WO2017047936A1 - 올레핀의 올리고머화 방법 - Google Patents
올레핀의 올리고머화 방법 Download PDFInfo
- Publication number
- WO2017047936A1 WO2017047936A1 PCT/KR2016/008980 KR2016008980W WO2017047936A1 WO 2017047936 A1 WO2017047936 A1 WO 2017047936A1 KR 2016008980 W KR2016008980 W KR 2016008980W WO 2017047936 A1 WO2017047936 A1 WO 2017047936A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon atoms
- chromium
- formula
- iii
- olefins
- Prior art date
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 39
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 230000000694 effects Effects 0.000 claims abstract description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 62
- -1 butylaluminoxane Chemical compound 0.000 claims description 23
- 239000003446 ligand Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical group [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 claims description 10
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 230000003606 oligomerizing effect Effects 0.000 claims description 4
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical group [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 claims description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- CNIGXAJYMNFRCZ-UHFFFAOYSA-K butanoate;chromium(3+) Chemical compound [Cr+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O CNIGXAJYMNFRCZ-UHFFFAOYSA-K 0.000 claims description 2
- WFOOTRPLCMPWIP-UHFFFAOYSA-K chromium(3+) pentanoate Chemical compound [Cr+3].CCCCC([O-])=O.CCCCC([O-])=O.CCCCC([O-])=O WFOOTRPLCMPWIP-UHFFFAOYSA-K 0.000 claims description 2
- NMXUZAZJTJAHGK-UHFFFAOYSA-K chromium(3+);dodecanoate Chemical compound [Cr+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O NMXUZAZJTJAHGK-UHFFFAOYSA-K 0.000 claims description 2
- IVKVYYVDZLZGGY-UHFFFAOYSA-K chromium(3+);octadecanoate Chemical compound [Cr+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O IVKVYYVDZLZGGY-UHFFFAOYSA-K 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical group ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 17
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 abstract 2
- 230000004913 activation Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 30
- 230000003197 catalytic effect Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004711 α-olefin Substances 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000005647 linker group Chemical group 0.000 description 6
- 238000011112 process operation Methods 0.000 description 6
- 239000003607 modifier Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003254 radicals Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 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 1
- GFOVGKSMIABDQZ-UHFFFAOYSA-N C(C)C1=C(N)C(=CC=C1)C.C(C)C=1C=CC=C(C1N)C Chemical compound C(C)C1=C(N)C(=CC=C1)C.C(C)C=1C=CC=C(C1N)C GFOVGKSMIABDQZ-UHFFFAOYSA-N 0.000 description 1
- 0 CP(*)N(N(P(*)*)P(*)*)P(*)* Chemical compound CP(*)N(N(P(*)*)P(*)*)P(*)* 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 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 1
- 230000003111 delayed effect Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 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
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- 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
- B01J31/1845—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 the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
- B01J31/188—Amide derivatives thereof
-
- 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
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/34—Polymerisation in gaseous state
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/69—Chromium, molybdenum, tungsten or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/69—Chromium, molybdenum, tungsten or compounds thereof
- C08F4/69008—Chromium, molybdenum, tungsten or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/69017—Bidentate ligand
- C08F4/69025—Neutral ligand
- C08F4/69086—PP
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- 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
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
-
- 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
- C07C2531/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
Definitions
- the present invention relates to a method for oligomerization of olefins, and more particularly, to a method capable of eliminating olefins with improved efficiency by controlling the activity of the oligomerization reaction of olefins.
- Linear alpha-olefins such as 1-nuxene and 1-octene are used as cleaning agents, lubricants, plasticizers, etc., and are particularly used as comonomers for controlling the density of polymers in the production of linear low density polyethylene (LLDPE). Used.
- LLDPE linear low density polyethylene
- the present invention is to provide a method for oligomerization of olefins that exhibits high selectivity for 1-nuxene and 1-octene, while providing excellent catalytic activity and enabling stable process operation.
- a catalyst mixture comprising at least one diphosphino aminyl moiety, a ligand comprising a diphosphino aminyl moiety, a creme source and a promoter represented by the following formula (1);
- a method for oligomerizing an olefin comprising:
- R ′′, R 12 and R 13 are the same as or different from each other, and each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
- a is an integer of 2 or more
- D is aluminum or boron
- R 21 is the same as or different from each other, and each independently C 1 -C A hydrocarbyl group of 20, or a hydrocarbyl group of 1 to 20 carbon atoms substituted with halogen.
- the meaning of "included” as used in the specification is to embody a specific characteristic, domain, integer, step, operation, element and / or component and other specific characteristics, domain, integer, step, operation, element, component and / or group. It does not exclude the presence or absence of a.
- the oligomerization catalyst system of the olefin has a problem that it is difficult to operate a stable process, such as the reaction rate is too high, the reaction rate is rapidly increased. Adjusting the reaction conditions at the beginning of the reaction to stabilize the process can adversely affect the oligomerization of the olefin, such as reduced activity of the catalyst system or poor selectivity to linear alpha-olefins throughout the reaction.
- a catalyst mixture comprising a ligand comprising at least one diphosphino aminyl moiety, a chromium source, and a promoter represented by the following formula (1);
- a method for oligomerization of an olefin comprising:
- R ′′, R 12 and R 13 are the same as or different from each other, and are each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
- a is an integer of 2 or more
- D is aluminum or boron
- R 21 are the same as or different from each other, and are each independently 1 to
- a catalyst system treated with an activity regulator represented by Chemical Formula 2 is used.
- the catalyst system may recover its inherent catalytic activity after a certain time while slowing the rate of rise of reaction or initial catalyst activity due to the action of the activity regulator.
- the reaction can be actively controlled when the activity regulator is applied when the reaction is difficult to control.
- the activity regulator plays a role of temporarily delaying the increase in catalyst activity, and enables stable process operation without inhibiting the inherent catalyst activity and selectivity of the catalyst system.
- whether the above-described action and effect is expressed may vary depending on the timing of addition of the activity regulator or the presence of a promoter.
- said ligand, creme After the catalyst mixture is prepared by mixing the source and the cocatalyst, the activity regulator is mixed with the catalyst mixture and the oligomerization reaction of the olefin is initiated, whereby the above-described action and effect of the activity regulator can be expressed. That is, the above action and effect may be obtained by adding the activity modifier at the time of starting reaction or after any reaction during formation of the catalyst mixture.
- the activity regulator may be mixed with a ligand, a chromium source and a promoter at the same time and introduced into the reactor; Alternatively, when mixed with a catalyst solution in which the promoter is not present, the action and effect by the activity regulator cannot be expected.
- a ligand comprising at least one diphosphino aminyl moiety, a creme source and the formula
- a step of preparing a catalyst mixture comprising the promoter represented by 1 is performed.
- the ligand included in the catalyst mixture conventional ligands used for oligomerization of olefins may be applied without particular limitation.
- the ligand comprising at least one diphosphino aminyl moiety may be advantageous for the expression of high selectivity for 1-nuxene and 1-octene.
- the ligand may be a compound represented by the following Chemical Formula 3 or Formula 4:
- R 1 to R 5 are each independently alkyl having 1 to 10 carbon atoms, alkenyl having 1 to 10 carbon atoms, cycloalkyl having 4 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, aryl having 6 to 15 carbon atoms, and 7 to 20 carbon atoms.
- L is a linker linked with carbon atoms of diphosphino aminyl 8
- R 6 to R 9 and R 6 ' to R 9' are each independently alkyl having 1 to 10 carbon atoms, alkenyl having 1 to 10 carbon atoms, cycloalkyl having 4 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms and having 6 to 6 carbon atoms. 15 aryl, C7-20 alkylaryl, or C7-20 arylalkyl.
- At least one hydrogen contained in the alkyl, alkenyl, cycloalkyl, alkoxy, aryl alkylaryl, and arylalkyl may be an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, or a cyano group. Can be substituted.
- R 1 to R 4 of Chemical Formula 3; And R 6 to R 9 and R 6 ' to R 9' of Formula 4 are each independently methyl, ethyl, propyl, propenyl, propynyl, butyl (butyl), cyclohexyl, 2-methylcyclohexyl,
- L is a linker that connects diphosphino aminyl residues with 2 to 8 carbon atoms.
- the linker is one or more selected from the group consisting of aliphatic groups of 1 to 10 carbon atoms, substituted or unsubstituted alicyclic groups of 4 to 10 carbon atoms, and substituted or unsubstituted aromatic groups of 6 to 15 carbon atoms. Groups can have a combined structure.
- the linker may be a linear or branched alkylene group or alkenylene group having 1 to 20 carbon atoms, or 1 to 10 carbon atoms, or 1 to 5 carbon atoms (eg, one or two alkylene groups or Alkenylene group); One or more (eg, one or two arylene groups) of an arylene group having 6 to 20 carbon atoms or 6 to 10 carbon atoms may be combined. In this case, the arylene group having 6 to 20 carbon atoms may be unsubstituted or substituted with an alkyl group having 1 to 5 carbon atoms.
- At least one terminal of the linker may be substituted or unsubstituted an aryl group having 6 to 20 carbon atoms, or 6 to 10 carbon atoms.
- the linker when the linker is composed of an aliphatic group having 5 to 20 carbon atoms, at least one terminal may be substituted with an aryl group having 6 to 20 carbon atoms, and the aryl group may be unsubstituted or substituted with an alkyl group having 1 to 5 carbon atoms.
- the chromium source included in the catalyst mixture is a compound complexed to the nitrogen atom of the diphosphino aminyl residue included in the ligand.
- the chromium source may be an organic or inorganic crescent compound in which the oxidation state of the crack is from 0 to 6, for example, a chromium metal or a compound in which any organic or inorganic radical is bound to the crack.
- the organic radical is Alkyl, alkoxy, ester, ketone, amido radical and the like having 1 to 20 carbon atoms per radical.
- the inorganic radicals may be halides, sulfates, oxides, and the like.
- the chromium source is a compound that may exhibit high activity in oligomerization of olefins and is easy to use and obtain, and may include chromium (III) acetylacetonate, chromium chloride tetrahydrofuran, and chromium (III). 1) selected from the group consisting of 2-ethylnucleosanate, chromium (III) acetate, chromium (III) butyrate, chromium (III) pentanoate, chromium (III) laurate, and chromium stearate It may be a compound of more than one species.
- the cocatalyst included in the catalyst mixture may be an organometallic compound capable of activating the complex compound by the ligand and the chromium source described above, and preferably may be a compound represented by Formula 1 below:
- R ′′, R 12 and R 13 are the same as or different from each other, and are each independently hydrogen, halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,
- a is an integer of 2 or more.
- the promoter may be at least one compound selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, and isobutyl aluminoxane.
- the cocatalyst may be a modified methyl aluminoxane (MMAO) which is a compound in which a part of the methyl group of the methyl aluminoxane is substituted with another alkyl group.
- MMAO modified methyl aluminoxane
- the modified methyl aluminoxane may be a compound in which 40 mol% or less, or 5 mol% to 35 mol% of the methyl group of the methyl aluminoxane is substituted with a linear or branched alkyl group having 3 to 10 carbon atoms.
- Commercially available examples of such modified methylaluminoxanes include MMAO-12, MMAO-3A, MMAO-7 and the like.
- the content ratio of the above-mentioned components constituting the catalyst mixture may be determined in consideration of catalyst activity and selectivity for linear alpha-olefins.
- the molar ratio of the ligand: chromium of the crum source: aluminum of the promoter in the catalyst mixture is in the range of 1: 1: 1: 10: 1: 10000, or 1: 1: 100 To 5: 1: 3000 may be advantageous for the expression of catalytic activity and selectivity.
- the above-mentioned components constituting the catalyst mixture may be added or mixed simultaneously or in any order in the presence of a suitable solvent.
- the solvent is heptane, toluene, cyclonucleic acid, methylcyclonucleic acid, 1-nuxene, 1-octene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone Can be used.
- a step of preparing a catalyst system in which an activity regulator represented by the following Chemical Formula 2 is added to the catalyst mixture is performed.
- D is aluminum or boron
- R 21 is the same as or different from each other, and each independently C 1 -C
- the activity regulator plays a role in delaying the increase in catalyst activity, and enables stable process operation without inhibiting the inherent catalyst activity and selectivity of the catalyst system.
- the action and effect described above can be expressed by adding the activity modifier at the time of reaction start after formation of the catalyst mixture.
- the activity modifier is one selected from the group consisting of trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, diethylaluminum chloride, and ethylaluminum dichloride.
- the above compound may be sufficient.
- methyl aluminoxane modified with the promoter it may be advantageous to use triethylaluminum as the activity regulator.
- Such activity modifiers may be added within a range that does not inhibit the inherent catalytic activity and selectivity of the catalyst system.
- the molar ratio of the size of the chromium source included in the catalyst system: D of the activity regulator is controlled to 1: 10 to 1: 3000, or 1: 100 to 1: 1200 It may be advantageous to delay the rise of the initial catalytic activity and again to restore the catalytic activity. Meanwhile, according to an embodiment of the invention, the step of contacting the olefin monomer with the catalyst system is performed.
- This step is to oligomerize the olefin monomer in the presence of the catalyst system described above, which can be carried out using a device and contacting techniques known to be applicable to oligomerization of olepin.
- the oligomerization reaction of the olepin may be a homogeneous liquid reaction in the presence or absence of an inert solvent, a slurry reaction in which the catalyst system is partially or completely insoluble, or an alpha-olefin which is a product as a main medium. It can be carried out with an acting bulk reaction or gaseous reaction.
- Gas phase ethylene may be used as the olefin monomer in the oligomerization reaction of the olefin.
- the oligomerization reaction of the relefin may be performed under an inert solvent such as benzene, toluene, xylene, cumene, heptane, cyclonucleic acid, methylcyclonucleic acid, methylcyclopentane, n-nucleic acid, 1-nuxene, 1-octene, and the like. have.
- an inert solvent such as benzene, toluene, xylene, cumene, heptane, cyclonucleic acid, methylcyclonucleic acid, methylcyclopentane, n-nucleic acid, 1-nuxene, 1-octene, and the like.
- the oligomerization reaction of the olefin may be performed at a temperature of about 0 to 200 ° C, or about 0 to 150 ° C, or about 30 to 100 ° C, or about 50 to 100 ° C.
- the reaction may be performed under a pressure of about 1 to 300 bar or 2 to 150 bar.
- the method for oligomerization of olefins according to the present invention provides high catalytic selectivity for 1-nuxene and 1-octene, while providing excellent catalytic activity and stable process operation.
- 1 is a graph showing the cumulative flow rate of the product over the reaction time in the oligomerization reaction of the olefin according to an embodiment and comparative example of the invention.
- chromium (III) acetylacetonate (17.5 mg, 0.05 mm)
- a ligand compound (1.1 eq. To Cr) prepared according to the above synthesis example was placed in a flask, and 100 ml of methylcyclonucleic acid was added thereto. By stirring, a ligand solution of 0.5 mM (Cr basis) was prepared.
- Parr reaction vessels of 600 ml capacity were prepared and vacuumed at 180 ° C. for 2 hours, after which the interior was replaced with argon and the temperature was lowered to 60 ° C.
- MMAO modified methylaluminoxane
- MMAO modified methylaluminoxane
- the oligomerization of ethylene was carried out in the same manner as in Example 1, except that no aluminum solution was added.
- the expression time of the catalytic activity is the time point when the end of the oligomerization reaction from the X segment when extending the section in which the flow rate of ethylene is constant after the start of the oligomerization reaction of ethylene to the trend line (that is, 15 after the start of reaction) Minutes).
- the conversion value of the catalytic activity is a value converted by giving a weight as much as the expression time of the catalytic activity to the catalytic activity value shown in the oligomerization reaction of ethylene.
- Example 1 In Example 1 and Comparative Example 1 are shown a graph of the cumulative flow rate of the product with the passage of reaction time in FIG.
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Abstract
Description
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JP2017566118A JP6647320B2 (ja) | 2015-09-15 | 2016-08-16 | オレフィンのオリゴマー化方法 |
US15/738,068 US10173948B2 (en) | 2015-09-15 | 2016-08-16 | Method for oligomerization of olefins |
CN201680040326.4A CN107849171B (zh) | 2015-09-15 | 2016-08-16 | 烯烃低聚方法 |
EP16846757.9A EP3296329B1 (en) | 2015-09-15 | 2016-08-16 | Method for oligomerization of olefins |
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US20180155254A1 (en) | 2018-06-07 |
KR20170032766A (ko) | 2017-03-23 |
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US10173948B2 (en) | 2019-01-08 |
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