KR20240004095A - Ethylene oligomerization catalyst including ligand compound, catalyst composition employing same, and method for preparing ethylene oligomer using same - Google Patents
Ethylene oligomerization catalyst including ligand compound, catalyst composition employing same, and method for preparing ethylene oligomer using same Download PDFInfo
- Publication number
- KR20240004095A KR20240004095A KR1020230038809A KR20230038809A KR20240004095A KR 20240004095 A KR20240004095 A KR 20240004095A KR 1020230038809 A KR1020230038809 A KR 1020230038809A KR 20230038809 A KR20230038809 A KR 20230038809A KR 20240004095 A KR20240004095 A KR 20240004095A
- Authority
- KR
- South Korea
- Prior art keywords
- aryl
- alkyl
- ethylene
- formula
- oligomerization catalyst
- Prior art date
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000005977 Ethylene Substances 0.000 title claims abstract description 77
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 150000001875 compounds Chemical class 0.000 title claims abstract description 66
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 60
- 239000003446 ligand Substances 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 claims abstract description 30
- -1 Phosphorus 1-hexene Chemical compound 0.000 claims abstract description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 125000003118 aryl group Chemical group 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 33
- 125000001424 substituent group Chemical group 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 20
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims description 18
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 11
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 150000001845 chromium compounds Chemical class 0.000 claims description 7
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 6
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 claims description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 claims description 3
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 3
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 claims description 3
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000013064 chemical raw material Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 description 44
- 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 16
- 239000000047 product Substances 0.000 description 15
- 239000011651 chromium Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 11
- 229940125904 compound 1 Drugs 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 229940126062 Compound A Drugs 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 125000006274 (C1-C3)alkoxy group Chemical group 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Chemical class CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- RNRYVHUOQODQHG-UHFFFAOYSA-N 2-diphenylphosphanyl-n-(2-diphenylphosphanylethyl)ethanamine Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCNCCP(C=1C=CC=CC=1)C1=CC=CC=C1 RNRYVHUOQODQHG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- JAGIUTGWNQNUTM-UHFFFAOYSA-N hex-1-ene;oct-1-ene Chemical compound CCCCC=C.CCCCCCC=C JAGIUTGWNQNUTM-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 125000006413 ring segment Chemical group 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000004665 trialkylsilyl group Chemical group 0.000 description 2
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- PXSCEAJMCLQOBY-UHFFFAOYSA-N 2,6,6-trimethyloxaluminane Chemical compound C[Al]1CCCC(C)(C)O1 PXSCEAJMCLQOBY-UHFFFAOYSA-N 0.000 description 1
- VWVRASTUFJRTHW-UHFFFAOYSA-N 2-[3-(azetidin-3-yloxy)-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound O=C(CN1C=C(C(OC2CNC2)=N1)C1=CN=C(NC2CC3=C(C2)C=CC=C3)N=C1)N1CCC2=C(C1)N=NN2 VWVRASTUFJRTHW-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical class CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- 125000005865 C2-C10alkynyl group Chemical group 0.000 description 1
- YLMXBNACRIGGFX-UHFFFAOYSA-N C=1[C-]=NNN=1 Chemical compound C=1[C-]=NNN=1 YLMXBNACRIGGFX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- WPPONCHFOIIFIJ-UHFFFAOYSA-N N1N=NN=[C-]1 Chemical compound N1N=NN=[C-]1 WPPONCHFOIIFIJ-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- SCCNXKACLAJZAP-UHFFFAOYSA-N chromium(3+);pyrrol-1-ide Chemical compound [Cr+3].C=1C=C[N-]C=1.C=1C=C[N-]C=1.C=1C=C[N-]C=1 SCCNXKACLAJZAP-UHFFFAOYSA-N 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 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 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- 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
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/107—Alkenes with six carbon atoms
-
- 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
- C07C2/34—Metal-hydrocarbon complexes
-
- 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
-
- 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
Abstract
본 발명은 리간드 화합물을 포함하는 에틸렌 올리고머화 촉매, 이를 채용한 촉매 조성물 및 이를 이용한 에틸렌 올리고머의 제조방법에 관한 것으로, 우수한 올리고머에 대한 선택성 및 1-헥센에 대한 선택성을 나타내어, 산업적으로 유용한 화학원료인 1-헥센을 높은 순도로 대량생산할 수 있다.The present invention relates to an ethylene oligomerization catalyst containing a ligand compound, a catalyst composition employing the same, and a method for producing ethylene oligomer using the same. It exhibits excellent selectivity for oligomers and selectivity for 1-hexene, and is an industrially useful chemical raw material. Phosphorus 1-hexene can be mass-produced with high purity.
Description
본 발명은 리간드 화합물을 포함하는 에틸렌 올리고머화 촉매, 이를 채용한 촉매 조성물 및 이를 이용한 에틸렌 올리고머의 제조방법에 관한 것이다.The present invention relates to an ethylene oligomerization catalyst containing a ligand compound, a catalyst composition employing the same, and a method for producing ethylene oligomer using the same.
에틸렌으로부터의 올레핀 올리고머화는 다양하고 유용한 화학제품의 원료로 이용된다. 구체적으로 올레핀 올리고머를 원료로 사용하여 고급 올레핀을 제공할 수 있으며, 산업적으로 중요한 공정들이 에틸렌으로부터의 알파 올레핀의 제조를 포함하고 있다. 특히 에틸렌으로부터 제조되는 알파 올레핀 중 에틸렌의 삼량체화를 통한 1-헥센의 제조가 매우 중요하다.Olefin oligomerization from ethylene is used as a raw material for a variety of useful chemical products. Specifically, olefin oligomers can be used as raw materials to provide higher olefins, and industrially important processes include the production of alpha olefins from ethylene. In particular, among alpha olefins produced from ethylene, the production of 1-hexene through trimerization of ethylene is very important.
그러나 상기 올리고머화에서 직면하게 되는 문제점은 단일 올리고머에 대한 선택성이 낮은 점이다. 즉, 목적하는 올리고머와 함께 다른 올리고머 및 폴리머 등 원하지 않는 부생성물(side product) 및 부산물(byproduct)도 형성될 수 있다. 예를 들어, 에틸렌을 올리고머화하여 1-헥센을 제조할 때 헥센의 다른 이성질체들인 2-헥센 및 3-헥센이 형성될 수 있을 뿐만 아니라, 에틸렌의 고급 올리고머들인 옥텐, 데센 및 도데센도 생성될 수 있고, 보다 고분자량의 폴리에틸렌도 형성될 수 있다.However, the problem encountered in the above oligomerization is that the selectivity for single oligomers is low. That is, along with the desired oligomer, unwanted side products and byproducts such as other oligomers and polymers may also be formed. For example, when 1-hexene is produced by oligomerizing ethylene, not only other isomers of hexene, 2-hexene and 3-hexene, can be formed, but also octene, decene, and dodecene, which are higher oligomers of ethylene. And higher molecular weight polyethylene can also be formed.
상기와 같이 생성된 부생성물 및 부산물은 공정상 또는 효율상으로 문제를 일으킬 수 있다. 생성된 폴리머는 올리고머화 반응기의 내부 부품, 파이프라인 및/또는 기타 장비에 침착(deposition)될 수 있어 이를 제거하기 위하여 공정 장비를 정지하는 기간이 필요로 될 수 있고, 제거를 위한 스팀 처리, 수처리 등의 물리적인 처리를 위한 기간 및 비용이 소모될 수 있다. 또한 목적하는 올리고머와 생성된 부생성물 및 부산물을 분리하기 위하여 추가의 공정 및 시간소요로 인하여 생산효율이 매우 낮아질 수 있다.By-products and by-products produced as described above may cause problems in the process or efficiency. The produced polymer may be deposited on the internal parts, pipelines, and/or other equipment of the oligomerization reactor, which may require a period of stopping the process equipment to remove it, and may require steam treatment or water treatment for removal. It may take time and cost for physical processing, etc. In addition, production efficiency may be very low due to additional processes and time required to separate the desired oligomer from the generated by-products and by-products.
한편, 에틸렌으로부터의 올레핀 올리고머화 반응은 지방족 탄화수소 용매 중에서 수행될 수 있다. 예를 들어, 1-헥센을 제조하기 위한 공정들에서 사이클로헥산, 메틸사이클로헥산, 헥산 및 헵탄이 이용될 수 있으며, 이들 용매는 유기 금속 촉매에 대한 우수한 용해도를 가질 수 있지만, 1-헥센과의 유사한 끓는점을 나타내므로 분리에 있어 증류 단을 높게 하고 열량을 많이 소비하는 등 비용적 시간적으로 문제점이 발생할 수 있다.Meanwhile, the olefin oligomerization reaction from ethylene can be performed in an aliphatic hydrocarbon solvent. For example, cyclohexane, methylcyclohexane, hexane, and heptane can be used in processes to produce 1-hexene, and while these solvents may have excellent solubility for organometallic catalysts, their Since they have similar boiling points, problems may arise in terms of cost and time, such as requiring a high distillation stage and consuming a lot of heat during separation.
높은 단일 알파 올레핀 선택성, 특히 높은 1-헥센 선택성에 관한 요구를 충족시키기 위하여, 새로운 공정들이 개발되고 있다. 셰브런 필립스(Chevron Phillips)에 의해 창안된 선택적 C6-상용화 공정(J.T.Dixon, M.J.Green, F.M.Hess, D.H.Morgan, "Advances in selective ethylene trimerisation - a critical overview", Journal of Organometallic Chemistry 689(2004) 3641-3668 참조)이 알려져 있으며, 사솔(Sasol)에 의해 출원된 특허 출원(WO 03/053891 A1)은 전형적인 CrCl3(비스-(2-디페닐포스피노-에틸)아민)(CrCl3(bis-(2-diphenylphosphino-ethyl)amine)/MAO(메틸알루미녹산) 형태의 크롬 기반의 선택적 에틸렌-삼량체화 촉매 시스템(chromium-based selective ethylene-trimerization catalyst systems)을 개시하고 있다. 그러나, 이러한 모든 촉매 시스템은 1-헥센 외에 상당한 양의 폴리에틸렌, 다른 알파 올레핀과 같은 부산물 및 부생성물이 생성된다.To meet the demand for high single alpha olefin selectivity, especially high 1-hexene selectivity, new processes are being developed. Selective C6-commercialization process created by Chevron Phillips (see JTDixon, MJGreen, FMHess, DHMorgan, "Advances in selective ethylene trimerisation - a critical overview", Journal of Organometallic Chemistry 689 (2004) 3641-3668) This is known, and the patent application filed by Sasol (WO 03/053891 A1) describes a typical CrCl 3 (bis-(2-diphenylphosphino-ethyl)amine) (CrCl 3 (bis-(2-diphenylphosphino) -ethyl)amine)/MAO (methylaluminoxane) type chromium-based selective ethylene-trimerization catalyst systems are disclosed. However, all these catalyst systems are 1-hexene. In addition, significant amounts of by-products and by-products such as polyethylene and other alpha olefins are produced.
즉, 목적하는 올레핀 이성질체에 대한 알파 올레핀의 증가된 선택도 및 고효율을 가지는 촉매 시스템에 대한 필요성이 여전히 남아 있다. 따라서, 향상된 선택도, 감소된 부생성물 및 부산물 형성, 목적하는 알파 올레핀의 향상된 수율, 향상된 경제성 및 향상된 효율을 달성할 수 있는 촉매 및 제조방법에 대한 연구가 필요하다.That is, there still remains a need for catalyst systems with increased selectivity of alpha olefins to the desired olefin isomers and high efficiency. Therefore, research is needed on catalysts and preparation methods that can achieve improved selectivity, reduced by-products and by-product formation, improved yield of the desired alpha olefin, improved economics, and improved efficiency.
본 발명의 목적은 리간드 화합물을 포함하는 우수한 1-헥센 선택성을 나타내는 에틸렌 올리고머화 촉매를 제공하는 것이다.The purpose of the present invention is to provide an ethylene oligomerization catalyst containing a ligand compound and exhibiting excellent 1-hexene selectivity.
본 발명의 또 다른 목적은 상기 촉매를 채용한 높은 온도에서도 우수한 활성과 향상된 선택성을 가지는 에틸렌 올리고머화 촉매 조성물을 제공하는 것이다.Another object of the present invention is to provide an ethylene oligomerization catalyst composition employing the above catalyst, which has excellent activity and improved selectivity even at high temperatures.
본 발명은 상기 촉매 조성물을 이용한 상업적으로 이용이 용이한 에틸렌 올리고머의 제조방법을 제공한다.The present invention provides a method for producing ethylene oligomers using the above catalyst composition, which is easily commercially available.
본 발명은 크롬 화합물 및 하기 화학식 1로 표시되는 리간드 화합물을 포함하는 에틸렌 올리고머화 촉매를 제공한다.The present invention provides an ethylene oligomerization catalyst comprising a chromium compound and a ligand compound represented by the following formula (1).
[화학식 1][Formula 1]
[상기 화학식 1에서,[In Formula 1 above,
L1 및 L2는 서로 독립적으로 (C2-C4)알킬렌이고;L 1 and L 2 are independently (C2-C4)alkylene;
R1 내지 R4는 서로 독립적으로 수소, (C1-C10)알킬, (C3-C20)시클로알킬, (C6-C20)아릴, (C6-C20)아릴(C1-C10)알킬 또는 (C1-C10)알콕시이며;R 1 to R 4 are each independently hydrogen, (C1-C10)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, or (C1-C10) ) alkoxy;
상기 R1 내지 R4의 아릴은 (C1-C10)알킬, (C6-C20)아릴, 트리(C1-C10)알킬실릴 및 (C1-C10)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.]The aryl of R 1 to R 4 is one or more substituents selected from the group consisting of (C1-C10)alkyl, (C6-C20)aryl, tri(C1-C10)alkylsilyl, and (C1-C10)alkoxy. May be replaced.]
상세하게 상기 화학식 1의 L1 및 L2는 서로 독립적으로 (C2-C3)알킬렌이고; R1 내지 R4는 서로 독립적으로 수소, (C1-C7)알킬, (C3-C12)시클로알킬, (C6-C12)아릴, (C6-C12)아릴(C1-C7)알킬 또는 (C1-C7)알콕시이며; 상기 R1 내지 R4의 아릴은 (C1-C7)알킬, (C6-C12)아릴, 트리(C1-C7)알킬실릴 및 (C1-C7)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.In detail, L 1 and L 2 of Formula 1 are independently (C2-C3)alkylene; R 1 to R 4 are each independently hydrogen, (C1-C7)alkyl, (C3-C12)cycloalkyl, (C6-C12)aryl, (C6-C12)aryl(C1-C7)alkyl, or (C1-C7) ) alkoxy; The aryl of R 1 to R 4 is one or more substituents selected from the group consisting of (C1-C7)alkyl, (C6-C12)aryl, tri(C1-C7)alkylsilyl, and (C1-C7)alkoxy. can be replaced.
보다 상세하게 상기 화학식 1의 L1 및 L2는 서로 독립적으로 (C2-C3)알킬렌이고; R1 내지 R4는 서로 독립적으로 수소, (C1-C7)알킬, (C6-C12)아릴 또는 (C6-C12)아릴(C1-C7)알킬이며; 상기 R1 내지 R4의 아릴은 (C1-C7)알킬, (C6-C12)아릴, 트리(C1-C7)알킬실릴 및 (C1-C7)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.In more detail, L 1 and L 2 of Formula 1 are independently (C2-C3) alkylene; R 1 to R 4 are independently hydrogen, (C1-C7)alkyl, (C6-C12)aryl, or (C6-C12)aryl(C1-C7)alkyl; The aryl of R 1 to R 4 is one or more substituents selected from the group consisting of (C1-C7)alkyl, (C6-C12)aryl, tri(C1-C7)alkylsilyl, and (C1-C7)alkoxy. can be replaced.
본 발명의 일 실시예에 따른 리간드 화합물은 하기 화학식 2로 표시되는 것일 수 있다.The ligand compound according to an embodiment of the present invention may be represented by the following formula (2).
[화학식 2][Formula 2]
[상기 화학식 2에서,[In Formula 2 above,
R11 내지 R14는 서로 독립적으로 수소, (C1-C5)알킬, (C6-C10)아릴 또는 (C6-C10)아릴(C1-C5)알킬이며;R 11 to R 14 are independently hydrogen, (C1-C5)alkyl, (C6-C10)aryl, or (C6-C10)aryl(C1-C5)alkyl;
상기 R11 내지 R14의 아릴은 (C1-C5)알킬, 트리(C1-C5)알킬실릴 및 (C1-C5)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.]The aryl of R 11 to R 14 may be substituted with one or more substituents selected from the group consisting of (C1-C5)alkyl, tri(C1-C5)alkylsilyl, and (C1-C5)alkoxy.]
또한 상기 화학식 2의 R11 내지 R13은 서로 독립적으로 (C1-C5)알킬, (C6-C10)아릴 또는 (C6-C10)아릴(C1-C5)알킬이며; R14는 수소 또는 (C1-C3)알킬이고; 상기 R11 내지 R13의 아릴은 (C1-C5)알킬, 트리(C1-C5)알킬실릴 및 (C1-C5)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.In addition, R 11 to R 13 in Formula 2 are independently (C1-C5)alkyl, (C6-C10)aryl, or (C6-C10)aryl(C1-C5)alkyl; R 14 is hydrogen or (C1-C3)alkyl; The aryl of R 11 to R 13 may be substituted with one or more substituents selected from the group consisting of (C1-C5)alkyl, tri(C1-C5)alkylsilyl, and (C1-C5)alkoxy.
구체적으로 본 발명의 일 실시예에 따른 리간드 화합물은 하기 화합물에서 선택되는 것일 수 있다.Specifically, the ligand compound according to an embodiment of the present invention may be selected from the following compounds.
본 발명은 일 실시예에 따른 에틸렌 올리고머화 촉매 및 유기 알루미늄 화합물을 포함하는 에틸렌 올리고머화 촉매 조성물을 제공한다.The present invention provides an ethylene oligomerization catalyst composition including an ethylene oligomerization catalyst and an organic aluminum compound according to an embodiment.
상기 유기 알루미늄 화합물은 메틸알루미녹산(MAO), 변형 메틸알루미녹산(MMAO), 에틸알루미녹산(EAO), 테트라이소부틸알루미녹산(TIBAO), 이소부틸알루미녹산(IBAO), 트리메틸알루미늄(TMA), 트리에틸알루미늄(TEA), 트리이소부틸알루미늄(TIBA), 트리-n-옥틸알루미늄, 메틸알루미늄 디클로라이드, 에틸알루미늄 디클로라이드, 디메틸알루미늄 클로라이드, 디에틸알루미늄 클로라이드, 알루미늄 이소프로폭사이드, 에틸알루미늄 세스퀴클로라이드 및 메틸알루미늄 세스퀴클로라이드로 이루어진 군으로부터 선택되는 하나 또는 둘 이상일 수 있다.The organic aluminum compounds include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethyl aluminoxane (EAO), tetraisobutylaluminoxane (TIBAO), isobutylaluminoxane (IBAO), trimethylaluminum (TMA), Triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethyl aluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethyl aluminum ceth. It may be one or more than one selected from the group consisting of methylaluminum sesquichloride and methylaluminum sesquichloride.
또한 본 발명은 일 실시예에 따른 에틸렌 올리고머화 촉매 조성물을 이용하는 에틸렌 올리고머의 제조방법을 제공한다.Additionally, the present invention provides a method for producing ethylene oligomer using an ethylene oligomerization catalyst composition according to an embodiment.
상기 에틸렌 올리고머의 제조방법은 생성되는 올리고머 전체 중 1-헥센이 60.0 내지 99.999 중량% 제조되는 것을 특징으로 할 수 있다.The method for producing the ethylene oligomer may be characterized in that 60.0 to 99.999% by weight of 1-hexene is produced based on the total oligomer produced.
또한 일 실시예에 있어서, 상기 에틸렌 올리고머의 제조방법은 벤젠, 글로로벤젠, 에틸벤젠, 톨루엔, 자일렌, 큐멘, 메시틸렌, 시클로헥산, 메틸시클로헥산, 메틸시클로펜탄, 헥산, 헵탄, 옥탄, 노난, 데칸, 헥센, 헵텐, 옥텐, 노넨, 데센, 애니솔, 에톡시벤젠 및 디메톡시벤젠로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 용매에서 수행되는 것일 수 있다.In addition, in one embodiment, the method for producing the ethylene oligomer includes benzene, glorobenzene, ethylbenzene, toluene, xylene, cumene, mesitylene, cyclohexane, methylcyclohexane, methylcyclopentane, hexane, heptane, octane, It may be performed in one or more solvents selected from the group consisting of nonane, decane, hexene, heptene, octene, nonene, decene, anisole, ethoxybenzene, and dimethoxybenzene.
본 발명의 특정 리간드 화합물을 포함하는 에틸렌 올리고머화 촉매 및 상기 촉매를 채용한 촉매 조성물은 향상된 1-헥센에 대한 선택성을 나타낼 수 있다.The ethylene oligomerization catalyst containing the specific ligand compound of the present invention and the catalyst composition employing the catalyst may exhibit improved selectivity for 1-hexene.
본 발명의 상기 촉매 조성물을 이용한 에틸렌 올리고머의 제조방법은 높은 온도에서도 놀랍도록 우수한 올리고머에 대한 선택성 및 1-헥센에 대한 선택성을 나타내어, 산업적으로 유용한 화학원료인 1-헥센을 높은 순도로 대량생산할 수 있다.The method for producing ethylene oligomer using the catalyst composition of the present invention exhibits surprisingly excellent selectivity for oligomers and selectivity for 1-hexene even at high temperatures, making it possible to mass-produce 1-hexene, an industrially useful chemical raw material, with high purity. there is.
이하, 본 발명의 리간드 화합물을 포함하는 에틸렌 올리고머화 촉매, 이를 채용한 촉매 조성물 및 이를 이용한 에틸렌 올리고머의 제조방법에 대하여 상세히 설명한다.Hereinafter, the ethylene oligomerization catalyst containing the ligand compound of the present invention, the catalyst composition employing the same, and the method for producing ethylene oligomer using the same will be described in detail.
본 발명에서 사용되는 단수 형태는 문맥에서 특별한 지시가 없는 한 복수 형태도 포함하는 것으로 의도할 수 있다.As used herein, the singular forms “a,” “an,” and “the” are intended to also include the plural forms, unless the context clearly dictates otherwise.
본 발명에 기재된 "포함한다"는 "구비한다", "함유한다", "가진다" 또는 "특징으로 한다" 등의 표현과 등가의 의미를 가지는 개방형 기재이며, 추가로 열거되어 있지 않은 요소, 재료 또는 공정을 배제하지 않는다.As used in the present invention, “comprises” is an open description with the same meaning as expressions such as “comprises,” “contains,” “has,” or “features,” and includes elements and materials that are not additionally listed. or does not exclude the process.
본 발명에 기재된 "알킬"은 탄소 및 수소 원자만으로 구성된 1가의 직쇄 또는 분쇄 포화 탄화수소 라디칼을 의미하는 것으로, 이러한 알킬 라디칼의 예는 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, t-부틸, 펜틸, 헥실, 옥틸, 노닐 등을 포함하지만 이에 한정되는 것은 아니다.As used herein, “alkyl” refers to a monovalent straight-chain or branched saturated hydrocarbon radical consisting only of carbon and hydrogen atoms. Examples of such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl. , pentyl, hexyl, octyl, nonyl, etc., but is not limited thereto.
본 발명에 기재된 "아릴"은 하나의 수소 제거에 의해서 방향족 탄화수소로부터 유도된 유기 라디칼로, 각 고리에 적절하게는 4 내지 7개, 바람직하게 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함하며, 다수개의 아릴이 단일결합으로 연결되어 있는 형태까지 포함한다. 융합 고리계는 포화 또는 부분적으로 포화된 고리와 같은 지방족 고리를 포함할 수 있고, 반드시 하나 이상의 방향족 고리를 포함하고 있다. 또한 상기 지방족 고리는 질소, 산소, 황, 카보닐 등을 고리 내에 포함할 수도 있다. 상기 아릴 라디칼의 구체적인 예로서는 페닐, 나프틸, 비페닐, 인데닐(indenyl), 플루오레닐, 페난트레닐, 안트라세닐, 트라이페닐레닐, 파이레닐, 크라이세닐, 나프타세닐, 9,10-다이하이드로안트라세닐 등을 포함한하지만 이에 한정되는 것은 아니다.“Aryl” as described in the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and is a single or fused ring system containing suitably 4 to 7 ring atoms, preferably 5 or 6 ring atoms in each ring. It includes a form in which multiple aryls are connected by a single bond. The fused ring system may include an aliphatic ring, such as a saturated or partially saturated ring, and must include at least one aromatic ring. Additionally, the aliphatic ring may contain nitrogen, oxygen, sulfur, carbonyl, etc. in the ring. Specific examples of the aryl radical include phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, 9,10-dihydro. Including, but not limited to, anthracenyl and the like.
본 발명에 기재된 "시클로알킬"은 하나 이상의 고리로 구성된 1가의 포화 카보시클릭 라디칼을 의미한다. 시클로알킬 라디칼의 예는 시클로프로필, 시클로부틸, 시클로펜틸, 시클로헥실, 시클로헵틸 등을 포함하지만, 이에 한정되는 것은 아니다.As used herein, “cycloalkyl” means a monovalent saturated carbocyclic radical consisting of one or more rings. Examples of cycloalkyl radicals include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.
본 발명에 기재된 "알콕시"는 -OCH3, -OCH2CH3, -O(CH2)2CH3, -O(CH2)3CH3, -O(CH2)4CH3, -O(CH2)5CH3 및 이와 유사한 것을 포함하는 -O-(알킬)을 의미하며, 여기에서 '알킬'은 상기 정의된 것과 같다.“Alkoxy” described in the present invention is -OCH 3 , -OCH 2 CH 3 , -O(CH 2 ) 2 CH 3 , -O(CH 2 ) 3 CH 3 , -O(CH 2 ) 4 CH 3 , -O means -O-(alkyl), including (CH 2 ) 5 CH 3 and the like, where 'alkyl' is as defined above.
본 발명에 기재된 "트리알킬실릴"은 실릴기에서의 3개의 수소가 각각 독립적으로 알킬로 치환된 기를 예로 들 수 있으며, 여기에서 '알킬'은 상기 정의된 것과 같다. 치환하기에 바람직한 알킬은 탄소수 1 내지 5의 알킬이며, 구체적으로 메틸, 에틸, 프로필 이소프로필, 부틸, sce-부틸, tert-부틸, 시클로부틸 등을 예로 들 수 있고, 보다 구체적으로 트리알킬실릴은 트리메틸실릴, 트리에틸실릴, t-부틸디메틸실릴, 비닐디메틸실릴 또는 프로필디메틸실릴일 수 있으나, 이에 한정되는 것은 아니다.“Trialkylsilyl” described in the present invention may be an example of a group in which three hydrogens in a silyl group are each independently substituted with alkyl, where ‘alkyl’ is as defined above. Preferred alkyl to be substituted is alkyl having 1 to 5 carbon atoms, and specific examples include methyl, ethyl, propyl isopropyl, butyl, sce-butyl, tert-butyl, cyclobutyl, etc. More specifically, trialkylsilyl is It may be trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, or propyldimethylsilyl, but is not limited thereto.
본 발명에 기재된 "할로겐"은 불소, 염소, 브롬 또는 요오드 원자를 의미한다.As used herein, “halogen” means a fluorine, chlorine, bromine or iodine atom.
본 발명에 기재된 "에틸렌 올리고머화"는 에틸렌이 소중합되는 것으로, 중합되는 에틸렌의 개수에 따라 삼량화(trimerization), 사량화(tetramerization)라고 한다. 특히 본 발명에서는 HDPE 및 LLDPE의 코모노머로 이용되는 에틸렌이 삼량화된 1-헥센을 제조하는 것을 의미한다.“Ethylene oligomerization” described in the present invention is the polymerization of ethylene, and is called trimerization or tetramerization depending on the number of ethylene polymerized. In particular, the present invention refers to producing 1-hexene trimerized with ethylene, which is used as a comonomer of HDPE and LLDPE.
본 발명은 크롬 화합물 및 하기 화학식 1로 표시되는 리간드 화합물을 포함하는 에틸렌 올리고머화 촉매를 제공한다.The present invention provides an ethylene oligomerization catalyst comprising a chromium compound and a ligand compound represented by the following formula (1).
[화학식 1][Formula 1]
[상기 화학식 1에서,[In Formula 1 above,
L1 및 L2는 서로 독립적으로 (C2-C4)알킬렌이고;L 1 and L 2 are independently (C2-C4)alkylene;
R1 내지 R4는 서로 독립적으로 수소, (C1-C10)알킬, (C3-C20)시클로알킬, (C6-C20)아릴, (C6-C20)아릴(C1-C10)알킬 또는 (C1-C10)알콕시이며;R 1 to R 4 are each independently hydrogen, (C1-C10)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, or (C1-C10) ) alkoxy;
상기 R1 내지 R4의 아릴은 (C1-C10)알킬, (C6-C20)아릴, 트리(C1-C10)알킬실릴 및 (C1-C10)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.]The aryl of R 1 to R 4 is one or more substituents selected from the group consisting of (C1-C10)alkyl, (C6-C20)aryl, tri(C1-C10)alkylsilyl, and (C1-C10)alkoxy. May be replaced.]
본 발명의 에틸렌 올리고머화 촉매는 크롬 공급원인 상기 크롬 화합물에 상기 화학식 1의 리간드 화합물이 배위결합된 착물 형태이거나, 상기 크롬 화합물 및 상기 화학식 1의 리간드 화합물을 포함하는 조성물 형태일 수 있다.The ethylene oligomerization catalyst of the present invention may be in the form of a complex in which the ligand compound of Formula 1 is coordinated with the chromium compound, which is a chromium source, or may be in the form of a composition containing the chromium compound and the ligand compound of Formula 1.
일 구체예에 있어, 상기 에틸렌 올리고머화 촉매는 (L)CrX3 (여기서, L은 상기 화학식 1의 리간드 화합물이고, X는 할로겐, C1-C10알킬카보닐옥시, 할로C1-C10알킬카보닐옥시, 아세틸아세토네이트, 피롤라이드, 피라졸라이드, 이미다졸라이드, 1,2,3-트리아졸라이드, 테트라졸라이드 또는 인돌라이드이다)의 구조를 가지는 착물일 수 있다.In one embodiment, the ethylene oligomerization catalyst is (L)CrX 3 (where L is the ligand compound of Formula 1, and , acetylacetonate, pyrrolide, pyrazolide, imidazolide, 1,2,3-triazolide, tetrazolide or indolide).
상기 크롬 화합물은 구체적으로 크롬 3가 화합물일 수 있으며, 예를 들어, 크롬(III) 클로라이드(CrCl3), 크롬(III) 아세테이트(Cr(OAc)3), 크롬(III) 2-에틸헥사노에이트(Cr(EH)3), 크롬(III) 아세틸아세토네이트(Cr(acac)3) 및 크롬(III) 피롤라이드로 이루어진 군으로부터 선택되는 하나 또는 둘 이상일 수 있으나, 이에 한정되는 것은 아니다.The chromium compound may specifically be a chromium trivalent compound, for example, chromium (III) chloride (CrCl 3 ), chromium (III) acetate (Cr(OAc) 3 ), chromium (III) 2-ethylhexano. It may be one or more than one selected from the group consisting of ate (Cr(EH) 3 ), chromium (III) acetylacetonate (Cr(acac) 3 ), and chromium (III) pyrrolide, but is not limited thereto.
본 발명의 에틸렌 올리고머화 촉매는 P-N-S의 구조를 나타내는 특정 리간드를 포함하여 높은 온도에서도 고활성을 나타내고, 폴리머 대비 올리고머에 대한 선택성이 매우 우수하며, 올리고머의 1-헥센에 대한 선택성도 현저하게 향상되어, 우수한 수율 및 선택성으로 1-헥센을 제조할 수 있다.The ethylene oligomerization catalyst of the present invention contains a specific ligand showing the structure of P-N-S, exhibits high activity even at high temperatures, has excellent selectivity for oligomers compared to polymers, and the selectivity of oligomers for 1-hexene is also significantly improved. , 1-hexene can be produced with excellent yield and selectivity.
일 실시예에 따른 상기 화학식 1의 L1 및 L2는 서로 독립적으로 (C2-C3)알킬렌이고; R1 내지 R4는 서로 독립적으로 수소, (C1-C7)알킬, (C3-C12)시클로알킬, (C6-C12)아릴, (C6-C12)아릴(C1-C7)알킬 또는 (C1-C7)알콕시이며; 상기 R1 내지 R4의 아릴은 (C1-C7)알킬, (C6-C12)아릴, 트리(C1-C7)알킬실릴 및 (C1-C7)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.According to one embodiment, L 1 and L 2 of Formula 1 are independently (C2-C3)alkylene; R 1 to R 4 are each independently hydrogen, (C1-C7)alkyl, (C3-C12)cycloalkyl, (C6-C12)aryl, (C6-C12)aryl(C1-C7)alkyl, or (C1-C7) ) alkoxy; The aryl of R 1 to R 4 is one or more substituents selected from the group consisting of (C1-C7)alkyl, (C6-C12)aryl, tri(C1-C7)alkylsilyl, and (C1-C7)alkoxy. can be replaced.
상세하게 상기 화학식 1의 L1 및 L2는 서로 독립적으로 (C2-C3)알킬렌이고; R1 내지 R4는 서로 독립적으로 수소, (C1-C7)알킬, (C6-C12)아릴 또는 (C6-C12)아릴(C1-C7)알킬이며; 상기 R1 내지 R4의 아릴은 (C1-C7)알킬, (C6-C12)아릴, 트리(C1-C7)알킬실릴 및 (C1-C7)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.In detail, L 1 and L 2 of Formula 1 are independently (C2-C3)alkylene; R 1 to R 4 are independently hydrogen, (C1-C7)alkyl, (C6-C12)aryl, or (C6-C12)aryl(C1-C7)alkyl; The aryl of R 1 to R 4 is one or more substituents selected from the group consisting of (C1-C7)alkyl, (C6-C12)aryl, tri(C1-C7)alkylsilyl, and (C1-C7)alkoxy. can be replaced.
보다 상세하게 상기 화학식 1의 L1 및 L2는 서로 독립적으로 (C2-C3)알킬렌이고; R1 내지 R3는 서로 독립적으로 (C1-C5)알킬, (C6-C10)아릴 또는 (C6-C10)아릴(C1-C5)알킬이며; R14는 수소 또는 (C1-C5)알킬이고; 상기 R1 내지 R3의 아릴은 (C1-C5)알킬, (C6-C10)아릴, 트리(C1-C5)알킬실릴 및 (C1-C5)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.In more detail, L 1 and L 2 of Formula 1 are independently (C2-C3)alkylene; R 1 to R 3 are each independently (C1-C5)alkyl, (C6-C10)aryl, or (C6-C10)aryl(C1-C5)alkyl; R 14 is hydrogen or (C1-C5)alkyl; The aryl of R 1 to R 3 is one or more substituents selected from the group consisting of (C1-C5)alkyl, (C6-C10)aryl, tri(C1-C5)alkylsilyl, and (C1-C5)alkoxy. can be replaced.
본 발명의 일 실시예에 따른 리간드 화합물은 하기 화학식 2로 표시되는 것일 수 있다.The ligand compound according to an embodiment of the present invention may be represented by the following formula (2).
[화학식 2][Formula 2]
[상기 화학식 2에서,[In Formula 2 above,
R11 내지 R14는 서로 독립적으로 수소, (C1-C5)알킬, (C6-C10)아릴 또는 (C6-C10)아릴(C1-C5)알킬이며;R 11 to R 14 are independently hydrogen, (C1-C5)alkyl, (C6-C10)aryl, or (C6-C10)aryl(C1-C5)alkyl;
상기 R11 내지 R14의 아릴은 (C1-C5)알킬, 트리(C1-C5)알킬실릴 및 (C1-C5)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.]The aryl of R 11 to R 14 may be substituted with one or more substituents selected from the group consisting of (C1-C5)alkyl, tri(C1-C5)alkylsilyl, and (C1-C5)alkoxy.]
또한 상기 화학식 2의 R11 내지 R13은 서로 독립적으로 (C1-C5)알킬, (C6-C10)아릴 또는 (C6-C10)아릴(C1-C5)알킬이며; R14는 수소 또는 (C1-C3)알킬이고; 상기 R11 내지 R13의 아릴은 (C1-C5)알킬, 트리(C1-C5)알킬실릴 및 (C1-C5)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.In addition, R 11 to R 13 in Formula 2 are independently (C1-C5)alkyl, (C6-C10)aryl, or (C6-C10)aryl(C1-C5)alkyl; R 14 is hydrogen or (C1-C3)alkyl; The aryl of R 11 to R 13 may be substituted with one or more substituents selected from the group consisting of (C1-C5)alkyl, tri(C1-C5)alkylsilyl, and (C1-C5)alkoxy.
본 발명의 일 실시예에 따른 상기 화학식 2의 R11 내지 R13은 서로 독립적으로 (C1-C5)알킬, 페닐 또는 벤질이며; R14는 수소 또는 메틸이고; 상기 R11 내지 R13의 페닐 및 벤질은 서로 독립적으로 (C1-C5)알킬, 트리(C1-C5)알킬실릴 및 (C1-C3)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다In Formula 2 according to an embodiment of the present invention, R 11 to R 13 are each independently (C1-C5)alkyl, phenyl, or benzyl; R 14 is hydrogen or methyl; The phenyl and benzyl of R 11 to R 13 may be each independently substituted with one or more substituents selected from the group consisting of (C1-C5)alkyl, tri(C1-C5)alkylsilyl, and (C1-C3)alkoxy. can
본 발명의 일 실시예에 따른 리간드 화합물은 하기 화학식 3으로 표시되는 것일 수 있다.The ligand compound according to an embodiment of the present invention may be represented by the following formula (3).
[화학식 3][Formula 3]
[상기 화학식 3에서,[In Formula 3 above,
R13은 서로 독립적으로 (C1-C5)알킬, 페닐 또는 벤질이고, 상기 R13의 페닐은 (C1-C5)알킬, 트리(C1-C5)알킬실릴 및 (C1-C3)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있으며; R 13 is independently (C1-C5) alkyl, phenyl or benzyl, and the phenyl of R 13 is selected from the group consisting of (C1-C5) alkyl, tri (C1-C5) alkylsilyl and (C1-C3) alkoxy. may be substituted with one or two or more substituents selected;
R14는 수소 또는 메틸이고; R 14 is hydrogen or methyl;
Ra 및 Rb는 서로 독립적으로 수소, (C1-C5)알킬, 트리(C1-C5)알킬실릴 또는 (C1-C3)알콕시이다.]R a and R b are independently hydrogen, (C1-C5)alkyl, tri(C1-C5)alkylsilyl, or (C1-C3)alkoxy.]
구체적으로 본 발명의 일 실시예에 따른 리간드 화합물은 하기 화합물에서 선택되는 것일 수 있다.Specifically, the ligand compound according to an embodiment of the present invention may be selected from the following compounds.
본 발명은 상기 특정 리간드 화합물의 제조방법을 제공하며, 하기 화학식 1로 표시되는 리간드 화합물은 하기 화학식 11의 화합물 및 화학식 12의 화합물을 반응시켜 제조할 수 있다.The present invention provides a method for producing the specific ligand compound, and the ligand compound represented by the following formula (1) can be prepared by reacting the compound of the formula (11) and the compound of the formula (12).
[화학식 1][Formula 1]
[화학식 11][Formula 11]
[화학식 12][Formula 12]
[상기 화학식 1, 11 및 12에서,[In Formulas 1, 11 and 12,
L1 및 L2는 서로 독립적으로 (C2-C4)알킬렌이고;L 1 and L 2 are independently (C2-C4)alkylene;
R1 내지 R4는 서로 독립적으로 (C1-C10)알킬, (C3-C20)시클로알킬, (C6-C20)아릴, (C6-C20)아릴(C1-C10)알킬 또는 (C1-C10)알콕시이며;R 1 to R 4 are each independently selected from (C1-C10)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, (C6-C20)aryl (C1-C10)alkyl, or (C1-C10)alkoxy. and;
X1는 할로겐이며;X 1 is halogen;
상기 R1 내지 R4의 아릴은 (C1-C10)알킬, (C6-C20)아릴, 트리(C3-C10)알킬실릴 및 (C1-C10)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.]The aryl of R 1 to R 4 is one or more substituents selected from the group consisting of (C1-C10)alkyl, (C6-C20)aryl, tri(C3-C10)alkylsilyl, and (C1-C10)alkoxy. May be replaced.]
또한 상기 화학식 11로 표시되는 화합물은 하기 화학식 13의 화합물 및 화학식 14의 화합물을 반응시켜 제조할 수 있다.Additionally, the compound represented by Formula 11 can be prepared by reacting the compound of Formula 13 and the compound of Formula 14 below.
[화학식 13][Formula 13]
[화학식 14][Formula 14]
[상기 화학식 13 및 14에서, L1, L2, R1, R2 및 R3는 상기 화학식 1에서의 정의와 동일하다.][In Formulas 13 and 14, L 1 , L 2 , R 1 , R 2 and R 3 are the same as defined in Formula 1.]
또한 상기 화학식 13으로 표시되는 화합물은 하기 화학식 15의 화합물 및 화학식 16의 화합물을 반응시켜 제조할 수 있다.Additionally, the compound represented by Formula 13 can be prepared by reacting the compound of Formula 15 and the compound of Formula 16 below.
[화학식 15][Formula 15]
[화학식 16][Formula 16]
[상기 화학식 15 및 16에서, L1, L2, R1 및 R2는 상기 화학식 1에서의 정의와 동일하고;[In Formulas 15 and 16, L 1 , L 2 , R 1 and R 2 are the same as defined in Formula 1;
X2는 할로겐이다.]X 2 is halogen.]
본 발명의 일 실시예에 따른 리간드 화합물의 제조방법은 제조과정에서 치환체가 변경된 원료 화합물을 이용하여 용이하게 다양한 치환기를 가지는 화학적 특성이 상이한 리간드를 확보할 수 있어, 촉매의 활성 조절 및 담지화에 유리할 수 있다.The method for producing a ligand compound according to an embodiment of the present invention can easily secure ligands with various substituents and different chemical properties by using raw material compounds whose substituents have been changed during the production process, thereby helping to control and support the activity of the catalyst. It can be advantageous.
본 발명은 일 실시예에 따른 에틸렌 올리고머화 촉매 및 유기 알루미늄 화합물을 포함하는 에틸렌 올리고머화 촉매 조성물을 제공한다.The present invention provides an ethylene oligomerization catalyst composition including an ethylene oligomerization catalyst and an organic aluminum compound according to an embodiment.
본 발명의 에틸렌 올리고머화 촉매를 채용하는 에틸렌 올리고머화 촉매 조성물은 높은 반응 온도에서도 우수한 촉매 활성과 매우 높은 1-헥센에 대한 선택성을 나타내어 산업적으로 화학원료로 유용한 1-헥센을 효율적으로 생산할 수 있다.The ethylene oligomerization catalyst composition employing the ethylene oligomerization catalyst of the present invention exhibits excellent catalytic activity and very high selectivity for 1-hexene even at high reaction temperatures, and can efficiently produce 1-hexene, which is industrially useful as a chemical raw material.
상기 유기 알루미늄 화합물은 AlR3(여기에서, R은 각각 독립적으로 C1-C12알킬, C6-C20아릴, C2-C10알케닐, C2-C10알키닐, C1-C12알콕시 또는 할로겐이다.)의 화합물일 수 있다. 구체적으로 상기 유기 알루미늄 화합물은 메틸알루미녹산(MAO), 변형 메틸알루미녹산(MMAO), 에틸알루미녹산(EAO), 테트라이소부틸알루미녹산(TIBAO), 이소부틸알루미녹산(IBAO), 트리메틸알루미늄(TMA), 트리에틸알루미늄(TEA), 트리이소부틸알루미늄(TIBA), 트리-n-옥틸알루미늄, 메틸알루미늄 디클로라이드, 에틸알루미늄 디클로라이드, 디메틸알루미늄 클로라이드, 디에틸알루미늄 클로라이드, 알루미늄 이소프로폭사이드, 에틸알루미늄 세스퀴클로라이드 및 메틸알루미늄 세스퀴클로라이드로 이루어진 군으로부터 선택되는 하나 또는 둘 이상일 수 있으나, 이에 한정되는 것은 아니다.The organoaluminum compound is a compound of AlR 3 (wherein R is each independently C1-C12 alkyl, C6-C20 aryl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C12 alkoxy or halogen). You can. Specifically, the organic aluminum compounds include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethyl aluminoxane (EAO), tetraisobutylaluminoxane (TIBAO), isobutylaluminoxane (IBAO), and trimethylaluminoxane (TMA). ), triethyl aluminum (TEA), triisobutyl aluminum (TIBA), tri-n-octyl aluminum, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethyl It may be one or more than one selected from the group consisting of aluminum sesquichloride and methylaluminum sesquichloride, but is not limited thereto.
본 발명의 일 실시예에 있어서, 에틸렌 올리고머화 촉매와 유기 알루미늄 화합물의 비율은 에틸렌 올리고머화 촉매의 크롬 : 유기 알루미늄 화합물의 알루미늄의 몰비로 나타낼 수 있으며, 1 : 1 내지 10,000일 수 있으며, 바람직하게 1 : 1 내지 2,000일 수 있고, 보다 바람직하게 1 : 1 내지 1,000일 수 있다.In one embodiment of the present invention, the ratio of the ethylene oligomerization catalyst and the organoaluminum compound may be expressed as a molar ratio of chromium in the ethylene oligomerization catalyst to aluminum in the organoaluminum compound, and may be 1:1 to 10,000, preferably. It may be 1:1 to 2,000, and more preferably 1:1 to 1,000.
상기 에틸렌 올리고머화 촉매 조성물의 개별 성분들은 용매의 존재 하에 동시에 배합되거나 임의의 순서대로 순차적으로 배합될 수 있다. 상기 배합은 -20 내지 250 ℃에서 수행될 수 있고, 바람직하게 20 내지 160 ℃에서 수행될 수 있다.The individual components of the ethylene oligomerization catalyst composition may be blended simultaneously in the presence of a solvent or sequentially in any order. The mixing may be carried out at -20 to 250°C, preferably at 20 to 160°C.
본 발명의 일 실시예에 따른 에틸렌 올리고머화 촉매 조성물은 촉매활성 및 1-헥센에 대한 선택성이 매우 높고, 촉매의 투입량이 조절될 수 있으며, 나아가 고온에서도 우수한 활성이 계속 유지되어 올레핀 제조공정에서 문제점인 관막힘 및 파울링이 일어나지 않아 매우 경제적이며 효율적이다.The ethylene oligomerization catalyst composition according to an embodiment of the present invention has very high catalytic activity and selectivity for 1-hexene, the amount of catalyst input can be adjusted, and further, excellent activity is maintained even at high temperatures, eliminating problems in the olefin production process. It is very economical and efficient as it does not cause pipe clogging or fouling.
또한 본 발명은 일 실시예에 따른 에틸렌 올리고머화 촉매 조성물을 이용하는 에틸렌 올리고머의 제조방법을 제공한다.Additionally, the present invention provides a method for producing ethylene oligomer using an ethylene oligomerization catalyst composition according to an embodiment.
일 실시예에 따른 에틸렌 올리고머의 제조방법은 상기 올리고머화 촉매 조성물과 통상적인 장치 및 접촉 기술을 이용하여 불활성 용매의 존재 하에서 균질 액상 반응, 2상 액체/액체 반응, 생성물이 주 매질로 작용하는 벌크상 반응 또는 가스상 반응으로 제조될 수 있으나, 바람직하게는 불활성 용매의 존재 하에서 균질 액상 반응일 수 있다.A method for producing ethylene oligomer according to an embodiment includes a homogeneous liquid phase reaction, a two-phase liquid/liquid reaction, and a bulk reaction in which the product acts as the main medium in the presence of an inert solvent using the oligomerization catalyst composition and conventional equipment and contact technology. It may be prepared by a phase reaction or a gas phase reaction, but is preferably a homogeneous liquid phase reaction in the presence of an inert solvent.
상기 에틸렌 올리고머의 제조방법으로 제조된 생성물의 폴리머는 전체 생성물 중 0.001 중량% 이상, 0.01 중량% 이상, 또는 0.1 중량% 이상, 40.0 중량% 이하, 30.0 중량% 이하 또는 20.0 중량% 이하일 수 있으며, 예를 들면, 0.001 내지 30.0 중량%, 구체적으로 0.01 내지 30.0 중량%, 더욱 구체적으로 0.1 내지 20.0 중량%일 수 있다. The polymer of the product prepared by the above ethylene oligomer production method may be 0.001% by weight or more, 0.01% by weight or more, or 0.1% by weight or more, 40.0% by weight or less, 30.0% by weight or less, or 20.0% by weight or less, e.g. For example, it may be 0.001 to 30.0% by weight, specifically 0.01 to 30.0% by weight, and more specifically 0.1 to 20.0% by weight.
상기 에틸렌 올리고머의 제조방법으로 제조된 생성물의 올리고머는 전체 생성물 중 60.0 중량% 이상, 70.0 중량% 이상 또는 80.0 중량% 이상, 99.999 중량% 이하, 99.99 중량% 이하 또는 99.9 중량% 이하일 수 있으며, 예를 들면, 70.0 내지 99.999 중량%, 구체적으로 70.0 내지 99.99 중량%, 더욱 구체적으로 80.0 내지 99.9 중량%일 수 있다.The oligomer of the product prepared by the above ethylene oligomer production method may be 60.0% by weight or more, 70.0% by weight or more, 80.0% by weight or more, 99.999% by weight or less, 99.99% by weight or less, or 99.9% by weight or less, for example For example, it may be 70.0 to 99.999% by weight, specifically 70.0 to 99.99% by weight, and more specifically 80.0 to 99.9% by weight.
또한 상기 제조방법은 올리고머 전체 중 1-헥센이 60.0 중량% 이상, 70.0 중량% 이상, 80.0 중량% 이상 또는 90.0 중량% 이상, 99.999 중량% 이하, 99.99 중량% 이하 또는 99.9 중량% 이하일 수 있으며, 예를 들면, 60.0 내지 99.999 중량%, 구체적으로 65.0 내지 99.99 중량%, 더욱 구체적으로 70.0 내지 99.9 중량%, 더욱더 구체적으로 80 내지 99.9 중량%일 수 있다.In addition, in the above production method, 1-hexene may be 60.0% by weight or more, 70.0% by weight, 80.0% by weight or more, 90.0% by weight or more, 99.999% by weight or less, 99.99% by weight or less, or 99.9% by weight or less, e.g. For example, it may be 60.0 to 99.999% by weight, specifically 65.0 to 99.99% by weight, more specifically 70.0 to 99.9% by weight, and even more specifically 80 to 99.9% by weight.
본 발명의 촉매 조성물을 이용한 에틸렌 올리고머의 제조방법은 높은 온도에서도 놀랍도록 우수한 올리고머에 대한 선택성 및 1-헥센에 대한 선택성을 나타내어, 산업적으로 유용한 화학원료인 1-헥센을 높은 순도로 대량생산할 수 있다.The method for producing ethylene oligomer using the catalyst composition of the present invention exhibits surprisingly excellent selectivity for oligomers and selectivity for 1-hexene even at high temperatures, enabling mass production of 1-hexene, an industrially useful chemical raw material, with high purity. .
또한 일 실시예에 있어서, 상기 에틸렌 올리고머의 제조방법은 벤젠, 글로로벤젠, 에틸벤젠, 톨루엔, 자일렌, 큐멘, 메시틸렌 등과 같은 방향족 탄화수소; 시클로헥산, 메틸시클로헥산, 메틸시클로펜탄 등과 같은 환형 지방족 탄화수소; 헥산, 헵탄, 옥탄, 노난, 데칸 등과 같은 지방족 탄화수소; 헥센, 헵텐, 옥텐, 노넨, 데센 등과 같은 올레핀류; 및 애니솔, 에톡시벤젠, 디메톡시벤젠 등과 같은 방향족 에테르;로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 용매에서 수행되는 것일 수 있다. 구체적으로 톨루엔, 자일렌, 노난, 헥산 또는 이들의 혼합물일 수 있으며, 보다 구체적으로 톨루엔, 노난 또는 이들의 혼합물일 수 있다.In addition, in one embodiment, the method for producing the ethylene oligomer includes aromatic hydrocarbons such as benzene, glorobenzene, ethylbenzene, toluene, xylene, cumene, mesitylene, etc.; Cyclic aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclopentane, etc.; aliphatic hydrocarbons such as hexane, heptane, octane, nonane, decane, etc.; olefins such as hexene, heptene, octene, nonene, decene, etc.; and aromatic ethers such as anisole, ethoxybenzene, dimethoxybenzene, etc.; and may be performed in one or more solvents selected from the group consisting of. Specifically, it may be toluene, xylene, nonane, hexane, or a mixture thereof, and more specifically, it may be toluene, nonane, or a mixture thereof.
본 발명의 일 실시예에 따른 올리고머화 반응은 -20 내지 250 ℃에서 수행될 수 있고, 바람직하게 20 내지 160 ℃, 보다 바람직하게 60 내지 120 ℃에서 수행될 수 있다.The oligomerization reaction according to an embodiment of the present invention may be performed at -20 to 250 °C, preferably 20 to 160 °C, and more preferably 60 to 120 °C.
또한 상기 올리고머화 반응은 1 내지 100 bar의 압력에서 수행될 수 있고, 바람직하게 5 내지 70 bar에서, 보다 바람직하게 10 내지 40 bar의 압력에서 수행될 수 있다.Additionally, the oligomerization reaction may be performed at a pressure of 1 to 100 bar, preferably at a pressure of 5 to 70 bar, and more preferably at a pressure of 10 to 40 bar.
본 발명의 일 실시에에 따른 에틸렌 올리고머의 제조방법은 임의 유형의 반응기를 포함하는 플랜트에서 수행될 수 있다. 상기 반응기는 예를 들어 배치식, 반배치식 및 연속식이 가능하나, 이에 한정되는 것은 아니다. 상기 플랜트에는 반응기, 상기 반응기 내부에 올레핀 반응기 및 올리고머화 촉매 조성물의 주입구, 상기 반응기로부터 올리고머화 반응 생성물의 유출을 위한 라인 및 올리고머화 반응 생성물을 분리하기 위한 하나 또는 둘 이상의 분리기가 조합되어 포함될 수 있다.The method for producing ethylene oligomer according to one embodiment of the present invention can be performed in a plant including any type of reactor. The reactor may be, for example, a batch type, a semi-batch type, and a continuous type, but is not limited thereto. The plant may include a combination of a reactor, an olefin reactor inside the reactor and an inlet of the oligomerization catalyst composition, a line for discharging the oligomerization reaction product from the reactor, and one or more separators for separating the oligomerization reaction product. there is.
이하, 구체적인 실시예를 통해 본 발명에 따른 리간드 화합물을 포함하는 에틸렌 올리고머화 촉매, 이를 채용한 촉매 조성물 및 이를 이용한 에틸렌 올리고머의 제조방법에 대하여 더욱 상세히 설명한다.Hereinafter, the ethylene oligomerization catalyst containing the ligand compound according to the present invention, the catalyst composition employing the same, and the method for producing ethylene oligomer using the same will be described in more detail through specific examples.
[제조예 A] 화합물 A의 제조[Preparation Example A] Preparation of Compound A
질소분위기 하에서 건조된 플라스크에 화합물 A-2(3.82 mL, 22 mmol) 및 건조된 THF 20 mL을 넣고, 5 ℃로 냉각시킨 뒤, 2.5 M n-BuLi in Hex(8.8 ml, 22 mmol)을 천천히 첨가하였다. 상온에서 20 분 동안 교반시킨 뒤 -78 ℃로 냉각시킨다. 화합물 A-1(3.0 g, 20 mmol) 및 건조된 THF 30 mL를 -78 ℃에서 혼합하고, 혼합된 용액을 1 시간 동안 천천히 첨가하였다. 상온에서 Toluene 100 mL 및 물 25 mL을 첨가한 뒤, 감압증류하였다. 유기층을 수세하고 MgSO4로 수분을 제거하고, 2-메틸-2-부탄올로 재결정 한 뒤, 진공건조하여 화합물 A를 얻었다(수율 51 %).Add Compound A-2 (3.82 mL, 22 mmol) and 20 mL of dried THF to a flask dried under a nitrogen atmosphere, cool to 5°C, and then slowly add 2.5 M n-BuLi in Hex (8.8 ml, 22 mmol). Added. Stir at room temperature for 20 minutes and then cool to -78°C. Compound A-1 (3.0 g, 20 mmol) and 30 mL of dried THF were mixed at -78°C, and the mixed solution was slowly added over 1 hour. 100 mL of toluene and 25 mL of water were added at room temperature, and then distilled under reduced pressure. The organic layer was washed with water, moisture was removed with MgSO 4 , recrystallized with 2-methyl-2-butanol, and dried in vacuum to obtain Compound A (yield 51%).
1H NMR (CDCl3, 500 MHz) δ 7.50 - 7.28 (m, 10H), 4.23 - 4.19 (m, 2H), 3.56 - 3.43 (m, 4H), 2.39 - 2.35 (m, 2H) 1 H NMR (CDCl 3 , 500 MHz) δ 7.50 - 7.28 (m, 10H), 4.23 - 4.19 (m, 2H), 3.56 - 3.43 (m, 4H), 2.39 - 2.35 (m, 2H)
[제조예 B] 화합물 B의 제조[Preparation Example B] Preparation of Compound B
상기 제조예 A에서 화합물 A-2를 대신하여 화합물 B-1을 사용한 것을 제외하고 제조예 A와 동일하게 실시하여 화합물 B를 얻었다(수율 54 %).Compound B was obtained in the same manner as Preparation Example A, except that Compound B-1 was used instead of Compound A-2 (yield 54%).
1H NMR (CDCl3, 500 MHz) δ 7.38 - 7.34 (m, 4H), 6.88 (d, 4H, J = 7.8 Hz), 4.18 (t, 2H, J = 8.0 Hz), 3.79 (s, 6H), 3.50 (t, 2H, J = 8.2 Hz), 3.41 - 3.36 (m, 2H), 2.26 (t, 2H, J = 7.6 Hz) 1H NMR (CDCl 3 , 500 MHz) δ 7.38 - 7.34 (m, 4H), 6.88 (d, 4H, J = 7.8 Hz), 4.18 (t, 2H, J = 8.0 Hz), 3.79 (s, 6H) , 3.50 (t, 2H, J = 8.2 Hz), 3.41 - 3.36 (m, 2H), 2.26 (t, 2H, J = 7.6 Hz)
[제조예 C] 화합물 C의 제조[Preparation Example C] Preparation of Compound C
상기 제조예 A에서 화합물 A-2를 대신하여 화합물 C-1을 사용한 것을 제외하고 제조예 A와 동일하게 실시하여 화합물 C를 얻었다(수율 41 %).Compound C was obtained in the same manner as Preparation Example A, except that Compound C-1 was used instead of Compound A-2 (yield 41%).
1H NMR (CDCl3, 500 MHz) δ 7.34 - 7.31 (m, 4H), 7.16 (d, 4H, J = 7.6 Hz), 4.18 (t, 2H, J = 8.1 Hz), 3.51 (t, 2H, J = 7.8 Hz), 3.43 - 3.38 (m, 2H), 2.34 (s, 6H), 2.30 (t, 2H, J = 7.4 Hz) 1H NMR (CDCl 3 , 500 MHz) δ 7.34 - 7.31 (m, 4H), 7.16 (d, 4H, J = 7.6 Hz), 4.18 (t, 2H, J = 8.1 Hz), 3.51 (t, 2H, J = 7.8 Hz), 3.43 - 3.38 (m, 2H), 2.34 (s, 6H), 2.30 (t, 2H, J = 7.4 Hz)
[제조예 1] 리간드 화합물 1의 제조[Preparation Example 1] Preparation of Ligand Compound 1
플라스크에 화합물 A(제조예 A(2.99 g, 10 mmol)), NaS-Me(0.70 g, 10 mmol), Et3N (1.39 mL, 10 mmol) 및 2-메틸-2-부탄올 20 mL을 넣고 3 시간 동안 환류시켰다. 반응물을 감압증류한 뒤, 컬럼 정제하여 리간드 화합물 1을 얻었다(수율 67 %).Add Compound A (Preparation A (2.99 g, 10 mmol)), NaS-Me (0.70 g, 10 mmol), Et 3 N (1.39 mL, 10 mmol), and 20 mL of 2-methyl-2-butanol to the flask. Refluxed for 3 hours. The reaction product was distilled under reduced pressure and purified by column to obtain Ligand Compound 1 (yield 67%).
1H NMR (CDCl3, 500 MHz) δ 7.45 - 7.41 (m, 4H), 7.34 - 7.32 (m, 6H), 2.80 - 2.74 (m, 4H), 2.61 (t, 2H, J = 6.6 Hz), 2.28 (t, 2H, J = 7.5 Hz), 2.08 (s, 3H), 1.57 (br, 1H) 1 H NMR (CDCl 3 , 500 MHz) δ 7.45 - 7.41 (m, 4H), 7.34 - 7.32 (m, 6H), 2.80 - 2.74 (m, 4H), 2.61 (t, 2H, J = 6.6 Hz), 2.28 (t, 2H, J = 7.5 Hz), 2.08 (s, 3H), 1.57 (br, 1H)
[제조예 2] 리간드 화합물 2[Preparation Example 2] Ligand Compound 2
상기 리간드 화합물 2는 Strem사로부터 구매하여 사용하였다.The Ligand Compound 2 was purchased and used from Strem.
[제조예 3] 리간드 화합물 3[Preparation Example 3] Ligand Compound 3
상기 리간드 화합물 3은 Strem사로부터 구매하여 사용하였다.The Ligand Compound 3 was purchased and used from Strem.
[제조예 4] 리간드 화합물 4[Preparation Example 4] Ligand Compound 4
상기 리간드 화합물 4는 Strem사로부터 구매하여 사용하였다.The ligand compound 4 was purchased and used from Strem.
[제조예 5] 리간드 화합물 5의 제조[Preparation Example 5] Preparation of Ligand Compound 5
상기 제조예 1에서 화합물 A(제조예 A)를 대신하여 화합물 B(제조예 B)를 사용한 것을 제외하고 제조예 1과 동일하게 실시하여 리간드 화합물 5를 얻었다(수율 17 %).Ligand Compound 5 was obtained in the same manner as Preparation Example 1, except that Compound B (Preparation Example B) was used instead of Compound A (Preparation Example A) in Preparation Example 1 (yield 17%).
1H NMR (CDCl3, 500 MHz) δ 7.37 - 7.34 (m, 4H), 6.87 (d, 4H, J = 8.9 Hz), 3.80 (s, 6H), 2.79 (t, 2H, J = 6.5 Hz), 2.77-2.72 (m, 2H), 2.61 (t, 2H, 6.6 Hz), 2.21 (t, 2H, 7.2 Hz), 2.01 (s, 3H), 1.72 (br, 1H) 1 H NMR (CDCl 3 , 500 MHz) δ 7.37 - 7.34 (m, 4H), 6.87 (d, 4H, J = 8.9 Hz), 3.80 (s, 6H), 2.79 (t, 2H, J = 6.5 Hz) , 2.77-2.72 (m, 2H), 2.61 (t, 2H, 6.6 Hz), 2.21 (t, 2H, 7.2 Hz), 2.01 (s, 3H), 1.72 (br, 1H)
[제조예 6] 리간드 화합물 6의 제조[Preparation Example 6] Preparation of Ligand Compound 6
상기 제조예 1에서 화합물 A(제조예 A)를 대신하여 화합물 C(제조예 C)를 사용한 것을 제외하고 제조예 1과 동일하게 실시하여 리간드 화합물 6을 얻었다(수율 32 %).Ligand Compound 6 was obtained in the same manner as Preparation Example 1, except that Compound C (Preparation Example C) was used instead of Compound A (Preparation Example A) in Preparation Example 1 (yield 32%).
1H NMR (CDCl3, 500 MHz) δ 7.32 (t, 4H, J = 7.6 Hz), 7.14 (d, 4H, J = 7.6 Hz), 2.81-2.74 (m, 4H), 2.62 (t, 2H, J = 6.6 Hz), 2.33 (s, 6H), 2.26 (t, 2H, 7.4 Hz), 2.17 (br, 1H), 2.07 (s, 3H) 1H NMR (CDCl 3 , 500 MHz) δ 7.32 (t, 4H, J = 7.6 Hz), 7.14 (d, 4H, J = 7.6 Hz), 2.81-2.74 (m, 4H), 2.62 (t, 2H, J = 6.6 Hz), 2.33 (s, 6H), 2.26 (t, 2H, 7.4 Hz), 2.17 (br, 1H), 2.07 (s, 3H)
[제조예 7] 리간드 화합물 7의 제조[Preparation Example 7] Preparation of Ligand Compound 7
플라스크에 리간드 화합물 1(제조예 1(151 mg, 0.5 mmol)), HCHO(30 mg, 1.0 mmol)을 dichloromethane 1.2 mL에 용해시킨 뒤, 15 분 동안 교반시켰다. NaBH(OAc)3 (212 mg, 1.0 mmol)을 서서히 넣고 24 시간 동안 환류시켰다. 반응물을 감압증류한 뒤, 컬럼 정제하여 리간드 화합물 7을 얻었다(수율 48 %).Ligand Compound 1 (Preparation Example 1 (151 mg, 0.5 mmol)) and HCHO (30 mg, 1.0 mmol) were dissolved in 1.2 mL of dichloromethane in a flask and stirred for 15 minutes. NaBH(OAc) 3 (212 mg, 1.0 mmol) was slowly added and refluxed for 24 hours. The reaction product was distilled under reduced pressure and purified by column to obtain Ligand Compound 7 (yield 48%).
1H NMR (CDCl3, 500 MHz) δ 7.45 - 7.41 (m, 4H), 7.35 - 7.31 (m, 6H), 2.80 - 2.60 - 2.50 (m, 6H), 2.27 (s, 3H), 2.26-2.22 (m, 2H), 2.09 (s, 3H) 1 H NMR (CDCl 3 , 500 MHz) δ 7.45 - 7.41 (m, 4H), 7.35 - 7.31 (m, 6H), 2.80 - 2.60 - 2.50 (m, 6H), 2.27 (s, 3H), 2.26-2.22 (m, 2H), 2.09 (s, 3H)
[비교제조예 1] 리간드 화합물 8의 제조[Comparative Preparation Example 1] Preparation of Ligand Compound 8
상기 리간드 화합물 8은 공지된 문헌(Organometallics 2001, 20, 4769-4771)을 참고하여 제조하였다.The ligand compound 8 was prepared with reference to a known document (Organometallics 2001, 20, 4769-4771).
[실시예 1] 올리고머화 촉매 1의 제조[Example 1] Preparation of oligomerization catalyst 1
크롬(III) 아세틸아세토네이트(Cr(acac)3) (175 mg, 0.52 mmol)와 리간드 화합물 1(제조예 1) 1.04 equiv.를 Toluene 5 mL에 용해시킨 뒤, 20 분 동안 교반시켰다. 0.45 μm 실린지 필터를 이용하여 여과된 액체를 진공건조시킨 뒤, 고체를 수득하였으며, 진공건조시켜 고체를 얻었다(수율 85%)Chromium (III) acetylacetonate (Cr(acac) 3 ) (175 mg, 0.52 mmol) and 1.04 equiv. of Ligand Compound 1 (Preparation Example 1) were dissolved in 5 mL of Toluene and stirred for 20 minutes. The filtered liquid was vacuum dried using a 0.45 μm syringe filter, and then a solid was obtained, which was then vacuum dried to obtain a solid (yield 85%).
1H NMR (C6D6, 500 MHz) δ 3.58 (br), 1.41 (br) 1H NMR (C 6 D 6 , 500 MHz) δ 3.58 (br), 1.41 (br)
[실시예 2] 올리고머화 촉매 2의 제조[Example 2] Preparation of oligomerization catalyst 2
크롬(III) 클로라이드 테트라하이드로퓨란(CrCl3(THF)3) (276 mg, 0.52 mmol)과 리간드 화합물 1(제조예 1) 1.04 equiv.를 Tetrahydrofuran 5 mL에 용해시킨 뒤, 20 분 동안 교반시켰다. 형성된 침전물을 필터를 이용하여 여과하고, diethyl ether로 세척한 고체를 진공건조시켜 얻었다(수율 99%)Chromium (III) chloride tetrahydrofuran (CrCl 3 (THF) 3 ) (276 mg, 0.52 mmol) and 1.04 equiv. of Ligand Compound 1 (Preparation Example 1) were dissolved in 5 mL of Tetrahydrofuran and stirred for 20 minutes. The formed precipitate was filtered using a filter, and the solid was washed with diethyl ether and vacuum dried (yield 99%).
1H NMR (DMSO, 500 MHz) δ 8.84 (br), 5.06 (br), 3.97 (br), 2.07 (br) 1 H NMR (DMSO, 500 MHz) δ 8.84 (br), 5.06 (br), 3.97 (br), 2.07 (br)
[실시예 3][Example 3]
크롬(III) 아세틸아세토네이트(Cr(acac)3) (6.99 mg, 20 μmol)와 리간드 화합물 1(제조예 1) 1.2 equiv.를 toluene 4.12 mL에 용해시킨 뒤, 10 분 동안 교반시켰다.Chromium (III) acetylacetonate (Cr(acac) 3 ) (6.99 mg, 20 μmol) and 1.2 equiv. of Ligand Compound 1 (Preparation Example 1) were dissolved in 4.12 mL of toluene and stirred for 10 minutes.
글로브박스에서 상기 교반시킨 분산 혼합액을 질소 및 진공으로 세척한 20 mL 오토클레이브 반응기에 투입하였다. MMAO-12(10% in Toluene, Aldrich) 0.86 mL(2 mmol, 크롬 촉매의 100 equiv.), nonane 20 μL을 첨가한 뒤 800 rpm으로 교반시켰다. 상기 오토클레이브 반응기 내의 온도를 50 ℃로 승온시킨 후 에틸렌을 20 bar로 충진하여 30 분 동안 올리고머화 반응을 수행하였다. 반응 종료 후, 반응기 내의 과량의 에틸렌을 배출시킨 뒤, 반응기를 10 ℃이하로 냉각시키고 메탄올 2.5 mL이 담긴 배출용기로 반응물을 배출하여 소량의 유기층 샘플을 GC-FID로 분석하였다. 나머지 유기층을 여과하여 고체 왁스 및 폴리머 생성물을 분리하였다. 고체 생성물을 오븐건조하여 중량을 측정하였다. GC분석한 실시예 3의 생성물을 표 2에 나타내었다.The stirred dispersion mixture in the glove box was introduced into a 20 mL autoclave reactor cleaned with nitrogen and vacuum. 0.86 mL (2 mmol, 100 equiv. of chromium catalyst) of MMAO-12 (10% in Toluene, Aldrich) and 20 μL of nonane were added and stirred at 800 rpm. The temperature in the autoclave reactor was raised to 50°C, and then ethylene was charged at 20 bar to perform an oligomerization reaction for 30 minutes. After completion of the reaction, excess ethylene in the reactor was discharged, the reactor was cooled to below 10°C, the reactant was discharged into a discharge container containing 2.5 mL of methanol, and a small amount of the organic layer sample was analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax and polymer product. The solid product was oven dried and its weight was measured. The product of Example 3 analyzed by GC is shown in Table 2.
[실시예 4 내지 10][Examples 4 to 10]
하기 표 1에 나타낸 조건으로, 온도, 압력, 촉매의 몰수 및 촉매에 대한 MMAO 당량을 다르게 한 것을 제외하고는 상기 실시예 3과 동일하게 실시하여 실시예 4 내지 10의 생성물의 GC분석한 결과를 표 2에 나타내었다.Under the conditions shown in Table 1 below, the results of GC analysis of the products of Examples 4 to 10 were conducted in the same manner as Example 3, except that the temperature, pressure, number of moles of catalyst, and MMAO equivalent to the catalyst were different. It is shown in Table 2.
(μmol)Cr(acac) 3
(μmol)
(bar)Pressure
(bar)
(℃)Temperature
(℃)
for oligomersActivity(g/g-Cr/h)
for oligomers
상기 표 2에 나타낸 바와 같이, 리간드 화합물 1(제조예 1)을 채용한 에틸렌의 올리고머화는 1-헥센에 대한 우수한 선택성을 나타내는 것을 알 수 있으며, 100 ℃의 고온에서도 촉매의 활성이 매우 높은 것을 확인할 수 있다. 상기 실시예 3 내지 10 중에서 적은 양의 크롬 화합물을 이용하면서도 촉매 활성이 매우 우수하였던 실시예 7의 조건을 채택하여 리간드 화합물의 변화에 따른 올리고머화의 촉매활성, 올리고머에 대한 선택성 및 1-헥센에 대한 선택성을 하기 실시예에서 확인하였다.As shown in Table 2, it can be seen that the oligomerization of ethylene using Ligand Compound 1 (Preparation Example 1) shows excellent selectivity for 1-hexene, and the catalyst activity is very high even at a high temperature of 100 ° C. You can check it. Among Examples 3 to 10, the conditions of Example 7, in which the catalytic activity was very excellent even though a small amount of chromium compound was used, were adopted to determine the catalytic activity of oligomerization, selectivity to oligomers, and 1-hexene according to changes in the ligand compound. Selectivity was confirmed in the examples below.
[실시예 11][Example 11]
크롬(III) 아세틸아세토네이트(Cr(acac)3) (0.7 mg, 2 μmol)와 리간드 화합물 1(제조예 1) 1.2 equiv.를 toluene 4.12 mL에 용해시킨 뒤, 10 분 동안 교반시켰다.Chromium (III) acetylacetonate (Cr(acac) 3 ) (0.7 mg, 2 μmol) and 1.2 equiv. of Ligand Compound 1 (Preparation Example 1) were dissolved in 4.12 mL of toluene and stirred for 10 minutes.
글로브박스에서 상기 교반시킨 분산 혼합액을 질소 및 진공으로 세척한 20 mL 오토클레이브 반응기에 투입하였다. MMAO-12(10% in Toluene, Aldrich) 0.86 mL(2 mmol, 크롬 촉매의 100 equiv.), nonane 20 μL을 첨가한 뒤 800 rpm으로 교반시켰다. 상기 오토클레이브 반응기 내의 온도를 100 ℃로 승온시킨 후 에틸렌을 20 bar로 충진하여 30 분 동안 올리고머화 반응을 수행하였다. 반응 종료 후, 반응기 내의 과량의 에틸렌을 배출시킨 뒤, 반응기를 10 ℃이하로 냉각시키고 메탄올 2.5 mL이 담긴 배출용기로 반응물을 배출하여 소량의 유기층 샘플을 GC-FID로 분석하였다. 나머지 유기층을 여과하여 고체 왁스 및 폴리머 생성물을 분리하였다. 고체 생성물을 오븐건조하여 중량을 측정하였다. GC분석한 실시예 11의 생성물의 결과를 표 3에 나타내었다.The stirred dispersion mixture in the glove box was introduced into a 20 mL autoclave reactor cleaned with nitrogen and vacuum. 0.86 mL (2 mmol, 100 equiv. of chromium catalyst) of MMAO-12 (10% in Toluene, Aldrich) and 20 μL of nonane were added and stirred at 800 rpm. The temperature in the autoclave reactor was raised to 100°C, and then ethylene was charged at 20 bar to perform an oligomerization reaction for 30 minutes. After completion of the reaction, excess ethylene in the reactor was discharged, the reactor was cooled to below 10°C, the reactant was discharged into a discharge container containing 2.5 mL of methanol, and a small amount of the organic layer sample was analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax and polymer product. The solid product was oven dried and its weight was measured. The results of GC analysis of the product of Example 11 are shown in Table 3.
[실시예 12 내지 17][Examples 12 to 17]
상기 실시예 11에서 리간드 화합물 1(제조예 1)을 사용하는 대신 리간드 화합물 2 내지 6(제조예 2 내지 6)을 각각 사용한 것을 제외하고는 상기 실시예 11과 동일하게 실시하여 실시예 12 내지 17의 생성물의 GC분석한 결과를 표 3에 나타내었다.Examples 12 to 17 were carried out in the same manner as Example 11, except that Ligand Compounds 2 to 6 (Preparation Examples 2 to 6) were used instead of Ligand Compound 1 (Preparation Example 1). The results of GC analysis of the product are shown in Table 3.
[실시예 18][Example 18]
상기 실시예 1(올리고머화 촉매 1) (1.2 mg, 2 μmol)를 toluene 4.12 mL에 용해시킨 뒤, 10 분 동안 교반시켰다.Example 1 (oligomerization catalyst 1) (1.2 mg, 2 μmol) was dissolved in 4.12 mL of toluene and stirred for 10 minutes.
글로브박스에서 상기 교반시킨 분산 혼합액을 질소 및 진공으로 세척한 20 mL 오토클레이브 반응기에 투입하였다. MMAO-12(10% in Toluene, Aldrich) 0.86 mL(2 mmol, 크롬 촉매의 100 equiv.), nonane 20 μL을 첨가한 뒤 800 rpm으로 교반시켰다. 상기 오토클레이브 반응기 내의 온도를 100 ℃로 승온시킨 후 에틸렌을 20 bar로 충진하여 30 분 동안 올리고머화 반응을 수행하였다. 반응 종료 후, 반응기 내의 과량의 에틸렌을 배출시킨 뒤, 반응기를 10 ℃이하로 냉각시키고 메탄올 2.5 mL이 담긴 배출용기로 반응물을 배출하여 소량의 유기층 샘플을 GC-FID로 분석하였다. 나머지 유기층을 여과하여 고체 왁스 및 폴리머 생성물을 분리하였다. 고체 생성물을 오븐건조하여 중량을 측정하였다. GC분석한 실시예 18의 생성물의 결과를 표 3에 나타내었다.The stirred dispersion mixture in the glove box was introduced into a 20 mL autoclave reactor cleaned with nitrogen and vacuum. 0.86 mL (2 mmol, 100 equiv. of chromium catalyst) of MMAO-12 (10% in Toluene, Aldrich) and 20 μL of nonane were added and stirred at 800 rpm. The temperature in the autoclave reactor was raised to 100°C, and then ethylene was charged at 20 bar to perform an oligomerization reaction for 30 minutes. After completion of the reaction, excess ethylene in the reactor was discharged, the reactor was cooled to below 10°C, the reactant was discharged into a discharge container containing 2.5 mL of methanol, and a small amount of the organic layer sample was analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax and polymer product. The solid product was oven dried and its weight was measured. The results of GC analysis of the product of Example 18 are shown in Table 3.
[실시예 19][Example 19]
상기 실시예 2(올리고머화 촉매 2) (0.9 mg, 2 μmol)를 toluene 4.12 mL에 용해시킨 뒤, 10 분 동안 교반시켰다.Example 2 (oligomerization catalyst 2) (0.9 mg, 2 μmol) was dissolved in 4.12 mL of toluene and stirred for 10 minutes.
글로브박스에서 상기 교반시킨 분산 혼합액을 질소 및 진공으로 세척한 20 mL 오토클레이브 반응기에 투입하였다. MMAO-12(10% in Toluene, Aldrich) 0.86 mL(2 mmol, 크롬 촉매의 100 equiv.), nonane 20 μL을 첨가한 뒤 800 rpm으로 교반시켰다. 상기 오토클레이브 반응기 내의 온도를 100 ℃로 승온시킨 후 에틸렌을 20 bar로 충진하여 30 분 동안 올리고머화 반응을 수행하였다. 반응 종료 후, 반응기 내의 과량의 에틸렌을 배출시킨 뒤, 반응기를 10 ℃이하로 냉각시키고 메탄올 2.5 mL이 담긴 배출용기로 반응물을 배출하여 소량의 유기층 샘플을 GC-FID로 분석하였다. 나머지 유기층을 여과하여 고체 왁스 및 폴리머 생성물을 분리하였다. 고체 생성물을 오븐건조하여 중량을 측정하였다. GC분석한 실시예 19의 생성물의 결과를 표 3에 나타내었다.The stirred dispersion mixture in the glove box was introduced into a 20 mL autoclave reactor cleaned with nitrogen and vacuum. 0.86 mL (2 mmol, 100 equiv. of chromium catalyst) of MMAO-12 (10% in Toluene, Aldrich) and 20 μL of nonane were added and stirred at 800 rpm. The temperature in the autoclave reactor was raised to 100°C, and then ethylene was charged at 20 bar to perform an oligomerization reaction for 30 minutes. After completion of the reaction, excess ethylene in the reactor was discharged, the reactor was cooled to below 10°C, the reactant was discharged into a discharge container containing 2.5 mL of methanol, and a small amount of the organic layer sample was analyzed by GC-FID. The remaining organic layer was filtered to separate the solid wax and polymer product. The solid product was oven dried and its weight was measured. The results of GC analysis of the product of Example 19 are shown in Table 3.
[비교예 1][Comparative Example 1]
상기 실시예 11에서 리간드 화합물 1(제조예 1)을 사용하는 대신 리간드 화합물 8(비교제조예 1)을 사용한 것을 제외하고는 상기 실시예 11과 동일하게 실시하여 생성물의 GC분석한 결과를 표 3에 나타내었다.Table 3 shows the results of GC analysis of the product in the same manner as in Example 11, except that Ligand Compound 8 (Comparative Preparation Example 1) was used instead of Ligand Compound 1 (Preparation Example 1) in Example 11. shown in
화합물chrome
compound
화합물Ligand
compound
(g/g-Cr/h)
for oligomersActivity
(g/g-Cr/h)
for oligomers
(올리고머화 촉매 1)Example 1
(Oligomerization catalyst 1)
(올리고머화 촉매 2)Example 2
(Oligomerization catalyst 2)
상기 표 3에 나타낸 바와 같이, 본 발명의 리간드 화합물 1 내지 7을 이용한 실시예 11 내지 17에서 올리고머에 대한 선택성이 70 % 이상으로, 기존 사용되고 있는 리간드 화합물 8을 이용한 비교예 1의 올리고머 선택성 14.8 %와 비교하여 본 발명의 실시예에서 현저하게 우수한 선택성을 나타내는 것을 알 수 있으며, 특히 실시예 11 및 16은 올리고머에 대한 선택성이 98 % 이상으로 매우 우수한 선택성을 나타내는 것을 알 수 있다.As shown in Table 3, the selectivity for oligomers in Examples 11 to 17 using Ligand Compounds 1 to 7 of the present invention was more than 70%, and the oligomer selectivity of Comparative Example 1 using Ligand Compound 8, which was previously used, was 14.8%. Compared to , it can be seen that the examples of the present invention exhibit significantly superior selectivity, and in particular, examples 11 and 16 exhibit very excellent selectivity for oligomers of over 98%.
또한 본 발명의 실시예는 1-헥센에 대한 선택성이 우수하였으며, 특히 실시예 11, 12, 15, 16, 17 및 19는 1-헥센에 대한 선택성이 놀랍도록 향상된 90 % 이상으로 확인되어, 본 발명의 리간드 화합물을 포함하는 올리고머화 촉매 및 촉매 조성물은 1-헥센 제조에 있어 매우 효율적인 것을 확인 할 수 있다.In addition, the examples of the present invention had excellent selectivity for 1-hexene, and in particular, Examples 11, 12, 15, 16, 17, and 19 were confirmed to have surprisingly improved selectivity for 1-hexene of more than 90%. It can be confirmed that the oligomerization catalyst and catalyst composition containing the ligand compound of the invention are very efficient in producing 1-hexene.
본 발명의 올리고머화 촉매는 높은 온도에서도 촉매활성과 선택성이 유지되며, 부산물의 생성이 적어 관막힘 및 파울링에 대한 문제가 없고, 이를 제거하기 위한 중합공정의 운전중단이 필요치 않아 매우 경제적이다. 나아가, 본 발명의 올리고머화 촉매는 높은 온도에서도 촉매의 활성이 매우 우수하여 소량의 촉매 및 소량의 유기 알루미늄 화합물 만으로도 올리고머를 제조할 수 있으며, 고온에서도 활성이 저하되지 않으며 선택성도 우수하여 에틸렌으로부터 1-헥센을 놀랍도록 우수한 선택성으로 제조할 수 있다.The oligomerization catalyst of the present invention maintains catalytic activity and selectivity even at high temperatures, has no problems with tube clogging and fouling due to low production of by-products, and is very economical because it does not require interruption of the polymerization process to remove them. Furthermore, the oligomerization catalyst of the present invention has excellent catalytic activity even at high temperatures, allowing oligomers to be produced with only a small amount of catalyst and a small amount of organoaluminum compounds. The activity does not decrease even at high temperatures and the selectivity is excellent, so that 1 -Hexene can be produced with surprisingly excellent selectivity.
이상과 같이 본 발명에서는 특정된 사항들과 한정된 실시예 및 비교예에 의해 설명되었으나 이는 본 발명의 보다 전반적인 이해를 돕기 위해서 제공된 것일 뿐, 본 발명은 상기의 실시예에 한정되는 것은 아니며, 본 발명이 속하는 분야에서 통상의 지식을 가진 자라면 이러한 기재로부터 다양한 수정 및 변형이 가능하다.As described above, the present invention has been described with specific details and limited examples and comparative examples, but these are provided only to facilitate a more general understanding of the present invention, and the present invention is not limited to the above examples. Those skilled in the art can make various modifications and variations from this description.
따라서, 본 발명의 사상은 설명된 실시예에 국한되어 정해져서는 아니되며, 후술하는 특허청구범위뿐 아니라 이 특허청구범위와 균등하거나 등가적 변형이 있는 모든 것들은 본 발명 사상의 범주에 속한다고 할 것이다.Accordingly, the spirit of the present invention should not be limited to the described embodiments, and the scope of the patent claims described below as well as all modifications that are equivalent or equivalent to the scope of this patent claim shall fall within the scope of the spirit of the present invention. .
Claims (11)
[화학식 1]
[상기 화학식 1에서,
L1 및 L2는 서로 독립적으로 (C2-C4)알킬렌이고;
R1 내지 R4는 서로 독립적으로 수소, (C1-C10)알킬, (C3-C20)시클로알킬, (C6-C20)아릴, (C6-C20)아릴(C1-C10)알킬 또는 (C1-C10)알콕시이며;
상기 R1 내지 R4의 아릴은 (C1-C10)알킬, (C6-C20)아릴, 트리(C1-C10)알킬실릴 및 (C1-C10)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.]An ethylene oligomerization catalyst comprising a chromium compound and a ligand compound represented by the following formula (1).
[Formula 1]
[In Formula 1 above,
L 1 and L 2 are independently (C2-C4)alkylene;
R 1 to R 4 are each independently hydrogen, (C1-C10)alkyl, (C3-C20)cycloalkyl, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, or (C1-C10) ) alkoxy;
The aryl of R 1 to R 4 is one or more substituents selected from the group consisting of (C1-C10)alkyl, (C6-C20)aryl, tri(C1-C10)alkylsilyl, and (C1-C10)alkoxy. May be replaced.]
상기 화학식 1의 L1 및 L2는 서로 독립적으로 (C2-C3)알킬렌이고;
R1 내지 R4는 서로 독립적으로 수소, (C1-C7)알킬, (C3-C12)시클로알킬, (C6-C12)아릴, (C6-C12)아릴(C1-C7)알킬 또는 (C1-C7)알콕시이며;
상기 R1 내지 R4의 아릴은 (C1-C7)알킬, (C6-C12)아릴, 트리(C1-C7)알킬실릴 및 (C1-C7)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있는, 에틸렌 올리고머화 촉매.According to paragraph 1,
In Formula 1, L 1 and L 2 are independently (C2-C3)alkylene;
R 1 to R 4 are each independently hydrogen, (C1-C7)alkyl, (C3-C12)cycloalkyl, (C6-C12)aryl, (C6-C12)aryl(C1-C7)alkyl, or (C1-C7) ) alkoxy;
The aryl of R 1 to R 4 is one or more substituents selected from the group consisting of (C1-C7)alkyl, (C6-C12)aryl, tri(C1-C7)alkylsilyl, and (C1-C7)alkoxy. Ethylene oligomerization catalyst, which may be substituted.
상기 화학식 1의 L1 및 L2는 서로 독립적으로 (C2-C3)알킬렌이고;
R1 내지 R4는 서로 독립적으로 수소, (C1-C7)알킬, (C6-C12)아릴 또는 (C6-C12)아릴(C1-C7)알킬이며;
상기 R1 내지 R4의 아릴은 (C1-C7)알킬, (C6-C12)아릴, 트리(C1-C7)알킬실릴 및 (C1-C7)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있는, 에틸렌 올리고머화 촉매.According to paragraph 1,
In Formula 1, L 1 and L 2 are independently (C2-C3)alkylene;
R 1 to R 4 are independently hydrogen, (C1-C7)alkyl, (C6-C12)aryl, or (C6-C12)aryl(C1-C7)alkyl;
The aryl of R 1 to R 4 is one or more substituents selected from the group consisting of (C1-C7)alkyl, (C6-C12)aryl, tri(C1-C7)alkylsilyl, and (C1-C7)alkoxy. Ethylene oligomerization catalyst, which may be substituted.
상기 리간드 화합물은 하기 화학식 2로 표시되는 것인, 에틸렌 올리고머화 촉매.
[화학식 2]
[상기 화학식 2에서,
R11 내지 R14는 서로 독립적으로 수소, (C1-C5)알킬, (C6-C10)아릴 또는 (C6-C10)아릴(C1-C5)알킬이며;
상기 R11 내지 R14의 아릴은 (C1-C5)알킬, 트리(C1-C5)알킬실릴 및 (C1-C5)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있다.]According to paragraph 1,
An ethylene oligomerization catalyst wherein the ligand compound is represented by the following formula (2).
[Formula 2]
[In Formula 2 above,
R 11 to R 14 are independently hydrogen, (C1-C5)alkyl, (C6-C10)aryl, or (C6-C10)aryl(C1-C5)alkyl;
The aryl of R 11 to R 14 may be substituted with one or more substituents selected from the group consisting of (C1-C5)alkyl, tri(C1-C5)alkylsilyl, and (C1-C5)alkoxy.]
상기 화학식 2의 R11 내지 R13은 서로 독립적으로 (C1-C5)알킬, (C6-C10)아릴 또는 (C6-C10)아릴(C1-C5)알킬이며;
R14는 수소 또는 (C1-C3)알킬이고;
상기 R11 내지 R13의 아릴은 (C1-C5)알킬, 트리(C1-C5)알킬실릴 및 (C1-C5)알콕시로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 치환기로 치환될 수 있는, 에틸렌 올리고머화 촉매.According to paragraph 4,
R 11 to R 13 in Formula 2 are independently (C1-C5)alkyl, (C6-C10)aryl, or (C6-C10)aryl(C1-C5)alkyl;
R 14 is hydrogen or (C1-C3)alkyl;
The aryl of R 11 to R 13 is an ethylene oligomer that may be substituted with one or more substituents selected from the group consisting of (C1-C5) alkyl, tri(C1-C5) alkylsilyl, and (C1-C5) alkoxy. fire catalyst.
상기 리간드 화합물은 하기 화합물에서 선택되는 것인, 에틸렌 올리고머화 촉매.
According to paragraph 1,
The ethylene oligomerization catalyst wherein the ligand compound is selected from the following compounds.
상기 유기 알루미늄 화합물은 메틸알루미녹산(MAO), 변형 메틸알루미녹산(MMAO), 에틸알루미녹산(EAO), 테트라이소부틸알루미녹산(TIBAO), 이소부틸알루미녹산(IBAO), 트리메틸알루미늄(TMA), 트리에틸알루미늄(TEA), 트리이소부틸알루미늄(TIBA), 트리-n-옥틸알루미늄, 메틸알루미늄 디클로라이드, 에틸알루미늄 디클로라이드, 디메틸알루미늄 클로라이드, 디에틸알루미늄 클로라이드, 알루미늄 이소프로폭사이드, 에틸알루미늄 세스퀴클로라이드 및 메틸알루미늄 세스퀴클로라이드로 이루어진 군으로부터 선택되는 하나 또는 둘 이상인, 에틸렌 올리고머화 촉매 조성물.In clause 7,
The organic aluminum compounds include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethyl aluminoxane (EAO), tetraisobutylaluminoxane (TIBAO), isobutylaluminoxane (IBAO), trimethylaluminum (TMA), Triethylaluminum (TEA), triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum dichloride, ethyl aluminum dichloride, dimethylaluminum chloride, diethylaluminum chloride, aluminum isopropoxide, ethyl aluminum ceth. An ethylene oligomerization catalyst composition comprising one or more selected from the group consisting of methylaluminum sesquichloride and methylaluminum sesquichloride.
상기 에틸렌 올리고머의 제조방법은 올리고머 전체 중 1-헥센이 60.0 내지 99.999 중량% 제조되는 것을 특징으로 하는, 에틸렌 올리고머의 제조방법.According to clause 9,
The method for producing an ethylene oligomer is characterized in that 60.0 to 99.999% by weight of 1-hexene is produced based on the total oligomer.
상기 에틸렌 올리고머의 제조방법은 벤젠, 글로로벤젠, 에틸벤젠, 톨루엔, 자일렌, 큐멘, 메시틸렌, 시클로헥산, 메틸시클로헥산, 메틸시클로펜탄, 헥산, 헵탄, 옥탄, 노난, 데칸, 헥센, 헵텐, 옥텐, 노넨, 데센, 애니솔, 에톡시벤젠 및 디메톡시벤젠로 이루어진 군으로부터 선택되는 하나 또는 둘 이상의 용매 하에서 수행되는 것인, 에틸렌 올리고머의 제조방법.According to clause 9,
The method for producing the ethylene oligomer is benzene, glorobenzene, ethylbenzene, toluene, xylene, cumene, mesitylene, cyclohexane, methylcyclohexane, methylcyclopentane, hexane, heptane, octane, nonane, decane, hexene, and heptene. A method for producing an ethylene oligomer, which is carried out under one or two or more solvents selected from the group consisting of octene, nonene, decene, anisole, ethoxybenzene, and dimethoxybenzene.
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US20170341998A1 (en) | 2016-05-27 | 2017-11-30 | Chevron Phillips Chemical Company Lp | Process Improvements for Chromium Based Ethylene Oligomerizations |
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US20170341998A1 (en) | 2016-05-27 | 2017-11-30 | Chevron Phillips Chemical Company Lp | Process Improvements for Chromium Based Ethylene Oligomerizations |
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