CN108017674A - A kind of ligand compound, its preparation method and its application - Google Patents
A kind of ligand compound, its preparation method and its application Download PDFInfo
- Publication number
- CN108017674A CN108017674A CN201610963007.2A CN201610963007A CN108017674A CN 108017674 A CN108017674 A CN 108017674A CN 201610963007 A CN201610963007 A CN 201610963007A CN 108017674 A CN108017674 A CN 108017674A
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- CN
- China
- Prior art keywords
- ligand compound
- alkyl
- compound
- ligand
- preparation
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- 239000003446 ligand Substances 0.000 title claims abstract description 55
- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000005977 Ethylene Substances 0.000 claims description 23
- -1 methoxyl group Chemical group 0.000 claims description 21
- 238000006384 oligomerization reaction Methods 0.000 claims description 17
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 5
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- ULNVTMFBEVVUMH-UHFFFAOYSA-N P.[Cl] Chemical compound P.[Cl] ULNVTMFBEVVUMH-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000172 C5-C10 aryl group Chemical group 0.000 claims 1
- 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 claims 1
- 150000007529 inorganic bases Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 13
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 5
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000010210 aluminium Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 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 2
- 238000011161 development Methods 0.000 description 2
- 239000003974 emollient agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WHTUPTBPHFOBOB-UHFFFAOYSA-N ClP1c2ccccc2Oc2c1cccc2 Chemical compound ClP1c2ccccc2Oc2c1cccc2 WHTUPTBPHFOBOB-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- YWMAPNNZOCSAPF-UHFFFAOYSA-N Nickel(1+) Chemical compound [Ni+] YWMAPNNZOCSAPF-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000006437 ethyl cyclopropyl group Chemical group 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000006431 methyl cyclopropyl group Chemical group 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229940006444 nickel cation Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
-
- 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
- B01J31/22—Organic complexes
-
- 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
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of ligand compound, includes the structure as shown in general formula I：Wherein, R is alkyl, cycloalkyl, aryl, aralkyl or alkaryl；R ' is hydrogen, alkyl, alkoxy or halogen.The invention further relates to a kind of preparation method and applications of the ligand compound.
Description
Technical field
The present invention relates to a kind of ligand compound, and in particular to ethylene oligomerisation catalyst ligand compound, especially ethene
Trimerization and four poly- catalyst ligand compounds, the invention further relates to the preparation method of catalyst ligand compound and in ethylene oligomerization
Application in technique.
Background technology
Ethylene oligomerization is one of most important reaction in olefinic polymerization industry., can will be cheap small by oligomerisation reaction
Molecular olefine is transformed into high value-added product.Ethylene oligomerization product-linear alpha-alkene (LAO) is important organises
Work raw material.Such as LAO C4-C8 are mainly used in production high-quality polyethylene as important Organic Ingredients and chemical intermediate
(PE) field.PE can be significantly improved by 1- hexenes or 1- octenes and the linear low density polyethylene (LLDPE) of ethylene copolymer production
Properties, can particularly significantly improve mechanical performance, optical property and the tear strength and impact strength of polyethylene,
Product is very suitable for the fields such as the agricultural mulch films such as packaging film and greenhouse, canopy room.LAO C10-C30 can be used as preparing daily cleaning
Agent, flotation agent, emulsifying agent, the emollient component of refrigeration machine and bore liquid emollient component, plasticizer, various additives, low viscosity are closed
Into oil, polymer and copolymer, oil and oil product additive, senior alkylamines, advanced organo-aluminum compound, advanced alkane virtue
Additive of base hydrocarbon, higher aliphatic and aliphatic acid, epoxides and heat carrier etc..On LAO C20-C30 bases
On can also composite adhesives, sealant and coating.In recent years, with the continuous development of polyolefin industry, in world wide to α-
The demand rapid development of alkene.Wherein most alpha-olefins is prepared to obtain by ethylene oligomerization.
Since the seventies in last century, the research of transient metal complex catalysis in olefine polymerization and oligomerisation is gradually subject to science
The attention of family, people start to make great efforts research raw catelyst and improve existing catalyst, improve the activity and catalysate of catalyst
Selectivity.In numerous explorations, research is earliest, with fastest developing speed, compare concentration is nickel cation type catalyst system and catalyzing, such as
The United States Patent (USP) reported already has US3686351 and US3676523, and Shell Co. Ltd's SHOP works based on the patented technology
Skill.O-P bridging type ligands are arrived involved in Shell Co. Ltd's SHOP techniques, but are containing virose organophosphorous groups in the catalyst,
And synthesis step is complicated, stability is poor.The many such as O-O, P-N, P-P and N-N type coordination Raney nickel were developed again later
Patent, such as JP11060627, WO9923096, WO991550, CN1401666, CN1769270 etc..However, obtained by above-mentioned patent
The shortcomings that catalyst generally existing preparation method obtained is relatively complicated.Other catalyst also have chromium system, zirconium system and aluminium system etc.,
Brookhart groups (Brookhart, M et al., J.Am.Chem.Soc., 1998,120,7143-7144；WO99/02472,
1999), Gibson groups (Gibson, V.C. et al., Chem.Commun., 1998,849-850；Chem.Eur.J.,2000,
Ethylene oligomerization can be catalyzed by 2221-2231) finding the trident pyridinimine complex of some Fe (II) and Co (II) respectively, not only be urged
The catalytic activity of agent is very high, and the selectivity of alpha-olefin is also very high.
It is undoubted, remain the demand to the new catalyst of excellent combination property in olefin(e) oligomerization field.
Notice is placed on the Novel Ligands compound how obtained for ethylene oligomerisation catalyst, so as to develop with high activity and choosing
The ethylene oligomerisation catalyst of selecting property, is worth paying close attention in the industry.
The content of the invention
Present inventor is found that a kind of ethene of brand new is neat when studying ethylene oligomerisation catalyst containing phosphorous
Poly- catalyst ligand, the ligand compound contain tri- kinds of hetero atoms of N, P, O, and structure is novel to be prepared simply, and cost is relatively low.Urged by this
The composition that agent ligand, transistion metal compound and co-catalyst are formed can effectively be catalyzed ethylene oligomerization reaction, especially
Ethylene trimer and four poly- reactions.Catalyst activity can be more than 2.5 × 107G/ (molCrh), up to 108G/ (molCrh) with
On, the overall selectivity of C6 and C8 components be able to can exceed more than 92% up to selectivity of more than 97%, the 1- octenes in C8 components
More than 99.4%, there is high activity, high selectivity, there is preferable prospects for commercial application and economic value.
The first aspect of the invention is related to a kind of ligand compound, and it includes the structure as shown in general formula I：
Wherein, R is alkyl, cycloalkyl, aryl, aralkyl or alkaryl；R ' is hydrogen, alkyl, alkoxy or halogen.
In a preferred embodiment of the present invention, the R is C1-C8Alkyl, C3-C8Cycloalkyl, C5-C10's
Aryl, C7-C12Aralkyl or C7-C12Alkaryl, be preferably selected from methyl, ethyl, isopropyl, cyclopropyl, cyclopenta, hexamethylene
Base and phenyl.
In a preferred embodiment of the present invention, the R ' is hydrogen, C1-C8Alkyl, C1-C6Alkoxy or halogen
Element, is preferably selected from hydrogen, methyl, ethyl, isopropyl, methoxyl group, chlorine and bromine.
In the present invention, term " C1-C8Alkyl " refers to saturated straight chain or branched hydrocarbyl containing 1-8 carbon atom, such as
C1-C6Straight chained alkyl and C3-C8Branched alkyl.As C1-C8Alkyl, it can be mentioned that methyl, ethyl, n-propyl, isopropyl,
Normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, n-hexyl and Sec-Hexyl；Particularly preferred methyl,
Ethyl, n-propyl and isopropyl.
In the present invention, term " C3-C8Cycloalkyl " refers to the group with cyclic structure containing 3-8 carbon atom.
As C3-C8Cycloalkyl, it can be mentioned that cyclopropyl, methylcyclopropyl groups, ethyl cyclopropyl, cyclobutyl, methyl-cyclobutyl, ethyl ring
Butyl, cyclopenta, methylcyclopentyl, ethylcyclopentyl, propyl group cyclopenta, cyclohexyl, suberyl and cyclooctyl.
In the present invention, term " C5-C10Aryl " refer to the base with aromatic structure containing 5-10 carbon atom
Group.As C5-C10Aryl, it can be mentioned that pyridine radicals, phenyl, naphthyl etc..
In the present invention, term " C1-C6Alkoxy " refers to C1-C6The group that alkyl is connected with an oxygen atom.
As C1-C6Alkoxy, it can be mentioned that methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, Zhong Ding
Epoxide, tert-butoxy, n-pentyloxy, secondary amoxy, positive hexyloxy and secondary hexyloxy；Particularly preferred methoxyl group and ethyoxyl.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, particularly preferred fluorine, chlorine and bromine.
In the present invention, term " C7-C12Aralkyl " refer to the aryl alkyl containing 7-12 carbon atoms, such as benzene first
Base, phenethyl, phenylpropyl, benzene butyl etc..Term " C7-C12Alkaryl " refer to that there is the alkylaryl of 7-12 carbon atoms,
Such as tolyl, ethylbenzene, propyl group phenyl.
The second aspect of the invention provides the preparation method of the ligand compound, including by the phosphine as shown in general formula II
Chlorine compound is dissolved in organic solvent, adds acid binding agent, it is R-NH to add general formula2Amine, obtained after the completion of reaction liganded
Compound I, R and R ' restriction be same as above.
In a preferred embodiment of preparation method of the present invention, phosphine chlorine compound II, acid binding agent and the R-
NH2Molar ratio be 1:(1-3):(0.2-1).In the scope, be conducive to obtain the ligand compound in high yield.
In a preferred embodiment of preparation method of the present invention, the acid binding agent is selected from organic amine and inorganic
At least one of bases, such as may be selected from triethylamine, tripropyl amine (TPA), tri-isopropyl amine, pyridine, potassium carbonate and sodium hydroxide at least
It is a kind of.Using acid binding agent, the direction for being conducive to reaction to generation ligand compound I carries out.
In a preferred embodiment of preparation method of the present invention, the organic solvent is selected from arene compounds
At least one of with aliphatic hydrocarbon compound, it preferably is selected from toluene, ether, tetrahydrofuran, hexane and dichloromethane at least
It is a kind of.
In a preferred embodiment of preparation method of the present invention, the reaction temperature of the reaction is 0~100
DEG C, preferably 20~30 DEG C.The reaction time of the reaction for 1~10 it is small when, preferably 2~4 it is small when.
The third aspect of the invention is related to a kind of ligand compound and is preparing ethylene oligomerization carbon monoxide-olefin polymeric
In application.
Ligand of the present invention, can form composition with transistion metal compound and co-catalyst, can effectively urge
Change ethylene oligomerization reaction, particularly ethylene trimer and four poly- reactions, there is good oligomerization activity.
The fourth aspect of the invention is related to a kind of application of ligand compound in ethylene oligomerization.According to the present invention
Ligand, can be used in ethylene oligomerization, have a good application prospect.
Carbon monoxide-olefin polymeric provided by the invention, ligand compound are the compound of brand new, it prepares simple, cost
It is relatively low.The carbon monoxide-olefin polymeric being made of the ligand compound can carry out ethylene trimer and four poly- reactions, and catalyst activity can
More than 2.5 × 107G/ (molCrh), up to 108More than g/ (molCrh), the overall selectivity of C6 and C8 components can exceed
92%, can have high activity, high selectivity more than more than 99.4% up to selectivity of more than 97%, the 1- octenes in C8 components
The features such as, there is preferable prospects for commercial application and economic value.
Embodiment
The following example is only used for that the present invention is described in detail, it will be appreciated that the scope of the present invention is not limited to
These embodiments.
In an embodiment of the present invention, nuclear magnetic resonance is detected using Bruker AV400 type Nuclear Magnetic Resonance；Gas phase
Chromatography is detected using 5890 chromatograph of Hewlett-Packard.
Wherein, the testing conditions of nuclear magnetic resonance are：Deuterochloroform is solvent, and room temperature is tested.
Wherein, the testing conditions of gas-chromatography are：Chromatographic column SE-54, High Purity Nitrogen carrier gas, fid detector；Column temperature uses two
Rank temperature programming.
Embodiment 1
Catalyst ligand 1 (such as general formula I, R=iPr, R '=H) preparation method include：
In the 10mL dichloromethane that 4.1mmol phosphine chlorine compounds II (R '=H) is dissolved under nitrogen protection, Ran Hou
11mmol triethylamines are slowly added dropwise in solution above under ice bath stirring.After being added dropwise, 2mmol R- are added
NH2(R=iPr).React 4 it is small when after, first filter out ammonium salt, then use column chromatography, obtain compound catalyst ligand 1.Yield
85.0%.1H NMR(400MHz,CDCl3):δ=7.41-7.38 (m, 4H), 7.20-7.18 (m, 4H), 7.06-6.94 (m,
4H),6.92-6.85(m,4H),3.02-2.88(m,1H),0.91(s,3H),0.90(s,3H)。
Embodiment 2
The preparation method of catalyst ligand 2 (such as general formula I, R=Cy, R '=H) is the same as ligand compound 1.Yield 91.7%.1H
NMR(400MHz,CDCl3)：δ=7.39-7.06 (m, 16H), 2.53-2.38 (m, 1H), 1.72-0.73 (m, 10H).
Embodiment 3
The preparation method of catalyst ligand 3 (such as general formula I, R=Ph, R '=H) is the same as ligand compound 1.Yield 88.6%.1H
NMR(400MHz,CDCl3)：δ=7.45-7.09 (m, 21H).
Embodiment 4
Catalyst ligand 4 (such as general formula I, R=iPr, R '=2-OCH3) preparation method with ligand compound 1.Yield
88.6%.1H NMR(400MHz,CDCl3)：δ=7.39-6.98 (m, 14H), 3.73 (s, 6H), 2.90 (m, 1H), 0.97 (s,
3H),0.94(s,3H)。
Embodiment 5
Catalyst ligand 5 (such as general formula I, R=iPr, R '=3-CH3) preparation method with ligand compound 1.Yield
88.6%.1H NMR(400MHz,CDCl3)：δ=7.43-6.90 (m, 14H), 3.02-2.88 (m, 1H), 2.33 (s, 6H),
0.98(s,3H),0.95(s,3H)。
Embodiment 6
The preparation method of catalyst ligand 6 (such as general formula I, R=Ph, R '=2-Cl) is the same as ligand compound 1.Yield
88.6%.1H NMR(400MHz,CDCl3)：δ=7.50-6.81 (m, 19H).
Embodiment 7 (Polymerization Example)
Ethylene oligomerization reaction uses stainless steel polymeric kettle.Autoclave is heated to 80 DEG C, with nitrogen displacement number after vacuumizing
It is secondary, it is then charged with when ethene to ethylene pressure is 3MPa and is down to room temperature.Then hexahydrotoluene is added at 60 DEG C, is added at the same time
2.5 μm of ol tetrahydrofurans chromium chlorides and 5 μm of ol ligand compounds 1 and 500 μm of ol triethyl aluminums, the cumulative volume of mixed liquor are
The molar ratio of 100mL, wherein chromium, ligand compound and co-catalyst are 1：2：200, reaction pressure 2MPa is controlled, is passed through ethene,
Carry out ethylene oligomerization reaction.
After the completion of reaction, system is cooled to room temperature, and gaseous products are collected in aerometer measuring tank, and liquid-phase product is collected
In conical flask, 1mL ethanol is added as terminator, terminates ethylene oligomerization reaction.Gas-chromatography is carried out after liquid phase gauging of products
Analysis.It is as follows to measure reaction result：Catalytic activity is 2.5 × 107G/ (molCrh), C6 compositional selectings are 29.0%, C8
Compositional selecting be 66.5%, C6 and the overall selectivity of C8 components be 95.5%, 1- octenes accounted in C8 99.6%, C10 and with
Upper component 4.0%.
Embodiment 8 (Polymerization Example)
Reaction pressure is changed to 4MPa, other same embodiments 7.It is as follows to measure reaction result：Catalytic activity for 5.6 ×
107G/ (molCrh), C6 compositional selectings are that 22.3%, C8 compositional selectings are 73.1%, C6 and the total of C8 components selects
Property is 95.4%, and 1- octenes account for 99.7%, C10 and above component 3.0% in C8.
Embodiment 9 (Polymerization Example)
Ligand compound 1 is changed to ligand compound 2, other same embodiments 8.It is as follows to measure reaction result：Catalytic activity
For 5.7 × 107G/ (molCrh), C6 compositional selectings are that 24.9%, C8 compositional selectings are 72.2%, C6 and C8 components
Overall selectivity is that 97.1%, 1- octenes account for 99.5%, C10 and above component 2.0% in C8.
Embodiment 10 (Polymerization Example)
Ligand compound 1 is changed to ligand compound 3, other same embodiments 8.It is as follows to measure reaction result：Catalytic activity
For 5.2 × 107G/ (molCrh), C6 compositional selectings are that 25.3%, C8 compositional selectings are 70.5%, C6 and C8 components
Overall selectivity is that 95.8%, 1- octenes account for 99.6%, C10 and above component 4.0% in C8.
Embodiment 11 (Polymerization Example)
Ligand compound 1 is changed to ligand compound 4, other same embodiments 8.It is as follows to measure reaction result：Catalytic activity
For 5.5 × 107G/ (molCrh), C6 compositional selectings are that 27.9%, C8 compositional selectings are 69.5%, C6 and C8 components
Overall selectivity is that 97.4%, 1- octenes account for 99.4%, C10 and above component 2.0% in C8.
Embodiment 12 (Polymerization Example)
Ligand compound 1 is changed to ligand compound 5, other same embodiments 8.It is as follows to measure reaction result：Catalytic activity
For 5.5 × 107G/ (molCrh), C6 compositional selectings are that 35.2%, C8 compositional selectings are 69.5%, C6 and C8 components
Overall selectivity is that 94.7%, 1- octenes account for 99.5%, C10 and above component 2.0% in C8.
Embodiment 13 (Polymerization Example)
Ligand compound 1 is changed to ligand compound 6, other same embodiments 8.It is as follows to measure reaction result：Catalytic activity
For 5.4 × 107G/ (molCrh), C6 compositional selectings are that 30.0%, C8 compositional selectings are 65.8%, C6 and C8 components
Overall selectivity is that 95.8%, 1- octenes account for 99.6%, C10 and above component 3.0% in C8.
Embodiment 14 (Polymerization Example)
Reaction temperature is changed to 45 DEG C by 60 DEG C, other conditions are the same as embodiment 8.It is as follows to measure reaction result：Catalytic activity
For 5.7 × 107G/ (molCrh) (i.e. 1.1 × 106G/ (g Crh)), C6 compositional selectings are 23.0%, C8 compositional selectings
Property be 72.8%, the overall selectivitys of C6 and C8 components accounts for 99.7%, C10 and above component for 95.8%, 1- octenes in C8
3.0%.
Embodiment 15 (Polymerization Example)
Co-catalyst is changed to modified methylaluminoxane (MMAO-3A) by triethyl aluminum, other conditions are the same as embodiment 8.Survey
It is as follows to obtain reaction result：Catalytic activity is 10.8 × 107G/ (molCrh), C6 compositional selectings select for 18.5%, C8 components
Selecting property is 74.0%, C6 and the overall selectivity of C8 components is that 92.5%, 1- octenes account for 99.6%, C10 and above component in C8
4.0%.
In the present invention：iPr represents isopropyl, and Cy represents cyclohexyl, and Ph represents phenyl.Ligand compound in the present invention
In preparation process, the yield being related to is with raw material R-NH2On the basis of calculate.In the present invention, selectively refer to the component anti-
Answer the mass percentage in gross product.In the present invention, the active unit of catalyst is g/ (molCrh), i.e., per hour
The gross mass of interior every mole of chromic salts catalytic polymerization generation product, can also be scaled g/ (gCrh), according to the atomic weight of chromium
Calculate, 52g/ (molCrh)=1g/ (gCrh).
It should be noted that embodiment described above is applied to explain the present invention, do not form to any of the present invention
Limitation.By referring to above-mentioned exemplary embodiments, invention has been described, it should be appreciated that wherein all words are
Descriptive and explanatory vocabulary, rather than limited vocabulary.Can be according to the rules within the scope of the claims to this
Modification is made in invention, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although described in it
The present invention relates to specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, phase
Instead, the present invention can be extended to other all methods and applications with identical function.
Claims (10)
1. a kind of ligand compound, includes the structure as shown in general formula I：
Wherein, R is alkyl, cycloalkyl, aryl, aralkyl or alkaryl；R ' is hydrogen, alkyl, alkoxy or halogen.
2. compound according to claim 1, it is characterised in that the R is C1-C8Alkyl, C3-C8Cycloalkyl, C5-C10
Aryl, C7-C12Aralkyl or C7-C12Alkaryl, be preferably selected from methyl, ethyl, isopropyl, cyclopropyl, cyclopenta, ring
Hexyl and phenyl.
3. compound according to claim 1 or 2, it is characterised in that the R ' is hydrogen, C1-C8Alkyl, C1-C6Alcoxyl
Base or halogen, are preferably selected from hydrogen, methyl, ethyl, isopropyl, methoxyl group, chlorine and bromine.
4. a kind of preparation method of ligand compound according to any one of claim 1-3, including will be such as general formula II institutes
The phosphine chlorine compound shown is dissolved in organic solvent, adds acid binding agent, it is R-NH to add general formula2Amine, obtained after the completion of reaction
Ligand compound I；Wherein, R is alkyl, cycloalkyl, aryl, aralkyl or alkaryl；R ' is hydrogen, alkyl, alkoxy or halogen,
5. according to the method described in claim 4, it is characterized in that, phosphine chlorine compound II, acid binding agent and the R-NH2Mole
Than for 1:(1-3):(0.2-1).
6. method according to claim 4 or 5, it is characterised in that the acid binding agent is selected from organic amine and inorganic base
At least one of, it preferably is selected from least one of triethylamine, tripropyl amine (TPA), tri-isopropyl amine, pyridine, potassium carbonate and sodium hydroxide.
7. method according to claim 4 or 5, it is characterised in that the organic solvent is selected from arene compounds and fat
At least one of race's hydrocarbon compound, preferably is selected from least one of toluene, ether, tetrahydrofuran, hexane and dichloromethane.
8. according to the method any one of claim 4-7, it is characterised in that reaction temperature is 0-100 DEG C, preferably 20-
30℃；When reaction time is 1-10 small, when preferably 2-4 is small.
9. any one the method in ligand compound according to any one of claim 1-3 or claim 4-9
Application of the ligand compound of preparation in ethylene oligomerization carbon monoxide-olefin polymeric is prepared.
10. any one the method in ligand compound according to any one of claim 1-3 or claim 4-9
Application of the ligand compound of preparation in ethylene oligomerization.
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| CN116328837A (en) * | 2021-12-24 | 2023-06-27 | 中国石油化工股份有限公司 | Ethylene oligomerization catalyst composition and application thereof |
| CN116328836A (en) * | 2021-12-24 | 2023-06-27 | 中国石油化工股份有限公司 | Porous organic polymer supported ethylene polymerization main catalyst, ethylene polymerization catalyst composition and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116328837A (en) * | 2021-12-24 | 2023-06-27 | 中国石油化工股份有限公司 | Ethylene oligomerization catalyst composition and application thereof |
| CN116328836A (en) * | 2021-12-24 | 2023-06-27 | 中国石油化工股份有限公司 | Porous organic polymer supported ethylene polymerization main catalyst, ethylene polymerization catalyst composition and application |
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