted with a hydrocarbyl group connected through an
oxygen bridging atom; optionally substituted C5-C14 aryloxy groups, i.e. the R1 and/or R2 groups are substituted with an optionally substituted aromatic group connected through an oxygen bridging atom; optionally branched C]_-C2o alkoxy (C]_-C2o) alkyl groups, i.e. the R1 and/or R2 groups are substituted with a C1-C20 hydrocarbyl group bearing a C1-C20 alkoxy group,- hydroxyl ; amino; (di-)C]_-Cg alkylamino; nitro; C^-Cg alkylsulphonyl ; C]_-Cg alkylthio (C^-Cg ) alkyl groups,- sulphate; heterocyclic groups, especially with at least one N and/or 0 ring atom; and tosyl groups.
Examples of suitable polar substituents include methoxy, ethoxy, isopropoxy, phenoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy, eicosanoxy, pentafluorophenoxy, trimethylsiloxy, dimethylamino, methylsulphonyl, tosyl, methoxymethyl, methylthiomethyl , 1 , 3-oxazolyl , hydroxyl, amino, methoxymethyl, phosphino, arsino, stibino, sulphate, nitro and the like. Preferably, the polar substituents in the R1 groups are independently selected from optionally branched C]_-
C20 alkoxy groups, optionally substituted C5-C14 aryloxy groups, and optionally branched C1-C20 alkyl (C]_- C2θ)alkoχy groups. More preferably, the polar substituents are independently selected from optionally branched C1-C20 alkoxy groups, especially optionally branched C]_-Cg alkoxy groups such as, for example, methoxy, ethoxy or isopropoxy of which methoxy is a particularly preferred polar substituent; alternatively,
longer optionally branched C]_-C2Q alkoxy groups such as optionally branched Cg-C2o alkoxy groups, for example decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, octadecyloxy or eicosanoxy groups, of which eicosanoxy is preferred, may be preferred as the polar substituents in order to increase the solubility of the ligand in organic media .
In one embodiment, the RA group is independently selected from substituted or unsubstituted aromatic groups bearing an optionally branched C]_-C2o alkoxy group on at least one of the ortho-positions, such as an o- anisyl group.
It is preferred that the R1 groups of the ligands having the formulae (I) and (II) are the same and bear the same number and type of polar substituent (s) . It is particularly preferred that each of said RA groups bears a polar substituent on only one of the two available ortho-positions .
The R^ groups of the ligands having the formulae (I) and (II) are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions. It is preferred that each of said R2 groups are independently selected from substituted or unsubstituted aromatic groups, including substituted or unsubstituted heteroaromatic groups, which do not contain a polar substituent at any of the ortho-positions.
Said R2 groups may be independently selected from a group comprising optionally substituted benzyl, phenyl, tolyl, xylyl, mesityl, biphenyl, naphthyl, anthracenyl, methoxy, ethoxy, phenoxy, tolyloxy, dimethylamino, diethylamino, methylethylamino, thiophenyl, pyridyl, thioethyl, thiophenoxy, trimethylsilyl , dimethylhydrazyl , methyl, ethyl, ethenyl, propyl, butyl, tert-butyl, propenyl , propynyl , cyclopentyl, cyclohexyl, ferrocenyl and tetrahydrofuranyl groups . In another embodiment of the ligand, said R2 groups may be independently selected from a group comprising optionally substituted phenyl, tolyl, biphenyl, naphthyl, thiophenyl and ethyl groups. In a preferred embodiment of the present invention, said R2 groups are independently selected from optionally substituted phenyl groups which do not contain a polar substituent at any of the ortho-positions, or alternatively, do not contain any polar substituents at all . Any polar substituent present in said R2 groups may be electron donating. Said R2 groups may optionally contain non-polar substituent.
IUPAC defines non-polar as an entity without a permanent electric dipole moment.
Suitable non-polar substituents may be a methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tert-butyl, pentyl , hexyl , cyclopentyl, 2-methylcyclohexyl , cyclohexyl, cylopentadienyl, phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, ethenyl, propenyl and benzyl group, or the like. Preferably, the non-polar substituent is not electron donating.
In one specific embodiment herein said R2 group is an unsubstituted phenyl group.
Optionally, any of the R-^- and R2 groups may independently be linked to one or more of each other or to the =N(R3) group to form a cyclic structure. In particular, when n is 2 then the two R2 groups may optionally be linked together to form a cyclic structure incorporating the phosphorus atom.
In another embodiment of the present invention, one or both of the phosphorus atoms of the ligands of the present invention may be independently oxidised by S, Se, N or 0. Typically, neither of the phosphorus atoms of the second ligand are oxidised by S, Se, N or 0.
The ligands according to general formulae (I) and (II) can be prepared by a process which comprises reacting: (i) a compound of formula (III) :
X-P(R1)m(R2)n (III) wherein X is a halide, and R1, R2, m and n are as defined above for ligands (I) and (II) ,- and (ii) a compound of formula (IV) :
(R1) 2P-N(R3)H (IV) wherein R^ and R3 are as defined above for ligands (I) and (II) ; in the presence of an HX-acceptor.
Suitable HX acceptors include neopentyl lithium, n- butyl lithium, sec-butyl lithium, lithium hydride, sodium hydride, potassium hydride, triethylamine, trimethylamine, tripropylamine and the like.
The ligands according to general formulae (I) and (II) can alternatively be prepared by a process which comprises reacting: (i) a compound of formula (V) : X-P(Rl)2 (V); wherein X is a halide and R1 is as defined above for general formulae (I) and (II) ; and (ii) a compound of formula (VI) :
(R1)m(R2)nP-N(R3)H (VI) ; wherein R1, R2, R3, m and n are as defined above for ligands of general formulae (I) and (II),-in the presence of an HX acceptor.
While not wishing to be bound by theory it is believed that in the presence of an activated metal component (a), e.g. activated chromium, an equilibrium exists between ligands of the P-P=N type and ligands of the P-N-P type as shown below:
(R1)2P-P(R1)m(R2)n =N(R3) ^ (R1)m(R2)nP-P(R1)2=N(R3) « (R1J2P-N(R3) -P (R1Jjn(R2Jn Therefore according to another aspect of the present invention there is provided a ligand system prepared by a process which comprises reacting: (i) a compound of formula (III) :
X-P(R1)m(R2)n (III) wherein X is a halide, and R1, R2, m and n are as defined above for ligands of general formulae (I) and (II); and (ii) a compound of formula (IV) :
(R1) 2P-N(R3)H (IV)
wherein R1 and R3 are as defined above for ligands of general formulae (I) and (II) ; in the presence of an HX- acceptor .
There is also provided herein a ligand system prepared by a process which comprises reacting: (i) a compound of formula (V) :
X-P(R1J2 (V); wherein X is a halide and R1 is as defined above for ligands of general formula (I) and (II) ; and (ii) a compound of formula (VI) :
(R1)m(R2)nP-N(R3)H (VI) ; wherein R1, R2, R3, m and n are as defined above for ligands of general formula (I) and (II); in the presence of an HX acceptor. Examples of ligands of the present invention include the two P-P=N forms of each of the P-N-P structures listed below: (2-methoxyphenyl) 2PN (methyl) P (2- methoxyphenyl ) (phenyl) t (2- methoxyphenyl) 2PN (methyl) P (phenyl) 2 , (2- ethoxyphenyl) 2PN (methyl) P (2-ethoxyphenyl) (phenyl) ^ (2- ethoxyphenyl) 2PN (methyl) P (phenyl) 2 , (2-methoxyphenyl) (2- ethoxyphenyl) PN (methyl) P (2-methoxyphenyl) (phenyl) (2- methoxyphenyl) (2-ethoxyphenyl) PN (methyl) P (phenyl) 2 , (2- isopropoxyphenyl) 2PN (methyl) P (2- isopropoxyphenyl) (phenyl) f (2- isopropoxyphenyl) 2PN (methyl) P (phenyl) 2 , (2- methoxyphenyl) 2PN (methyl) P (2-methoxyphenyl) (3- methoxyphenyl) (2 -methoxyphenyl) 2PN (methyl) P (3 -
_ o i _
methoxyphenyl) 2 , (2-methoxyphenyl) 2PN (methyl) P (2- methoxyphenyl) (4 -methoxyphenyl) t (2- methoxyphenyl) 2PN (methyl) P (4 -methoxyphenyl) 2 (2- methoxyphenyl) 2PN (methyl) P (2-methoxyphenyl) (4- fluorophenyl) (2-methoxyphenyl) 2PN (methyl) P (4- fluorophenyl) 2 , (2-methoxyphenyl) 2PN (methyl) P (2- ethoxyphenyl) (4 -fluorophenyl) ; (2- methoxyphenyl ) 2PN (methyl) P (2 -methoxyphenyl) (4- dimethylamino-phenyl) t (2-methoxyphenyl) 2PN (methyl) P (4- dimethylamino-phenyl) 2 (2-methoxyphenyl) 2PN (methyl) P (2- methoxyphenyl) (4- (4 -methoxyphenyl) -phenyl) (2- methoxyphenyl) 2PN (methyl) P (4- (4 -methoxyphenyl) -phenyl) 2 , (2-methoxyphenyl) 2PN (methyl) P (2-methoxyphenyl) (4- dimethylamino-phenyl) (2-methoxyphenyl) 2PN (methyl) P (4- dimethylamino-phenyl) 2 (2-methoxyphenyl) 2PN (methyl) P (2 - methoxyphenyl) (4- (4 -methoxyphenyl) -phenyl) ^ (2- methoxyphenyl) 2PN (methyl) P (4- (4 -methoxyphenyl) -phenyl) 2 , (2-methoxyphenyl) 2PN (methyl) P (2-methoxyphenyl) (ethyl) (2-methoxyphenyl) 2PN (methyl) P (ethyl) 2/ (2- methoxyphenyl) 2PN (methyl) P (2 -methoxyphenyl) (2- ethylphenyl) (2-methoxyphenyl) 2PN (methyl) P (2- ethylphenyl)2 , (2-methoxyphenyl) 2PN (methyl) P(2- methoxyphenyl) (2-naphthyl) f (2- methoxypheny1 ) 2PN (methy1 ) P (2 -naphthy1) 2 , (2 - methoxyphenyl) 2PN (methyl) P (2-methoxyphenyl) (4-biphenyl) t (2-methoxyphenyl) 2PN (methyl) P (4-biphenyl) 2 , (2- methoxypheny1) 2PN (methyl) P (2-methoxyphenyl) (4-
methylphenyl) f (2-methoxyphenyl) 2PN (methyl) P (4- methylphenyl) 2 , (2-methoxyphenyl) 2PN (methyl) P (2- methoxyphenyl) (2-thiophenyl) t (2- methoxyphenyl) 2PN (methyl) P (2-thiophenyl) 2 (2- methoxyphenyl) 2PN (methyl) P (2-methoxyphenyl) (3- methylphenyl) (2-methoxyphenyl) 2PN (methyl) P (3- methylphenyl) 2 , (2-methoxyphenyl) 2PN (ethyl) P (2- methoxyphenyl) (phenyl) ( (2- methoxyphenyl) 2pN(ethyl) P (phenyl) 2 , (2-methoxyphenyl) 2 PN(propyl)P (2-methoxyphenyl) (phenyl) (2-methoxyphenyl) 2
PN (propyl) P (phenyl) 2, (2~ methoxyphenyl) 2PN (isopropyl) P (2-methoxyphenyl) (phenyl) (2-methoxyphenyl) 2PN ( isopropyl) P (phenyl) 2 (2 - methoxyphenyl) 2PN (butyl) P (2-methoxyphenyl) (phenyl) (2- methoxyphenyl) 2PN (butyl) P (phenyl) 2/ (2- methoxyphenyl) 2PN (tert-butyl) P (2-methoxyphenyl) (phenyl) (2-methoxyphenyl) 2PN (tert-butyl) P (phenyl) 2 , (2- methoxyphenyl ) 2?N (phenyl) P (2 -methoxyphenyl) (phenyl) (2- methoxyphenyl) 2PN (phenyl) P (phenyl) 2 (2- methoxyphenyl) 2PN (cyclohexyl) P (2-methoxyphenyl) (phenyl) (2-methoxyphenyl) 2PN (cyclohexyl) P (phenyl) 2 (2- methoxyphenyl) 2PN (1-cyclohexylethyl) P (2- methoxyphenyl ) (phenyl) (2-methoxyphenyl) 2PN (1- cyclohexylethyl) P (phenyl) 2 , (2-methoxyphenyl) 2PN (2- methylcyclohexyl) P (2-methoxyphenyl) (phenyl) (2- methoxyphenyl) 2PN (2 -methylcyclohexyl) P (phenyl) 2 (2- methoxyphenyl) 2PN (decyl) P (2-methoxyphenyl) (phenyl) (2-
methoxypheny1 ) 2PN (decy1 ) P (phenyl ) 2 (2 - methoxyphenyl) 2PN (allyl) P (2-methoxyphenyl) (phenyl) (2- methoxypheny1) 2PN (allyl) P (phenyl) 2 (2- methoxypheny1) 2pN(4 -methoxyphenyl) P (2- methoxyphenyl) (phenyl) / (2-methoxyphenyl) 2PN (4- methoxyphenyl) P (phenyl) 2 , (2-methoxyphenyl) 2PN(4-tert- butylphenyl) P (2-methoxyphenyl) (phenyl) (2- methoxypheny1) 2PN (4-tert-butylphenyl) P (phenyl) 2 (2- methoxyphenyl ) 2PN ( (CH2 ) 3 -N-morpholine) P ( 2 - methoxyphenyl) (phenyl) (2-methoxyphenyl) 2PN ( (CH2) 3 -N- morpholine) P (phenyl) 2 (2-methoxyphenyl) 2PN (Si (CH3 ) 3 ) P (2- methoxypheny1 ) (phenyl ) (2 - methoxyphenyl) 2PN (Si (CH3 ) 3 ) P (phenyl) 2 (2- methoxyphenyl) 2PN (benzyl) P (2-methoxyphenyl) (phenyl) (2- methoxyphenyl) 2PN (benzyl) P (phenyl) 2 ; (2- methoxyphenyl) 2PN (1-cyclohexyl-ethyl) P (2 - methoxyphenyl) (phenyl) t (2-methoxyphenyl) 2PN ( 1- cyclohexyl-ethyl) P (phenyl) 2 , (2- methoxyphenyl) 2PN[CH2CH2CH2Si (OMe3) ] P(2- methoxyphenyl) (phenyl) (2- methoxyphenyl) 2PN[CH2CH2CH2Si (OMe3) ] P(phenyl) 2, (2- methoxyphenyl) 2PN (2-methylcyclohexyl) P (2- methoxyphenyl) (phenyl) # (2-methoxyphenyl) 2PN (2 - methylcyclohexyl) P (phenyl) 2 , (2- eicosanoxyphenyl) 2PN (methyl) P (2- eicosanoxyphenyl) (phenyl) , (2- eicosanoxyphenyl) 2PN (methyl) P (phenyl) 2 # (2-
methoxyphenyl) ( 2-eicosanoxyphenyl) PN (methyl) P (phenyl) 2 ,
(2-methoxyphenyl) ( 2-eicosanoxyphenyl) PN (methyl) P (2- eicosanoxyphenyl) (phenyl) , (2- eicosanoxyphenyl) 2PN (methyl) P (4- eicosanoxyphenyl) (phenyl), (2-methoxyphenyl) ( 2- eicosanoxyphenyl) PN (methyl) P (4 -eicosanoxyphenyl) (phenyl) , (2-eicosanoxyphenyl) 2PN (methyl) P (4-eicosanoxyphenyl) 2 /
(2-methoxyphenyl) ( 2-eicosanoxyphenyl) PN (methyl) P (4 - eicosanoxyphenyl) 2 / (2-eicosanoxyphenyl) 2PN (methyl) P (2- eicosanoxyphenyl) (4 -eicosanoxyphenyl ), (2-methoxyphenyl) (
2-eicosanoxyphenyl) PN (methyl) P (2-eicosanoxyphenyl) (4- eicosanoxyphenyl) , and the like.
For example, the two P-P=N forms of the (2- methoxyphenyl) 2PN (methyl) P (phenyl) 2 ligand are (2- methoxyphenyl) 2P-P (phenyl) 2=N (methyl) and (phenyl) 2P-P (2 - methoxyphenyl) 2=N (methyl ) .
The ligands and ligand systems of the present invention can be used in a catalyst system which comprises : (a) a source of chromium, molybdenum or tungsten;
(b) a ligand or ligand system as described herein; and
(c) a cocatalyst .
The source of chromium, molybdenum or tungsten, component (a) , for the catalyst system of the present invention can include simple inorganic and organic salts of chromium, molybdenum or tungsten. Examples of simple inorganic and organic salts are halides, acetylacetonates , carboxylates , oxides, nitrates, sulfates and the like. Further sources of chromium,
molybdenum or tungsten can also include co-ordination and organometallic complexes, for example chromium trichloride tris-tetrahydrofuran complex, (benzene) tricarbonylchromium, chromium hexacarbonyl , and the like. Preferably, the source of chromium, molybdenum or tungsten, component (a) , for the catalyst system are selected from simple inorganic and organic salts of chromium, molybdenum or tungsten.
In one embodiment of the present invention, the source of chromium, molybdenum or tungsten, component (a) , for the catalyst system is a simple inorganic or organic salt of chromium, molybdenum or tungsten, which is soluble in a solvent such as those disclosed in WO 02/04119. The source of chromium, molybdenum or tungsten can also include a mixture of any combination of simple inorganic salts, simple organic salts, co-ordination complexes and organometallic complexes.
In a preferred embodiment herein, component (a) is a source of chromium, particularly chromium (III) .
Preferred sources of chromium for use herein are simple inorganic and organic salts of chromium and coordination or organometallic complexes of chromium. More preferred sources of chromium for use herein are the simple inorganic and organic salts of chromium, such as salts of carboxylic acids, preferably salts of alkanoic acids containing 1 to 30 carbon atoms, salts of aliphatic-β-diketones and salts of β-ketoesters (e.g. chromium (III) 2-ethylhexanoate, chromium (III) octanoate and chromium (III) acetylacetonate) , and halide salts of chromium, such as chromium trichloride, chromium
trichloride tris-tetrahydrofuran complex, chromium tribromide, chromium trifluoride, and chromium tri- iodide . Specific examples of preferred sources of chromium for use herein are chromium (III) acetylacetonate, also called chromium tris(2,4- pentanedionate) , Cr(acac)3, chromium trichloride, CrCl3, and chromium trichloride tris-tetrahydrofuran complex, CrCl3 (THF)3.
The cocatalyst, component (c) , may in principle be any compound or mixture of compounds that generates an active catalyst system with the source of chromium, molybdenum or tungsten, component (a) , and the ligand, component (b) .
Compounds which are suitable for use as a cocatalyst include organoaluminium compounds, organoboron compounds, organic salts, such as methyllithium and methylmagnesium bromide and inorganic acids and salts, such as tetrafluoroboric acid etherate, silver tetrafluoroborate , sodium hexafluoroantimonate and the like. Particularly preferred cocatalysts are organoaluminium compounds . Suitable organoaluminium compounds for use herein are those having the formula AlR4 3, wherein each R4 group is independently selected from C^-C3O alkyl (preferably C]_-C]_2 alkyl) , oxygen containing moieties or halides, and compounds such as LiAlH4 and the like. Non- limiting examples of suitable organoaluminium compounds include trimethylaluminium (TMA) , triethylaluminium (TEA) , tri-n-butyl aluminium, tri-isobutylaluminium (TIBA) , tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium dichloride,
dimethylaluminium chloride, diethylaluminium chloride and aluminoxanes (also called alumoxanes) . Mixtures of organoaluminium compounds are also suitable for use herein. In a preferred embodiment herein, the cocatalyst is an aluminoxane cocatalyst. These aluminoxane cocatalysts may comprise any aluminoxane compound or a mixture of aluminoxane compounds . Aluminoxanes may be prepared by the controlled addition of water to an alkylaluminium compound, such as those mentioned above, or are available commercially. Non- limiting examples of suitable aluminoxanes include methyl aluminoxane (MAO) , modified methyl aluminoxane (MMAO) , tetraisobutyl dialuminoxane (TIBAO) , tetra-n-butyl dialuminoxane and tetra-n-octyl dialuminoxane. In this context it should be noted that the term "aluminoxane" as used within this specification includes commercially available aluminoxanes, which are derived from the corresponding trialkylaluminium by addition of water and which may contain from 2 to 15 %wt . , typically about 5 %wt . , but optionally about 10 %wt . , of aluminium.
Other suitable co-catalysts include those mentioned in WO 02/04119, WO 2004/056478 and WO 2004/056479, the disclosures of which are incorporated herein in their entirety by reference.
The quantity of cocatalyst in the catalyst system the present invention is typically enough to provide a ratio in the range from 0.1 to 20,000, preferably from 1 to 2000, more preferably 1 to 1000, most preferably 1 to 500, aluminium or boron atoms per atom of chromium, molybdenum or tungsten.
The catalyst system of the present invention may independently comprise more than one ligand as defined above .
The amount of chromium, molybdenum or tungsten, namely component (a) , and the amount of ligand, component (b) , can be present in the system in a molar ratio in the range of from 100:1 to 1:100, preferably from 10:1 to 1:10. More preferably, the chromium, molybdenum or tungsten, component (a) , and the ligand, component (b) , are present in a molar ratio in the range of from 3:1 to 1:3. Most preferably the amount of component (a) and the amount of component (b) are present in a molar ratio of from 1:0.9 to 1:1.1.
The three catalyst components of the catalyst system, (a) , (b) and (c) , may be added together simultaneously or sequentially in any order so as to provide an active catalyst. The three catalyst components of the catalyst system, (a) , (b) and (c) , may be contacted in the presence of any suitable solvent. Suitable solvents are known to those skilled in the art, suitable solvents may include any inert solvent that does not react with the co-catalyst component, such as saturated aliphatic, unsaturated aliphatic, aromatic, halogenated hydrocarbons and ionic liquids. Typical solvents include, but are not limited to, benzene, toluene, xylene, ethylbenzene, cumene, propane, butane, pentane, heptane, decane, dodecane, tetradecane, methylcyclohexane, methylcycopentane, cyclohexane, 1- hexene , 1-octene and the like. Other examples of suitable solvents are those disclosed in WO 02/04119, such as
hydrocarbon solvents and polar solvents such as diethyl ether, tetrahydrofuran, acetonitrile and the like.
In one embodiment of the present invention, the catalyst system is formed by adding the co-catalyst component, (c) , to a catalyst precursor composition comprising components (a) and (b) .
The catalyst system of the present invention may be prepared either in the presence (i.e. "in-situ") or absence of the olefinic monomer. The three catalyst components of the catalyst system, (a) , (b) and (c) , may be combined fully in the absence of the olefinic monomer, or the olefinic monomer may be included prior to contacting the components of the catalyst system, simultaneously with the components of the catalyst system or at any point in the process of contacting the components of the catalyst .
The three components of the catalyst system, (a) , (b) and (c) , may be combined at a temperature in the range of from -100 to 200 0C, preferably 0 to 150 0C, more preferably 20 to 100 0C.
The catalyst system of the present invention may be unsupported or supported on a support material . Examples of suitable support materials can be found in WO 02/04119, WO 2004/056478 and WO 2004/056479. The olefinic monomers suitable for use in the trimerization and tetramerization process of the present invention can be any olefinic monomers, which can be converted into a trimer or tetramer. Suitable olefinic monomers include, but are not necessarily limited to, ethylene, propylene, optionally branched C4-C24, preferably C4-C20/ α-olefins, optionally branched C4-C24,
preferably C4-C20/ internal olefins, optionally branched C 4"C24' Preferably C4-C2C vinylidene olefins, optionally branched C4-C24/ preferably C4-C2O' cyclic olefins and optionally branched C4-C24, preferably C4-C20/ dienes, as well as optionally branched C4-C24, preferably C4-C20/ functionalized olefins. Examples of suitable olefinic monomers include, but are not necessarily limited to, linear α-olefins, such as ethylene, 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 and 1-eicosene; branched α- olefins such as 4-methylpent-l-ene and 2 -ethyl-1-hexene; linear and branched internal-olefins such as 2-butene; styrene; cyclohexene; norbornene and the like.
Mixtures of olefinic monomers can also be used in the process of the present invention.
Preferred olefinic monomers for use in the trimerization and tetramerization process of the present invention are propylene and ethylene. Especially preferred is ethylene.
The catalyst system and process of the present invention are particularly useful for the simultaneous trimerization and tetramerization of ethylene to 1-hexene and 1-octene.
The simultaneous trimerization and tetramerization reaction can be performed in solution phase, slurry phase, gas phase or bulk phase.
When the simultaneous trimerization and tetramerization is performed in solution or slurry phase,
a diluent or solvent, which is substantially inert under trimerization and tetramerization conditions may be employed. Suitable diluents or solvents are aliphatic and aromatic hydrocarbons, halogenated hydrocarbons and olefins which are substantially inert under trimerization and tetramerization conditions may be employed, such as those disclosed in WO 02/04119, WO2004/056478 and WO2004/056479.
The trimerization and tetramerization process of the present invention may be performed in any one of a number of suitable reactors, which are well known to one skilled in the art. Typically the trimerization and tetramerization process of the present invention is carried out in a batch, semi-batch or continuous mode. The simultaneous trimerization and tetramerization process of the present invention may be carried out under the following range of reaction conditions. Typically, the temperature will be in the range from about 0 0C to about 200 °C, preferably from about 10 °C to about 150 0C, more preferably from about 40 °C to about 150 0C, even more preferably from about 70 0C to about 150 0C. The process of present invention may also conveniently be performed at temperature range of from about 20 0C to about 120 0C. However, it may be commercially desirable to perform the process of the present invention at an elevated temperature, therefore, the process of the present invention is highly suitable to be applied at a temperature in the range of from about 70 0C to about 100 0C. The pressure range under which the process of the present invention may be performed is typically in the range of from below atmospheric pressure to about 100
barg. Preferably, the pressure will be in the range from about 0.1 to about 80 barg, more preferably from about 0.5 to about 70 barg, especially in the range of from about 1 to about 60 barg. Temperatures and pressures outside those stated above may also be employed, however, the reaction product will either have an excess of heavy and/or solid by-products or an insignificant amount of the trimer or tetramer.
By varying the temperature and pressure it is possible for the ratio of trimers and tetramers produced in the process of the present invention to be varied. The process of the present invention can be used as a tuneable process for the trimerization and tetramerization of olefinic monomers. By the term "tuneable" as used herein, it is meant that by varying the reaction conditions of the process of the present invention, the amount of trimers and tetramers in the product composition produced by the process of the present invention may be varied. This may be useful for a tuneable, continuous or semi-continuous, process for the trimerization and tetramerization of olefinic monomers, wherein the product composition can be changed (e.g. from producing a higher proportion of trimers to a higher proportion of tetramers, or vice-versa,) by changing the reactor conditions without having to interrupt the olefinic monomer feed or the trimerization and tetramerization product flow. In particular, this may be especially useful for a tuneable, continuous or semi- continuous, process for the trimerization and tetramerization of ethylene, wherein the product composition can be changed (e.g. from producing a higher
proportion of 1-hexene to a higher proportion of 1- octene, or vice-versa) by changing the reactor conditions without having to interrupt the olefinic monomer feed or the trimerization and tetramerization product flow. In one embodiment of the present invention, there is a process for the trimerization and tetramerization of olefinic monomers, wherein the process comprises contacting at least one olefinic monomer under trimerization and tetramerization reaction conditions with a catalyst system of the present invention, wherein the process is a continuous or semi-continuous process and the reaction conditions are varied during the process. Variation of the reaction conditions can be performed to make continual adjustments to a process to ensure a consistent product slate or can be performed to a process to change the product slate produced. A preferred version of this embodiment is a process for the trimerization and tetramerization of ethylene, wherein the process comprises contacting ethylene with a catalyst system of the present invention, wherein the process is a continuous or semi-continuous process and the reaction conditions are varied during the process.
Separation of the products, reactant and catalyst can be performed by any technique known to one skilled in the art, such as distillation, filtration, centrifugation, liquid/liquid separation, extraction, etc .
Further details regarding reactors, solvents, separation techniques, and the like, can be found in WO 02/04119.
The use of the process of the present invention for the catalytic trimerization and tetramerization of olefinic monomers provides a simplified method of producing trimers and tetramers of the olefinic monomer with reduced formation of by-products compared with equivalent trimerization and tetramerization processes. In particular, the use of the process of the present invention for the catalytic trimerization and tetramerization of ethylene to 1-hexene and 1-octene provides a process with very high selectivity for 1- hexene and 1-octene over all the other products formed in the Cg and Cg fractions respectively and with reduced formation of by-products compared with equivalent trimerization and tetramerization processes. The overall yield of 1-hexene and 1-octene in the process for the trimerization and tetramerization of ethylene of the present invention depends upon the reaction conditions employed.
Typically, the trimerization and tetramerization selectivity (i.e. the amount of trimers and tetramers of the olefinic monomers in the overall product composition) of the process of the present invention is at least 65 %wt , preferably at least 70 %wt , more preferably at least 75 %wt , of the overall product composition. The trimerization and tetramerization selectivity for the trimerization and tetramerization of ethylene (i.e. the amount of Cg and Cg fraction in the overall product composition) using the process of the present invention is at least 60 %wt , preferably at least 70 %wt , more preferably at least 80 %wt , of the overall product composition .
The amount of 1-hexene produced by the trimerization and tetramerization of ethylene using the process of the present invention is typically in the range of from 10 %wt to 90 %wt, preferably from 11 %wt to 85 %wt, more preferably from 12 %wt to 80 %wt, of the overall product composition. The amount of 1-octene produced by the trimerization and tetramerization of ethylene using the process of the present invention is typically in the range of from 10 %wt to 90 %wt, preferably from 11 %wt to 85 %wt, more preferably from 12 %wt to 80 %wt, of the overall product composition.
The 1-hexene selectivity (i.e. the amount of 1- hexene present in the Cg fraction of the product composition) in the trimerization and tetramerization of ethylene using the process of the present invention is preferably at least 85 %wt , more preferably at least 90 %wt , most preferably at least 92 %wt of the Cg fraction of the product composition.
The 1-octene selectivity (i.e. the amount of 1- octene present in the Cβ fraction of the product composition) in the trimerization and tetramerization of ethylene using the process of the present invention is preferably at least 85%wt, more preferably at least 90 %wt , most preferably at least 92 %wt of the Cβ fraction of the product composition.
The amount of solids produced in the trimerization and tetramerization of ethylene using the process of the present invention is typically at most about 5 %wt . Lower levels of solid olefin waxes and polyethylene produced in the trimerization and tetramerization of ethylene are
desirable in commercial operations as this can reduce the amount of fouling of the reactor equipment, reduce the amount of waste by-products and reduce the amount of operational "downtime" due to maintenance and cleaning of the reactor equipment .
The amount of C]_Q produced in the trimerization and tetramerization of ethylene using the process of the present invention is typically at most about 10 %wt .
The amount of Ci_2~c14 produced in the trimerization and tetramerization of ethylene using the process of the present invention is typically at most about 10 %wt . In one embodiment of the present invention, the olefinic product composition of the trimerization and tetramerization of ethylene using the process of the present invention typically comprises a combined total content of 1-hexene and 1-octene of at least 70 %wt of the overall product composition, wherein the 1-hexene content is at least 10 %wt of the overall product composition, the 1-hexene selectivity is at least 90 %wt of the Cg fraction of the product composition, the 1- octene content is at least 10 %wt of the overall product composition, the 1-octene selectivity is at least 90 %wt of the Cs fraction of the product composition, and the amount of solids produced is at most about 5 %wt of the overall product composition.
In another embodiment of the present invention, the olefinic product composition of the trimerization and tetramerization of ethylene using the process of the present invention comprises a total content of compounds other than 1-hexene and 1-octene of at most 40 %wt of the
overall product composition, preferably at most 30 %wt and more preferably at most 20 %wt, wherein the 1-hexene content is at least 10 %wt of the overall product composition, the 1-hexene selectivity is at least 90 %wt of the Cg fraction of the product composition, the 1- octene content is at least 10 %wt of the overall product composition, the 1-octene selectivity is at least 90 %wt of the Cg fraction of the product composition, and the amount of solids produced is at most about 5 %wt of the overall product composition.
The process of the present invention is illustrated by the following non- limiting examples. Examples
General Procedures and Characterisation All chemicals used in preparations were purchased from Aldrich and used without further purification unless mentioned otherwise.
All the operations with the catalyst systems were carried out under nitrogen atmosphere. All solvents used were dried using standard procedures. Anhydrous toluene (99.8% purity) was dried over 4A molecular sieves (final water content of about 3 ppm) . Anhydrous heptane (99.8% purity) was dried by passage over 4A molecular sieves (final water content of about 1 ppm) . Ethylene (99.5% purity) was purified over a column containing 4A molecular sieves and BTS catalyst (BASF) in order to reduce water and oxygen content to <1 ppm.
The oligomers obtained were characterised by Gas Chromatography (GC) , in order to evaluate oligomer distribution using a HP 5890 series II apparatus and the following chromatographic conditions:
Column: HP-I (cross-linked methyl siloxane) , film thickness = 0.25/xm, internal diameter = 0.25 mm, length 60 m (by Hewlett Packard); injection temperature: 325°C; detection temperature: 325°C; initial temperature: 400C for 10 minutes; temperature programme rate:
10.0°C/minute ; final temperature: 325°C for 41.5 minutes; internal standard: n-hexylbenzene . The yields of the C4-
C30 olefins were obtained from the GC analysis.
The term "trimerization selectivity" when used in relation to the trimerization of ethylene to 1-hexene means the amount of Cg -fraction formed within the product composition, as determined by GC.
The term "tetramerization selectivity" when used in relation to the tetramerization of ethylene to 1-octene means the amount of Cβ-fraction formed within the product composition, as determined by GC.
The term "1-hexene selectivity" when used in relation to the trimerization of ethylene to 1-hexene means the amount of 1-hexene formed within the Cg- fraction of the product composition, as determined by GC. The overall yield of 1-hexene in the trimerization of ethylene is the product of the "trimerization selectivity" multiplied by the "1-hexene selectivity" . The term "1-octene selectivity" when used in relation to the tetramerization of ethylene to 1-octene means the amount of 1-octene formed within the Cβ- fraction of the product composition, as determined by GC. The overall yield of 1-octene in the tetramerization of ethylene is the product of the "tetramerization selectivity" multiplied by the "1-octene selectivity".
The amount of "solids", mainly consisting of heavy wax and polyethylene, has been determined by weighing, after its isolation from the reactor wall and appendages, followed by washing with toluene on a glass filter (P3) and by vacuum drying .
The amount of "total product" is the sum of the amount of largely olefinic product derived from GC analysis and the amount of solids.
The NMR data was obtained at room temperature with a Varian 300 MHz or 400 MHz apparatus. Catalyst systems
The catalyst compositions of the present invention were prepared from catalyst precursor compositions containing ligands B, C, D, E, F and G and a chromium source, these components are described below. Chromium source
Chromium tris (2 , 4-pentanedionate) , also called chromium tris (acetylacetonate) , i.e. Cr(acac)3, was used as the chromium source in the simultaneous tri- and tetramerization reactions of ethylene. Ligand composition E
The reaction product between (2- methoxyphenyl) 2PNH (methyl) and (phenyl) 2PCl (ligand component E) was prepared by the following method. Under a nitrogen atmosphere 1.015 g (3.62 mmol) (2- methoxyphenyl) 2PC1 in was added to 10 ml methylamine (2M in THF) in 50 ml pentane . The resulting mixture was stirred overnight at room temperature. The precipitate was removed by centrifugation. The solvents were removed from the resulting solution under vacuum. Washing with pentane yielded 0.85g (3.09mmol; (84%)) (2-
methoxyphenyl) 2PNH (methyl) as a white solid. 31P-NMR (in C6D6) signal at δ 31.6.
Under a nitrogen atmosphere, 70 mg (0.90 mmol) of neopentyl lithium was slowly added to 235 mg (0.85mmol) of (2 -methoxyphenyl ) 2PNH (methyl) in 55 ml dry toluene. To the resulting mixture 187 mg (0.85 mmol) (phenyl) 2PC1 in 5 ml toluene was slowly added. The mixture was stirred overnight at room temperature. To the mixture 25 ml of pentane was added. The precipitate was removed by centrifugation. The solvent was removed under vacuum and the resulting precipitate was washed with pentane. The product was isolated as a white solid. 31P-NMR (in C6D6) signals at δ 70.4 and 57.9 (JPP=289Hz) .
According to 31P-NMR the product consisted at least predominantly of a P-P=N (methyl) structure with on one P atom two phenyl groups and on the other P atom two 2- methoxyphenyl groups, either (phenyl) 2P (2- methoxyphenyl) 2PN (methyl) or (2- methoxypheny1 ) 2P (phenyl ) 2PN (methyl) . Upon complexation of a Pd[II] compound,
PdCl2 [cyclooctadiene] , by this ligand composition E with the P-P=N(methyl) structure isomerization to the P- N (methyl) -P structure, i.e. (phenyl) 2PN (methyl) P (2- methoxyphenyl) 2 , can be evidenced by 31P NMR (by analogy to NMR and X-ray diffraction analysis by P.J. Dyson, et al., Eur. J. Inorg . Chem. 2004, 530 and P.J. Dyson et al., Inorganica Chimica Acta, 359, (2006), 2635-2643). It is assumed that a similar mechanism applies to the formation of chromium complexes. This can not be
evidenced by NMR spectroscopy, due to the paramagnetic character of the chromium compounds . Ligand composition B (comparative)
The (2-methoxyphenyl) 2PN (CH3 ) P (2-methoxyphenyl) 2 ligand was prepared by first forming a solution of 1.59 g (5 mmol) (2-methoxyphenyl) 2PNEt2 in 20 ml diethyl ether. To this solution 10 ml of a 1 M HCl solution in diethyl ether (10 mmol HCl) was added under an inert atmosphere at room temperature. The suspension thus formed was stirred overnight. The diethyl ether was removed from the product under vacuum and 20 ml of dry toluene was added. The resulting solution was filtered and the toluene was removed from the filtrate under vacuum to yield a white solid (2-methoxyphenyl) 2PCl product. A solution of 0.51 g (5 mmol) of triethylamine in 20 ml of dry dichloromethane was added to the (2- methoxyphenyl) 2PC1 product. To the resulting mixture,
1.25 ml of a 2 M H2NMe solution in THF (2.5 mmol) was added and allowed to stir overnight. The solvents were removed from the resulting solution in vacuo and 20 ml of dry toluene was added. The mixture was then filtered. The toluene was removed from the filtrate under vacuum, and 10 ml of methanol was added to the residue to produce a suspension, which was filtered once more, to leave the solid white (2-methoxyphenyl) 2PN (CH3 ) P (2- methoxyphenyl) 2 product which was isolated. Ligand composition C (comparative)
The (phenyl) 2PN (isopropyl) P (phenyl) 2 ligand was prepared by the following method. At 0 0C, under a nitrogen atmosphere, 15 ml triethylamine was added to 6.3
g (phenyl) 2PCI in 80 ml of dry dichloromethane . To the resulting mixture, 0.844 g isopropylamine was added and allowed to stir overnight at room temperature. The solvents were removed from the resulting solution in- vacuo and 50 ml of dry toluene was added. The mixture was then filtered over a small layer of silica. The toluene was removed from the filtrate under vacuum, (phenyl) 2PN (isopropyl) P (phenyl) 2 product was isolated as a white solid. Crystallization from ethanol yielded (phenyl) 2PN (isopropyl) P (phenyl) 2 as white crystals. Ligand composition D (comparative)
The (phenyl) 2PN (isopropyl) P (2 -methoxyphenyl) 2 ligand was prepared by the following method.
Under a nitrogen atmosphere, 12 ml triethylamine was added to 3.39 g isopropylamine in 10 ml dry toluene. To the resulting mixture, 5.15 ml (phenyl) 2?C1 was slowly added and allowed to stir overnight at room temperature. The precipitate was removed by filtration. The solvents were removed from the resulting solution in vacuo. To the evaporation residue pentane was added and subsequently the solvent was removed in vacuo from the pentane solution, yielding (phenyl) 2PNH (isopropyl) as a colourless oil, which crystallized on standing at room temperature . Under a nitrogen atmosphere, 3 ml triethyl amine was added to 0.9 g of the isolated (phenyl) 2PNH (isopropyl) in
5 ml of dry dichloromethane. To the resulting mixture,
1.1 g (2-methoxyphenyl) 2PCI was added and allowed to stir for a week at room temperature. To the resulting reaction mixture 5-10 ml of dry toluene was added. The
precipitate was removed by centrifugation. The solvents were removed from the resulting solution in vacuo. The resulting mixture was first washed with pentane and thereupon stirred with methanol yielding a white solid. The white solid was washed with pentane and dried in vacuo. Yield 0.7 g of (phenyl) 2PN (isopropyl) P (2- methoxyphenyl) 2 • 31P-NMR (in C6D6) broad signals δ 55.9 and 24.8.
Ligand composition F The reaction product of (2 -methoxyphenyl ) ?PNH (methyl) and
(cyclohexyl) ;>PC1
Under a nitrogen atmosphere, 38 mg (0.404 mmol) of Me3SiCH2Li was slowly added to 101 mg (0.367 mmol) of (2- methoxyphenyl) 2PNH (methyl) in 15 ml dry toluene. To the resulting mixture 95 mg (0.408 mmol) (cyclohexyl) 2PC1
(Aldrich) in 5 ml toluene was slowly added. The mixture was stirred for 2 hours at room temperature. To the mixture 5 ml hexane was added. The precipitate was removed by centrifugation. The solvent was removed under vacuum. The resulting sticky material was extracted with 10-15 ml hexane. Cooling this hexane solution to -20 0C resulted in the isolation of the product as a white solid. 31P-NMR (in d8-toluene) signals at δ 90.4 and 49.5 (JpP=247Hz) . According to 31P-NMR the product consisted at least predominantly of a P-P=N (methyl) structure with on one P atom two cyclohexyl groups and on the other P atom two 2-methoxyphenyl groups, either (cyclohexyl) 2P (2 - methoxyphenyl) 2PN (methyl) or (2- methoxyphenyl) 2P (cyclohexyl) 2PN (methyl) (see Scheme 1).
Scheme 1
Ligand composition G (comparative)
The reaction product of (2- methoxyphenyl) 2PNH ( isopropyl) and (2-methoxyphenyl) 2PCl (ligand composition G) was prepared as follows. Under a nitrogen atmosphere, 3 ml triethylamine was added to 1.5 ml isopropylamine (17.6 mmol) in 5 ml dry toluene. To the resulting mixture, 2.2 g (7.84 mmol) (2- methoxyphenyl) 2PC1 in 20 ml toluene was slowly added and allowed to stir overnight at room temperature. The precipitate was removed by centrifugation. The solvents were removed from the resulting solution in vacuo. Washing with pentane yielded (2- methoxyphenyl) 2PNH (isopropyl) as a white solid. 31P-NMR (in C6D6) δ 21.8. Under a nitrogen atmosphere, 80 mg (1.0 mmol) of neopentyl lithium was slowly added to 300 mg (0.99 mmol) of (2-methoxyphenyl) 2PNH (isopropyl) in 30 ml dry toluene. To the resulting mixture 277 mg (0.99 mmol) (2- methoxyphenyl) 2PC1 was slowly added. The mixture was stirred overnight at room temperature. The precipitate was removed by centrifugation. The solvent was removed in vacuo. The residue was washed with pentane. The product has according to 31P-NMR at least predominantly the P- P=N (isopropyl) structure, i.e. (2-methoxyphenyl) 2P (2- methoxyphenyl) 2PN (isopropyl) , and was used without
further pur i f i cat ion . 31P - NMR ( in C6D6 ) δ 0 . 0 and - 3 5 . 4
( JpP= 258Hz ) .
Co-catalyst
The co-catalyst used in the experiments below was: methyl aluminoxane (MAO) in toluene, [Al] = 5.20%wt, supplied by Crompton GmbH, Bergkamen, Germany;
Examples 1 - 8
Catalyst system preparation for simultaneous trimerization and tetramerization in a batch autoclave In a Braun MB 200 -G dry box chromium tris (acetylacetonate) (typically 30 μmol) and the amount of ligand component B, C, D, E, F or G as indicated in
Table 1, were placed in a glass bottle, to which dry toluene (typically 4 g) was added to obtain the catalyst precursor solution. Finally the bottle was sealed with a septum cap.
These catalyst precursor solutions (the chromium tris (acetylacetonate) solutions are introduced as catalyst precursor solution which is to be activated by the pre-dosed MAO in- situ in the autoclave) , or part of these solutions, were used in the simultaneous tri- and tetramerization reaction of ethylene.
Simultaneous trimerization and tetramerization reactions of ethylene in a 1.0-litre batch autoclave Simultaneous tri- and tetramerization experiments were performed in a 1.0-litre steel autoclave equipped with jacket cooling with a heating/cooling bath (ex.
Julabo, model ATS-2) and a turbine/gas stirrer and baffles.
The reactor was scavenged by introducing 250 ml toluene, MAO (0.6 g solution) and subsequent stirring at 700C under nitrogen pressure of 0.4-0.5 MPa for 30 min. The reactor contents were discharged via a tap in the base of the autoclave. The reactor was evacuated to about 0.4 kPa and loaded with approximately 250 ml toluene (or heptane) , heated to 40 0C and pressurised with ethylene to 15 barg or as indicated in Table 1.
Whilst stirring, a MAO-solution (typically an intake of 3.12 g, 6 mmol Al) was added to the reactor with the aid of toluene to attain an Al/Cr atomic ratio of 200 (typically, the total volume injected was about 25 ml: the MAO-solution diluted with toluene to 8 ml was injected and the injector system was rinsed twice with 8 ml toluene) and the stirring at 800 rpm was continued for 30 minutes.
The Cr-catalyst precursor system (typically 30 μmol on Cr intake), prepared as described above, was introduced into the stirred reactor using an injection system with the aid of toluene (the total volume injected was about 25 ml: the catalyst solution diluted with toluene to 8 ml was injected and the injector system was rinsed twice with 8 ml toluene) . The initial loading of the reactor was about 300 ml of largely toluene. The addition of the catalyst system resulted, after an induction period of some 5 minutes, in an exotherm (generally some 5-100C), which generally reached a maximum within 1 minute and was followed by establishment of the temperature of 400C and the pressure of 15 barg, unless indicated differently in Table 1.
After consuming the desired volume of ethylene, the simultaneous tri- and tetramerization was stopped by- rapid cooling to room temperature (in about 5 minutes), followed by venting of the ethylene, decanting the product mixture into a collection bottle using a tap in the base of the autoclave. Exposure of the mixture to air resulted in rapid deactivation of the catalyst.
After addition of π-hexylbenzene (0.5-3.5 g) as internal standard to the crude product, the amount of the c 4"c30 olefins and purity of Cg, Cg and C^g olefins was determined by gas chromatography. The experimental data is reported in Table 1.
In the case of experiments under 30 or 50 barg of ethylene pressure a similarly equipped 0.5-litre steel autoclave has been used, loaded (similarly to the above- described procedure for the 1.0-litre autoclave) with 150 ml of toluene, a MAO-solution and a Cr-catalyst system. The amounts of the Cr-catalyst system, MAO-solution, solvent and ethylene consumption were typically half of those used in the corresponding 1.0-litre experiments to maintain the same Al/Cr atomic ratio (of about 200) and final alpha olefin concentration as much as practicable. The experimental data is provided in Table 1 below.
* % of 1-hexene by weight of the Cg portion of the product composition.
** % of 1-octene by weight of the Cg portion of the product composition. t Predominantly branched and/or internal olefins, unless indicated differently, tt About 50% of 1-decene by weight of the Ci0 portion of the product composition.
## During 10 minutes at 40 0C.
C6 Hydrocarbons containing 6 carbon atoms .
1 -C
6 1-hexene.
C8 Hydrocarbons containing 8 carbon atoms .
1 -C
8 1-octene.
C10 Hydrocarbons containing 10 carbon atoms .
- C
C12 Hydrocarbons containing 12 and/or 14 carbon atoms .
Solids The amount of wax and polyethylene isolated by filtration. Total product The amount of C4-C100 olefins, derived from GC analysis, including the amount of solids .
As can be seen from the experimental data in Table 1 ligands having the formula (R1) 2P-P (R1) m (R2) n=N (R3) or P(R1)m(R2)n-P(R1)2=N(R3) wherein m = 0, n = 2, R1 = o- anisyl, R2 = phenyl or cyclohexyl, R3 = Me (Examples 1 to 4) show an attractive combination of high activity and high combined 1-hexene and 1-octene selectivity and low solids formation, even at high temperatures (> 70 0C) . This is contrast to ligands having a different pattern of
R1/ R2 or R3 groups as per Comparative Example 5. It is noteworthy that comparative ligand G, which differs from comparative ligand B in its predominant P-P=N structure and in R3 (for ligand G, R3 is isopropyl rather than methyl) , gives a two orders of magnitude lower activity than ligand B (Comparative Example 8), an increased amount of solids, but a similar 1-hexene and 1-octene selectivity under similar reaction conditions. It is also worth noting that ligand E, which differs from comparative ligand D in its predominant P-P=N structure and in R3 (for ligand E, R3 is methyl rather than isopropyl) gives a twice as high activity and a higher 1- octene selectivity than ligand D. It should be mentioned that comparative ligand C, having a predominant P-N-P structure, an isopropyl group on N and two phenyl groups on each P, also shows a higher 1-octene selectivity than comparative ligand D, but at the expense of increased solids formation at elevated temperatures (> 70 0C) . Thus, the catalyst activity towards selective production of 1-hexene and 1-octene at high temperatures (> 70 0C) is greatly enhanced when two ortho-anisyl groups are present on one of the phosphorus atoms (see Examples 6 and 7 of Table 1 for Comparison) .
Claims
1. A ligand having the general formula (I) : (R1)2P-P(R1)ra(R2)n=N(R3) (D wherein R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof ; the RI groups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho- positions; and the R2 groups are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions; with the proviso that m is 0 or 1, n is 1 or 2 and the total of m + n is 2.
2. A ligand having the general formula (II) :
P(Rl)m(R2)n-P(R1)2=N(R3) (II) wherein R3 is selected from hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a heterohydrocarbyl group, a substituted heterohydrocarbyl group, a silyl group or derivative thereof ; the R1 groups are independently selected from an optionally substituted aromatic group bearing a polar substituent on at least one of the ortho- positions; and the R2 groups are independently selected from hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl and substituted heterohydrocarbyl groups with the proviso that when the group is aromatic it does not contain a polar substituent at any of the ortho-positions; with the proviso that m is 0 or 1, n is 1 or 2 and the total of m + n is 2.
3. A ligand according to Claim 1 or 2 , wherein R^ is selected from C]- -Ci5 alkyl groups, substituted Ci- C15 alkyl groups, C2-C15 alkenyl groups, substituted
C2-C15 alkenyl groups, C3-C15 cycloalkyl groups, substituted C3-C15 cycloalkyl groups, C5-C15 aromatic groups, substituted C5-C15 aromatic groups, C1~C15 alkoxy groups and substituted C1-C15 alkoxy groups, preferably C1-C15 alkyl groups.
4. A ligand according to any of Claims 1 to 3 wherein wherein m is 0 and n is 2.
5. A ligand according to any one of Claims 1 to 4 , wherein the R2 groups are independently selected from substituted or unsubstituted aromatic groups, including substituted or unsubstituted heteroaromatic groups, which do not contain a polar substituent at any of the ortho-positions, preferably independently selected from optionally substituted phenyl groups which do not contain a polar substituent at any of the ortho-positions.
6. A ligand according to any one of Claims 1 to 5 , wherein the R1 group is independently selected from substituted or unsubstituted aromatic groups bearing an optionally branched Ci-C2O alkoxy group on at least one of the ortho-positions, preferably an o- anisyl group.
7. A process of preparing a ligand according to any of Claims 1 to 6 which comprises reacting:
(i) a compound of formula (III) : X-P(R1)m(R2)m (III) wherein X is a halide, and R1, R2, m and n are as defined above for ligands of general formulae (I) and (II) ; and (ii) a compound of formula (IV) : (R1)2P-N(R3)H (IV) wherein R^ and R^ are as defined above for ligands of general formulae (I) and (II) ; in the presence of an HX-acceptor.
8. A process of preparing a ligand according to any of Claims 1 to 6 which comprises reacting:
(i) a compound of formula (V) :
X-P(R1J2 (V) wherein X is a halide and R1 is as defined above for ligands of general formulae (I) and (II); and (ii) a compound of formula (VI) :
(R1)m(R2)nP-N(R3)H (VI) wherein R1, R2, R^, m and n are as defined above for ligands of general formulae (I) and (II) ; in the presence of an HX-acceptor.
9. A ligand system prepared by reacting: (i) a compound of formula (III) : X- P ( R1 ) m ( R2 ) m ( III ) wherein X is a halide, and R1, R2, m and n are as defined above for ligands of general formulae (I) and (II) ; and (ii) a compound of formula (IV) :
(R1J2P-N(R3JH (IV) wherein R1 and R3 are as defined above for ligands of general formulae (I) and (II) ; in the presence of an HX-acceptor.
10. A ligand system prepared by reacting: (i) a compound of formula (V) :
X-P(R1J2 (V) wherein X is a halide and R1 is as defined above for ligands of general formulae (I) and (II); and (ii) a compound of formula (VI) :
(R1)m(R2)nP-N(R3)H, (VI) wherein R1, R2, R3, m and n are as defined above for ligands of general formulae (I) and (II) ; in the presence of an HX-acceptor.
11. A catalyst system comprising: a) a source of chromium, molybdenum or tungsten; b) a ligand according to any of Claims 1 to 6 or a ligand system according to Claim 9 or 10; and c) a cocatalyst .
12. A process for the simultaneous trimerization and tetramerization of olefinic monomers, wherein the process comprises contacting at least one olefinic monomer with the catalyst system of Claim 11 at a pressure in the range of from below atmospheric to 100 barg and at a temperature in the range of from
0 0C to 200 0C.
13. A process according to Claim 12, wherein the olefinic monomer is ethylene.
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| JP2009542083A JP5421118B2 (en) | 2006-12-22 | 2007-12-20 | Ligand and catalyst for oligomerization of olefin monomers |
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| WO2011045701A1 (en) | 2009-10-16 | 2011-04-21 | Sasol Technology (Proprietary) Limited | Separation of components from a multi-component hydrocarbon stream which includes ethylene |
| WO2013168098A1 (en) | 2012-05-09 | 2013-11-14 | Sasol Technology (Proprietary) Limited | Separation of components from a multi-component hydrocarbon stream |
| WO2013168099A1 (en) | 2012-05-09 | 2013-11-14 | Sasol Technology (Proprietary) Limited | A process for oligomerising a hydrocarbon to form at least one co-monomer product |
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| FR3014331B1 (en) * | 2013-12-06 | 2016-01-01 | IFP Energies Nouvelles | NOVEL NICKEL CATALYTIC COMPOSITION AND USE THEREOF IN OLEFIN OLIGOMERIZATION PROCESS |
| WO2016012948A1 (en) * | 2014-07-24 | 2016-01-28 | Sabic Global Technologies B.V. | Catalyst composition and process for oligomerization of ethylene to produce 1-hexene and/or 1-octene |
| WO2017010998A1 (en) * | 2015-07-14 | 2017-01-19 | Chevron Phillips Chemical Company Lp | Olefin compositions |
| CN108097322B (en) * | 2017-12-11 | 2020-11-06 | 天津科技大学 | Catalyst system for selective oligomerization of ethylene and ethylene oligomerization reaction method |
| CN108607612B (en) * | 2018-04-16 | 2020-11-06 | 天津科技大学 | Catalyst system for ethylene selective oligomerization, preparation method and ethylene oligomerization reaction method |
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- 2007-12-20 WO PCT/EP2007/064398 patent/WO2008077911A1/en active Application Filing
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| WO2011045701A1 (en) | 2009-10-16 | 2011-04-21 | Sasol Technology (Proprietary) Limited | Separation of components from a multi-component hydrocarbon stream which includes ethylene |
| WO2013168098A1 (en) | 2012-05-09 | 2013-11-14 | Sasol Technology (Proprietary) Limited | Separation of components from a multi-component hydrocarbon stream |
| WO2013168099A1 (en) | 2012-05-09 | 2013-11-14 | Sasol Technology (Proprietary) Limited | A process for oligomerising a hydrocarbon to form at least one co-monomer product |
| US9399179B2 (en) | 2012-05-09 | 2016-07-26 | Sasol Technology Proprietary Limited | Separation of components from a multi-component hydrocarbon stream |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010513413A (en) | 2010-04-30 |
| US20120178889A1 (en) | 2012-07-12 |
| US8476181B2 (en) | 2013-07-02 |
| CA2673190C (en) | 2015-02-17 |
| CN101600722B (en) | 2015-11-25 |
| SG191440A1 (en) | 2013-07-31 |
| US8252874B2 (en) | 2012-08-28 |
| ZA200904273B (en) | 2010-04-28 |
| US20090069517A1 (en) | 2009-03-12 |
| JP5421118B2 (en) | 2014-02-19 |
| EP2114967A1 (en) | 2009-11-11 |
| CN101600722A (en) | 2009-12-09 |
| CA2673190A1 (en) | 2008-07-03 |
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