WO2015072812A1 - 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 - Google Patents
리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 Download PDFInfo
- Publication number
- WO2015072812A1 WO2015072812A1 PCT/KR2014/011078 KR2014011078W WO2015072812A1 WO 2015072812 A1 WO2015072812 A1 WO 2015072812A1 KR 2014011078 W KR2014011078 W KR 2014011078W WO 2015072812 A1 WO2015072812 A1 WO 2015072812A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkyl
- formula
- aryl
- hydrogen
- substituted
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 23
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003446 ligand Substances 0.000 title description 9
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- XYQQGESWGNLKIO-UHFFFAOYSA-N acetic acid;chromium;dihydrate Chemical compound O.O.[Cr].[Cr].[Cr].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O XYQQGESWGNLKIO-UHFFFAOYSA-N 0.000 claims description 3
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- GWKHNQIALWXRPA-GECNZSFWSA-N chromium (Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one (E)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one Chemical compound [Cr].CC(C)(C)C(\O)=C/C(=O)C(C)(C)C.CC(C)(C)C(\O)=C/C(=O)C(C)(C)C.CC(C)(C)C(\O)=C\C(=O)C(C)(C)C GWKHNQIALWXRPA-GECNZSFWSA-N 0.000 claims 1
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000011651 chromium Substances 0.000 description 17
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920000092 linear low density polyethylene Polymers 0.000 description 6
- 239000004707 linear low-density polyethylene Substances 0.000 description 6
- -1 polyethylene Polymers 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 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 5
- 230000000052 comparative effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- CHEANNSDVJOIBS-MHZLTWQESA-N (3s)-3-cyclopropyl-3-[3-[[3-(5,5-dimethylcyclopenten-1-yl)-4-(2-fluoro-5-methoxyphenyl)phenyl]methoxy]phenyl]propanoic acid Chemical compound COC1=CC=C(F)C(C=2C(=CC(COC=3C=C(C=CC=3)[C@@H](CC(O)=O)C3CC3)=CC=2)C=2C(CCC=2)(C)C)=C1 CHEANNSDVJOIBS-MHZLTWQESA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- PLGVIJOQDDMWAO-UHFFFAOYSA-N CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F PLGVIJOQDDMWAO-UHFFFAOYSA-N 0.000 description 1
- KQJMQTVOZCSENE-UHFFFAOYSA-N CCNC1=CC=CC=C1.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCNC1=CC=CC=C1.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F KQJMQTVOZCSENE-UHFFFAOYSA-N 0.000 description 1
- HFEVWLDHPOCPTP-UHFFFAOYSA-N CCNCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCNCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F HFEVWLDHPOCPTP-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- DAQQLFRDNPFAOY-UHFFFAOYSA-N Cl.Cl.Cl.C1CCOC1.C1CCOC1.C1CCOC1 Chemical compound Cl.Cl.Cl.C1CCOC1.C1CCOC1.C1CCOC1 DAQQLFRDNPFAOY-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- SHPVKUQHCZKKRP-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC SHPVKUQHCZKKRP-UHFFFAOYSA-N 0.000 description 1
- RPXNIXOOFOQCKJ-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC RPXNIXOOFOQCKJ-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052787 antimony Chemical group 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- WUZCBSQKHJJABD-YNEVXYPXSA-K chromium(3+);(z)-3-oxo-1-phenylbut-1-en-1-olate Chemical compound [Cr+3].CC(=O)\C=C(/[O-])C1=CC=CC=C1.CC(=O)\C=C(/[O-])C1=CC=CC=C1.CC(=O)\C=C(/[O-])C1=CC=CC=C1 WUZCBSQKHJJABD-YNEVXYPXSA-K 0.000 description 1
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 description 1
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- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 125000005843 halogen group Chemical group 0.000 description 1
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- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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- B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
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- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
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- 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
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- C07C2/08—Catalytic processes
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- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
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- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
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- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
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- C07C2531/24—Phosphines
Definitions
- the present invention relates to a ligand compound, a catalyst system for olepin oligomerization, and an urepin oligomerization method using the same.
- Linear alpha-eulre pin (Linear alpha- olefin) is the comonomer, and commercially widely used as an important material or the like used cleaning agent, a lubricant, a plasticizer, particularly 1-nuclear Sen and 1-octene linear low density polyethylene (Linear Low Density Polyethylene o, LLDPE) is widely used as a comonomer for controlling the density of polyethylene.
- LLDPE Linear Low Density Polyethylene
- Conventional processes for the production of LLDPE include copolymerization with comonomers such as alpha-olefins such as 1-nuxene and 1-octene to control the density by forming a branch in the polymer backbone with ethylene. It was done.
- X is phosphorus, arsenic or antimony
- Y is a linking group such as -N (R5)-, and at least one of Rl, R2, R3 and R4 has a polar or electron-donating substituent.
- (0-ethylphenyl) 2 PN (Me) P (eethyl) which is a compound which does not exhibit catalytic activity for 1-nucleene under catalytic conditions, does not have a polar substituent in at least one of Rl, R2, R3 and R4.
- Phenyl) 2 C3 ⁇ 4em. Commun., 2002, 858).
- the ligand containing the heteroatoms of the prior art described above is 1-octene or
- the present invention provides a novel ligand compound capable of limerizing and polymerizing olefins with high catalytic activity, selectivity, a catalyst system for olefin oligomerization comprising the same, and a lelpene oligomerization method using the same.
- X is Ci- 20 alkylene or C 6 - 14 arylene and,
- Ri to R 4 are each independently a Cn alkyl, C 2 - 20 alkenyl, C 6 - 14 aryl group, a d- C 6 alkyl substituted by 4 - 14 aryl, C 6 - 14 aryl group substituted with an alkyl 4-d- Or C 6 — 14 aryl substituted with C 4 alkoxy,
- R 5 to R 14 are each independently hydrogen, d- 20 alkyl, C 2 - 20 alkenyl, C 6 - 14 aryl group substituted by - 14 aryl, C 6 alkyl substituted with -4 - 14 aryl, C 6 a substituted C 6 to -4 alkyl or d- 4 alkoxy-14 is aryl.
- X is methylene or phenylene.
- Ri to R 4 are the same as each other. More preferably, the above. Ri to R4 are phenyl.
- R5 and 3 ⁇ 4 are hydrogen.
- R 7 and R 8 are the same as each other, and are hydrogen or methyl.
- R 9 is hydrogen or iso-propyl.
- Rio is hydrogen.
- the Rll to Rl3 are hydrogen.
- R 14 is hydrogen or methyl.
- X is methylene or phenylene
- R to R4 are phenyl and R 5 and R 6 are hydrogen
- R / and Rs are the same as each other and hydrogen or methyl
- Rg is hydrogen
- S is isopropyl
- R 10 to R 13 are hydrogen and R 14 is hydrogen or methyl.
- Representative examples of the compound represented by Formula 1 are as follows:
- Reaction Formula 1 A, X, and R 5 to R 14 are as defined above.
- Step 1 is a reaction for substituting an A substituent for the amine group of the starting material, wherein the starting material and ⁇ 3 ⁇ 43 ⁇ 4 ⁇ are reacted. It is preferable to react triethylamine together, and it is preferable to use dichloromethane as a solvent. If the structure of the A substituent and the structure of R 2 (PR ⁇ R) and the structure of R 3 and R 4 (PR 3 R 4 ) are the same, the compound represented by the formula (1) can be prepared by the step 1. If the structure of the substituent A and R 2 ( ⁇ ⁇ 2 ) and R 3 and P and the structure (PR 3 R 4 ) is different, step 2 may be carried out to prepare a compound represented by the formula (1).
- Step 2 is the same as step 1, except that PR 3 R 4 C1 is used as the reaction material.
- the present invention provides a catalyst system for olefin oligomerization comprising a compound represented by the formula (1), a transition metal source and a promoter.
- the term 'lephine oligomerization' means that the olefin is polymerized. When three olefins are polymerized, they are called trimerization, and when four olefins are polymerized, they are called tetramerization. multimerization).
- the present invention means the selective production of 1-nuxene and 1-octene which are the main comonomers of LLDPE from ethylene.
- the selective olefin oligomerization reaction is closely related to the catalyst system used.
- the catalyst system used during the olefin oligomerization reaction includes a transition metal source serving as a main catalyst and a cocatalyst, in which the structure of the active catalyst can be changed according to the chemical structure of the ligand, and thus the olephine selectivity and The activity is different.
- the catalyst system for olefin oligomerization according to the present invention may selectively prepare 1-nuxene and 1-octene using the compound represented by Formula 1 as a ligand. Theoretically limited .
- the compound represented by Formula 1 has two A substituents capable of coordinating with the main catalyst, and has a structure in which the A substituents in the compound are linked by a linker of a cyclonucleic acid-X structure. Due to the flexible linker, it is believed that the two A substituents, which are active sites for the oligomerization reaction, effectively interact with each other to increase the activity and selectivity of the catalyst.
- the source of the transition metal serves as a main catalyst, crumb (III) acetylacetonate, trichloride tristetrahydrofuran, crumb (III) ⁇ 2-ethylnucleoanoate, chromium (111) tris (2, 2, 6) , 6-tetramethyl-3, 5-heptanedionate), crumb (III) benzoylacetonate, chromium (III) nucleofluoro-2, 4-pentanedionate and chromium (III) acetate hydroxide It is preferable that it is any one or more selected from. .
- the cocatalyst is not particularly limited as long as it is an organometallic compound including a Group 13 metal, and can be generally used in the multimerization of olefins under a catalyst of a transition metal compound.
- the cocatalyst may be any one or more selected from the group consisting of compounds represented by the following Chemical Formulas 3 to 5.
- Each R 15 is independently halogen, alkyl or haloalkyl, c is an integer of 2 or more,
- D is aluminum or boron
- R 16 is CMO alkyl or ⁇ -20 haloalkyl
- L is a neutral Lewis base
- Q is Br 3+ or Al 3+
- E are each independently a C 6 - 20, and alkyl, wherein - 20 aryl or.
- the C 6 - 20 aryl or eu 20 alkyl is substituted with one or more substituents selected from the group consisting of unsubstituted or substituted by halogen, eu 20 alkyl, d-20 alkoxy and phenoxy.
- substituents selected from the group consisting of unsubstituted or substituted by halogen, eu 20 alkyl, d-20 alkoxy and phenoxy.
- Examples of the compound represented by the formula (3) include methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane or butyl aluminoxane.
- Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethylchloroaluminum, Triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trinuclearaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri—P-lrylaluminum, Dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron or tributyl boron
- Examples of the compound represented by the formula (5) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-lryl) ) Boron, tripropyl ammonium tetra (p-lryl) boron, triethyl ammonium tetra (0, P-dimethylphenyl) boron, trimethyl ammonium tetra (0, ⁇ -dimethylphenyl) boron, tributyl ammonium tetra ( ⁇ -trifluoromethylphenyl) boron, trimethylammonium tetra ( ⁇ -trifluoromethylphenyl) boron,
- the molar ratio of the compound represented by the formula (1): transition metal source: promoter is about 1: 1: 1 to about 10: 1: 10,000, and preferably about 1: 1: 100 to about 5: 1: 3, 000.
- the present invention is not limited thereto.
- the three components are simultaneously or sequentially in any order, in the presence or absence of monomers in any suitable solvent. Can be added together to obtain an active catalyst.
- Suitable solvents include, but are not limited to, heptane, toluene, 1-nuxene, diethyl ether, tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene, methanol, acetone, and the like.
- the present invention provides a method for producing an olefin oligomer comprising the step of multimerizing the olefin in the presence of the catalyst system for olefin pin oligomerization.
- the olefin oligomerization according to the present invention is a form in which a homogeneous liquid phase reaction in the presence or absence of an inert solvent or a catalyst system is not partially dissolved or completely dissolved using a conventional apparatus and contact technology with the catalyst system for olefin oligomerization.
- Phosphorous slurry reaction, two-phase liquid / liquid reaction, or bulk olefin reaction in which the product olefin serves as the main medium or gas phase reaction is possible, and homogeneous liquid reaction is preferred.
- the urepin oligomerization reaction may be carried out in any inert solvent that does not react with the catalyst compound and the activator.
- Suitable inert solvents include, but are not limited to, benzene, toluene, xylene, cumene, heptane, cyclonucleic acid, methylcyclonucleic acid, methylcyclopentane, nucleic acid, pentane, butane, isobutane and the like.
- the solvent may be used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum.
- Hitting the pin eulre meohwa reaction may be carried out at a temperature between about 5 0 C to a temperature of about 200 ° C, preferably from about 30 ° C to about 150 ° C.
- the olepin oligomerization reaction may be carried out at a pressure of about 1 bar to about 300 bar, preferably at a pressure of about 2 bar to about 150 bar.
- 1-nuxene and 1-octene can be selectively synthesized. .
- olefins can be oligomerized with higher catalytic activity and selectivity than conventional catalyst systems.
- Parr reactor of 600 mL capacity was prepared and vacuumed at 120 ° C. for 2 hours, then the inside was replaced with argon and the temperature was lowered to 45 ° C.
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Abstract
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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CN201480005990.6A CN104955829B (zh) | 2013-11-18 | 2014-11-18 | 配体化合物、用于烯烃低聚反应的催化剂体系及使用其的烯烃低聚方法 |
US14/760,158 US9498773B2 (en) | 2013-11-18 | 2014-11-18 | Catalyst system for olefin oligomerization, and method for olefin oligomerization using the same |
JP2015550348A JP5954914B2 (ja) | 2013-11-18 | 2014-11-18 | リガンド化合物、オレフィンオリゴマー化用触媒系、およびこれを用いたオレフィンオリゴマー化方法 |
EP14862021.4A EP2927236A4 (en) | 2013-11-18 | 2014-11-18 | LIGAND COMPOUND, CATALYST SYSTEM FOR OLIGOMERIZING OLEFINS, AND OLIGOMERIZATION METHOD OF OLEFINS USING THE SAME |
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KR1020140160180A KR20150058034A (ko) | 2013-11-18 | 2014-11-17 | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
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US (1) | US9498773B2 (ko) |
EP (1) | EP2927236A4 (ko) |
JP (1) | JP5954914B2 (ko) |
KR (1) | KR20150058034A (ko) |
CN (1) | CN104955829B (ko) |
WO (1) | WO2015072812A1 (ko) |
Cited By (1)
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JP2018508591A (ja) * | 2015-06-01 | 2018-03-29 | エルジー・ケム・リミテッド | 1−オクテン組成物 |
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WO2015072811A1 (ko) * | 2013-11-18 | 2015-05-21 | 주식회사 엘지화학 | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
KR101757369B1 (ko) | 2014-12-11 | 2017-07-12 | 주식회사 엘지화학 | 리간드 화합물, 유기크롬 화합물, 올레핀 올리고머화용 촉매 시스템, 및 이를 이용한 올레핀의 올리고머화 방법 |
WO2016186282A1 (ko) | 2015-05-15 | 2016-11-24 | 주식회사 엘지화학 | 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법 |
KR101768194B1 (ko) | 2015-05-15 | 2017-08-16 | 주식회사 엘지화학 | 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법 |
KR20160134464A (ko) | 2015-05-15 | 2016-11-23 | 주식회사 엘지화학 | 혼성 담지 촉매계, 및 이를 이용한 폴리올레핀의 제조방법 |
EP3118227A4 (en) * | 2015-06-01 | 2017-11-15 | LG Chem, Ltd. | 1-octene composition |
KR102058142B1 (ko) | 2015-09-02 | 2019-12-20 | 주식회사 엘지화학 | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
KR101761830B1 (ko) | 2015-10-21 | 2017-07-26 | 주식회사 엘지화학 | 리간드 화합물, 올레핀 올리고머화용 촉매계, 및 이를 이용한 올레핀 올리고머화 방법 |
KR102545533B1 (ko) * | 2016-05-27 | 2023-06-21 | 에스케이이노베이션 주식회사 | 올리고머화 촉매 및 이를 이용한 에틸렌 올리고머의 제조방법 |
KR102521448B1 (ko) * | 2017-12-20 | 2023-04-13 | 주식회사 엘지화학 | 파라핀 혼합물 및 이의 제조 방법 |
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- 2014-11-17 KR KR1020140160180A patent/KR20150058034A/ko not_active Application Discontinuation
- 2014-11-18 US US14/760,158 patent/US9498773B2/en active Active
- 2014-11-18 CN CN201480005990.6A patent/CN104955829B/zh active Active
- 2014-11-18 JP JP2015550348A patent/JP5954914B2/ja active Active
- 2014-11-18 WO PCT/KR2014/011078 patent/WO2015072812A1/ko active Application Filing
- 2014-11-18 EP EP14862021.4A patent/EP2927236A4/en not_active Withdrawn
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Also Published As
Publication number | Publication date |
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JP2016503815A (ja) | 2016-02-08 |
US20160045906A1 (en) | 2016-02-18 |
CN104955829B (zh) | 2018-03-09 |
KR20150058034A (ko) | 2015-05-28 |
EP2927236A1 (en) | 2015-10-07 |
JP5954914B2 (ja) | 2016-07-20 |
CN104955829A (zh) | 2015-09-30 |
EP2927236A4 (en) | 2016-07-27 |
US9498773B2 (en) | 2016-11-22 |
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