WO2015076485A1 - 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 - Google Patents
리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 Download PDFInfo
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- WO2015076485A1 WO2015076485A1 PCT/KR2014/008028 KR2014008028W WO2015076485A1 WO 2015076485 A1 WO2015076485 A1 WO 2015076485A1 KR 2014008028 W KR2014008028 W KR 2014008028W WO 2015076485 A1 WO2015076485 A1 WO 2015076485A1
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- WO
- WIPO (PCT)
- Prior art keywords
- carbon atoms
- group
- formula
- olefin
- catalyst system
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 239000003446 ligand Substances 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000003606 oligomerizing effect Effects 0.000 title abstract 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005977 Ethylene Substances 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 62
- 238000006384 oligomerization reaction Methods 0.000 claims description 38
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052796 boron Inorganic materials 0.000 claims description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 239000006071 cream Substances 0.000 claims 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 10
- -1 polyethylene Polymers 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- KZIMLUFVKJLCCH-UHFFFAOYSA-N 5-[2-(1h-imidazol-5-yl)ethylamino]-5-oxopentanoic acid Chemical compound OC(=O)CCCC(=O)NCCC1=CNC=N1 KZIMLUFVKJLCCH-UHFFFAOYSA-N 0.000 description 1
- UKWYITQGGIIKFL-UHFFFAOYSA-N CCN(CC)CC.[B+3] Chemical compound CCN(CC)CC.[B+3] UKWYITQGGIIKFL-UHFFFAOYSA-N 0.000 description 1
- HFEVWLDHPOCPTP-UHFFFAOYSA-N CCNCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCNCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F HFEVWLDHPOCPTP-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- SHPVKUQHCZKKRP-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC SHPVKUQHCZKKRP-UHFFFAOYSA-N 0.000 description 1
- RPXNIXOOFOQCKJ-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC RPXNIXOOFOQCKJ-UHFFFAOYSA-N 0.000 description 1
- CTNCAPKYOBYQCX-UHFFFAOYSA-N [P].[As] Chemical group [P].[As] CTNCAPKYOBYQCX-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 229910052787 antimony Chemical group 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- IZMHKHHRLNWLMK-UHFFFAOYSA-M chloridoaluminium Chemical compound Cl[Al] IZMHKHHRLNWLMK-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 238000012777 commercial manufacturing Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- ISEJRLXHKSHKPM-UHFFFAOYSA-N dimethyl(2-methylpropyl)alumane Chemical compound CC(C)C[Al](C)C ISEJRLXHKSHKPM-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- DKQVJMREABFYNT-UHFFFAOYSA-N ethene Chemical group C=C.C=C DKQVJMREABFYNT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229930189585 ingamine Natural products 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-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
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000002902 organometallic compounds Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WNFSFUSCVXIYGN-UHFFFAOYSA-N phenylaluminum Chemical compound [Al]C1=CC=CC=C1 WNFSFUSCVXIYGN-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 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
-
- 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
-
- 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
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- 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
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- 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
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
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- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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Definitions
- the present invention relates to a ligand compound, a catalyst system for olefin oligomerization, and a method for olephine oligomerization using the same.
- Linear alpha-olef in is a comonomer. It is an important material used in detergents, lubricant plasticizers, etc., and is widely used commercially.
- 1-nuxene and 1-octene are widely used as comonomers for controlling the density of polyethylene in the production of linear low density polyethylene (LLDPE).
- LLDPE Linear Low-Density Polyethylene
- alpha-lephine differs in the field of application and the market size, the technology for selectively producing a specific olefin is of great commercial importance, and recently, 1-nuxene or 1 is selected through selective ethylene oligomerizat ion. There is a lot of research on cation catalyst technology to produce octene with high selectivity.
- the ligand containing the heteroatoms of the prior art described above is still a situation for the demand for multi-reaction reaction activity and high selectivity that is consistently persisted during reaction reaction of 1-octene or 1-nucleene.
- the present invention is to provide a novel ligand compound capable of remerizing and ethylene ethylene with high catalytic activity, selectivity, a catalyst system for leulevine oligomerization comprising the same, and an olefin oligomerization method using the same.
- the ligand compound according to one aspect of the present invention may be represented by the following formula (1).
- X is RrN, 0, or S Ri is hydrogen.
- R 2 to R 5 are each independently an aryl group having 6 to 40 carbon atoms
- R 6 and R 7 are H or an alkyl group having 1 to 20 carbon atoms.
- the ligand compound represented by the formula (1); Chromium source; And a promoter.
- X is Rr "N, 0, or S
- Ri is hydrogen, N, 0, F.
- R 2 to R 5 are each independently an aryl group having 6 to 40 carbon atoms
- R 6 and R 7 are H or an alkyl group having 1 to 20 carbon atoms.
- a method for irrelevant oligomerization is to multi-reduce reaction of relevin in the presence of a catalyst system for relevin oligomerization, including a ligand compound represented by the following Chemical Formula 1, a chromium source, and a promoter It may include a step.
- X is R -N, 0, or S
- Ri is hydrogen.
- N 0, F.
- R 2 to 1 are each independently an aryl group having 6 to 40 carbon atoms, and R 6 and R 7 are H or an alkyl group having 1 to 20 carbon atoms.
- ethylene can be oligomerized with a high selectivity compared to a conventional catalyst system.
- the present invention provides a ligand compound represented by the following formula (1).
- X is R ⁇ N, 0, or S
- Ri is hydrogen.
- An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, or an arylalkyl group, with or without one or more hetero elements of N, 0, F, S or P, R 2 to 3 ⁇ 4 are each independently an aryl group having 6 to 40 carbon atoms, and R 6 and R 7 are H or an alkyl group having 1 to 20 carbon atoms.
- the ligand compound represented by Formula 1 represented by Formula 1; Crum source; And a catalyst system for olefin oligomerization comprising a promoter.
- the lelpene oligo comprising the step of multi-reaction of the lelpene in the presence of a catalyst system for olefin oligomerization comprising the ligand compound represented by the formula (1), the source of crum, and the promoter A method of merging is provided.
- Ligand compound of the present invention may be represented by the formula (1).
- X 0, or S
- Ri is hydrogen, an alkyl group having 1 to 20 carbon atoms with or without one hetero atom of N, 0, F, S or P, an aryl group having 40 to 6 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, or It is an arylalkyl group, R ⁇ 2> -Rs is respectively independently a C6-C40 aryl group, R ⁇ 6> and R ⁇ 7> is H or a C1-C20 alkyl group. More specifically, according to one embodiment of the present invention, an example of the ligand compound represented by Formula 1 may be represented by one of the following structural formula, but the present invention is not limited thereto. The following compounds can be prepared by conventional methods for preparing ligands, and are more specific in the examples that follow. The compound represented by Chemical Formula 1 may be synthesized by the following method, but is not limited thereto.
- the catalyst system for olepin oligomerization comprises a ligand compound represented by the following formula: a source of creme; And a promoter.
- X is Ri-N, 0, or S
- Ri is hydrogen, N.
- R 2 to R 5 are each independently an aryl group having 6 to 40 carbon atoms.
- R 6 and R 7 are H or an alkyl group having 1 to 20 carbon atoms.
- catalyst system in the leulevine oligomerization catalyst system of the present invention means that the compound represented by the formula (1) and the cocatalyst are added together or simultaneously in any order and in the presence or absence of monomer in any suitable solvent to be activated. It means that can be obtained with the catalyst composition.
- the source of the cracks may be a crack or a precursor of a crack.
- the crum or crum precursors may include crum (III) acetylacetonoate, cadmium tetrastetrahydrofuran or crum (II 1) —2-ethylnucleoanoate, but the present invention is limited thereto. no.
- the catalyst system for olepin oligomerization of the present invention includes a cocatalyst.
- the cocatalyst is an organometallic compound including a Group 13 metal, and is not particularly limited as long as it can be used in the multimerization of olefins under a catalyst of a transition metal compound.
- the promoter may be at least one selected from the group consisting of compounds represented by Formulas 2 to 4 below, but the present invention is not limited thereto.
- R 6 is the same as or different from each other, and each independently a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or 1 to C carbon atoms substituted with halogen. Is a hydrocarbyl radical of 20 and c is an integer of 2 or greater.
- R 7 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
- L is a neutral Lewis base
- [L—H] + is a Bronsted acid
- Q is boron or aluminum in the +3 type oxidation state
- each E is independently an aryl having 6 to 20 carbon atoms unsubstituted or substituted with one or more hydrogen atoms with a halogen, a hydrocarbyl having 1 to 20 carbon atoms, an alkoxy functional group or a phenoxy functional group. Group or an alkyl group having 1 to 20 carbon atoms.
- the compound represented by the formula (2) may be methyl aluminoxane (MA0), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like.
- alkyl compound represented by Formula 3 examples include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum and diethyl.
- Chloro aluminum Triisopropylaluminum, tri-S—butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trinuclear aluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-P-rylylaluminum, Dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron tripropyl boron ⁇ tributyl boron and the like.
- Triphenylphosphonium tetraphenylaluminum Trimethylphosphonium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra (P-trifluoromethylphenyl) boron,
- Triphenylcarbonium tetrapentafluorophenylboron and the like Triphenylcarbonium tetrapentafluorophenylboron and the like.
- alumoxane can be used, more preferably methylalumoxane (MA0) which is an alkylalumoxane.
- MA0 methylalumoxane
- the catalyst for olepin oligomerization may include a ligand compound represented by the general formula (1), a crum source and a cocatalyst.
- the molar ratio of the ligand compound: crum source: promoter may be about 1: 1: 1 to about 10: 1: 10,000,000. And preferably about 1: 1: 100 to about 5: 1: 3,000.
- the present invention is not limited thereto.
- a catalyst system comprising a ligand compound represented by the formula (1), a creme source, and a cocatalyst
- the three component stones of the catalyst system are added together or simultaneously and in any order, in the presence or absence of monomers in any suitable solvent.
- Suitable solvents include heptane, toluene, 1-nuxene, diethyl ether, tetrahydrofuran. Acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone and the like.
- Elevine oligomerization method may include the step of multi-reacting the leulevine in the presence of a catalyst system for olefin oligomerization comprising a ligand compound represented by the following formula (1), a crum source, and a promoter .
- X is Ri-N, 0, or S
- Ri is hydrogen, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 40 carbon atoms, a heteroaryl group of 3 to 30 carbon atoms, or without one or more hetero atoms of N, 0, F, S or P, or
- An arylalkyl group, R 2 to R 5 are each independently an aryl group having 6 to 40 carbon atoms,
- R 6 and R 7 are H or an alkyl group having 1 to 20 carbon atoms.
- the oligomerization of olefins is achieved by the partial dissolution of the homogeneous liquid reaction or catalyst system in the presence or absence of the inert solvent using the catalyst system according to the examples described above and conventional apparatus and contacting techniques.
- Slurry reactions or two-phase liquid / liquid reactions or products in the form of totally insoluble form may be prepared as bulk reactions or gaseous reactions in which lepin acts as the main medium, but homogeneous liquid reactions are preferred.
- the oligomerization reaction of the olefin can be carried out in any inert solvent bath that does not react with the catalyst compound and the active agent.
- Suitable inert solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane cyclonucleic acid, methylcyclonucleic acid, methylcyclopentane, nucleic acid, pentane, butane, isobutane and the like.
- the solvent may be used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkyl aluminum.
- the olefin oligomerization reaction may be carried out at a temperature of about 5 to about 200 1:, preferably of about 30 to about 150 ⁇ :.
- the olefin oligomerization reaction may be carried out at a pressure of about 1 to about 300 bar, preferably at a pressure of about 2 to about 150 bar.
- the use of the compound according to the present invention or the catalyst system including the same shows high selectivity to 1-nuxene 1-octene.
- the reactor was opened and 0.5 mL of nonane (GC internal standard) was added. About 2 mL of the liquid part was quenched with water and the organic part was filtered with a PTFE syringe filter to make a GC sample. The distribution of liquid products was analyzed by GC. 300 mL of ethanol / HCl (10 vol%) was added to the remaining reaction solution, followed by stirring and filtering to obtain a polymer. The polymer was dried overnight in a 65 ° C vacuum oven.
- GC internal standard GC internal standard
- Example 2 Except for using the ligand (synthesis example 2) prepared according to the synthesis example was carried out in the same manner as in Example 1.
- Example 3 Except for using the ligand (synthesis example 2) prepared according to the synthesis example was carried out in the same manner as in Example 1.
- Example 3 The same procedure as in Example 1 was carried out except that the ligand (Synthesis Example 3) prepared according to the synthesis example was used. Comparative Example 1
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Abstract
Description
Claims
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CN201480004047.3A CN104884165B (zh) | 2013-11-19 | 2014-08-28 | 配体化合物、用于烯烃低聚反应的催化剂体系及使用其的用于烯烃低聚反应的方法 |
US14/651,152 US9409833B2 (en) | 2013-11-19 | 2014-08-28 | Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same |
JP2015549292A JP6027695B2 (ja) | 2013-11-19 | 2014-08-28 | リガンド化合物、オレフィンオリゴマー化用触媒系、およびこれを用いたオレフィンオリゴマー化方法 |
EP14863289.6A EP2918340B1 (en) | 2013-11-19 | 2014-08-28 | Ligand compound, catalyst system for oligomerizing olefin, and method for oligomerizing olefin using same |
US15/195,378 US9643170B2 (en) | 2013-11-19 | 2016-06-28 | Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same |
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US15/195,378 Division US9643170B2 (en) | 2013-11-19 | 2016-06-28 | Ligand compound, catalyst system for olefin oligomerization, and method for olefin oligomerization using the same |
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KR101768194B1 (ko) * | 2015-05-15 | 2017-08-16 | 주식회사 엘지화학 | 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법 |
KR101757370B1 (ko) | 2015-06-01 | 2017-07-12 | 주식회사 엘지화학 | 1-옥텐 조성물 |
SG11202000016XA (en) | 2017-07-06 | 2020-01-30 | Mitsui Chemicals Inc | Catalyst for olefin multimerization and method for producing olefin multimer in presence of said catalyst |
EP4342903A1 (en) * | 2022-03-14 | 2024-03-27 | Lg Chem, Ltd. | Ligand compound, organic chrome compound, and catalyst composition comprising same |
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JP6027695B2 (ja) | 2016-11-16 |
US9409833B2 (en) | 2016-08-09 |
US20150329440A1 (en) | 2015-11-19 |
EP2918340A4 (en) | 2016-07-06 |
EP2918340B1 (en) | 2017-03-15 |
CN104884165B (zh) | 2017-05-24 |
EP2918340A1 (en) | 2015-09-16 |
CN104884165A (zh) | 2015-09-02 |
JP2016506404A (ja) | 2016-03-03 |
US9643170B2 (en) | 2017-05-09 |
KR101601936B1 (ko) | 2016-03-09 |
US20160303552A1 (en) | 2016-10-20 |
KR20150057470A (ko) | 2015-05-28 |
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