KR20140006725A - Novel ligand compound and transition metal compound comprising the same - Google Patents
Novel ligand compound and transition metal compound comprising the same Download PDFInfo
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- KR20140006725A KR20140006725A KR1020130079013A KR20130079013A KR20140006725A KR 20140006725 A KR20140006725 A KR 20140006725A KR 1020130079013 A KR1020130079013 A KR 1020130079013A KR 20130079013 A KR20130079013 A KR 20130079013A KR 20140006725 A KR20140006725 A KR 20140006725A
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- South Korea
- Prior art keywords
- group
- carbon atoms
- transition metal
- added
- mmol
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 91
- 239000003446 ligand Substances 0.000 title claims abstract description 70
- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 66
- 125000004432 carbon atom Chemical group C* 0.000 claims description 70
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000001769 aryl amino group Chemical group 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 9
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007809 chemical reaction catalyst Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 112
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 96
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- 239000000203 mixture Substances 0.000 description 48
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 45
- 239000000243 solution Substances 0.000 description 45
- -1 trimethylsilylmethyl group Chemical group 0.000 description 37
- 239000007787 solid Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000012043 crude product Substances 0.000 description 20
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 18
- 239000012044 organic layer Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- 229920000098 polyolefin Polymers 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 150000002736 metal compounds Chemical class 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000012190 activator Substances 0.000 description 7
- 229910052796 boron Chemical group 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000012267 brine Substances 0.000 description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
- FYELSNVLZVIGTI-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-5-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1CC)CC(=O)N1CC2=C(CC1)NN=N2 FYELSNVLZVIGTI-UHFFFAOYSA-N 0.000 description 4
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-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=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 4
- BIQBSUXXWXMZCC-UHFFFAOYSA-N 2-tert-butyl-1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2NC(C(C)(C)C)CCC2=C1 BIQBSUXXWXMZCC-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- MBZWJMJCPXTGNN-UHFFFAOYSA-N O=C(C1=CC=CC=C1)C1=CC=CC2=C1NC(CC2)C1=CC=CC=C1 Chemical compound O=C(C1=CC=CC=C1)C1=CC=CC2=C1NC(CC2)C1=CC=CC=C1 MBZWJMJCPXTGNN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-BJUDXGSMSA-N methanone Chemical compound O=[11CH2] WSFSSNUMVMOOMR-BJUDXGSMSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 3
- NENRIWVIKRHKGH-UHFFFAOYSA-N 2-naphthalen-1-yl-1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2C(C3NC4=CC=CC=C4CC3)=CC=CC2=C1 NENRIWVIKRHKGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BDRBFQDULWPNDG-UHFFFAOYSA-N C1(=CC=CC=C1)C(=O)C=1C=CC=C2CC(NC12)C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C(=O)C=1C=CC=C2CC(NC12)C1=CC=CC=C1 BDRBFQDULWPNDG-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 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
- 239000007789 gas Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- GOGFAXSDYXYPQM-UHFFFAOYSA-N phenyl(1,2,3,4-tetrahydroquinolin-8-yl)methanone Chemical compound C(C1=CC=CC=C1)(=O)C=1C=CC=C2CCCNC12 GOGFAXSDYXYPQM-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 description 2
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- ZZOVZJBWXVZVLN-UHFFFAOYSA-N 2,3-dihydro-1h-indol-7-yl(phenyl)methanone Chemical compound C=1C=CC=2CCNC=2C=1C(=O)C1=CC=CC=C1 ZZOVZJBWXVZVLN-UHFFFAOYSA-N 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- QAUGNTRYNWFNBL-UHFFFAOYSA-N 2-phenyl-1,2,3,4-tetrahydroquinoline Chemical compound C1CC2=CC=CC=C2NC1C1=CC=CC=C1 QAUGNTRYNWFNBL-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
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- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
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- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
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- 125000001624 naphthyl group Chemical group 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 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
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
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- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- LPZOCVVDSHQFST-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CC LPZOCVVDSHQFST-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- XZPFOJPRFUSEIH-UHFFFAOYSA-N 2-phenyl-2,3-dihydro-1h-indole Chemical compound N1C2=CC=CC=C2CC1C1=CC=CC=C1 XZPFOJPRFUSEIH-UHFFFAOYSA-N 0.000 description 1
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- FPCRQIUTHZCKEY-UHFFFAOYSA-N CC(C(N=CC1=C2NCCC2=CC=C1)=C1C)=CC=C1C1=CC=CC=C1 Chemical compound CC(C(N=CC1=C2NCCC2=CC=C1)=C1C)=CC=C1C1=CC=CC=C1 FPCRQIUTHZCKEY-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
- JEVCOCKVSCRHMR-UHFFFAOYSA-N CCN(CC)C1=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 CCN(CC)C1=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 JEVCOCKVSCRHMR-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- DXQXWMYUGOTNGJ-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]boron Chemical compound [B]C1=CC=C(C(F)(F)F)C=C1 DXQXWMYUGOTNGJ-UHFFFAOYSA-N 0.000 description 1
- XIBZTAIPROXEDH-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.CCN(CC)C1=CC=CC=C1 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.CCN(CC)C1=CC=CC=C1 XIBZTAIPROXEDH-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
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- GXNDYZPMZKJDSS-UHFFFAOYSA-N hex-1-ene Chemical compound CCCCC=C.CCCCC=C GXNDYZPMZKJDSS-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 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
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-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
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-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
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-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
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
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Abstract
Description
본 발명은 신규한 리간드 화합물 및 상기 리간드 화합물을 포함하는 전이금속 화합물에 관한 것이다.The present invention relates to a novel ligand compound and a transition metal compound comprising the ligand compound.
올레핀 중합용 메탈로센 촉매는 오랜 기간 발전해왔다. 메탈로센 화합물은 일반적으로 알루미녹산, 보레인, 보레이트 또는 다른 활성화제를 이용하여 활성화시켜 사용한다. 예를 들어, 사이클로펜타다이에닐기를 포함한 리간드와 두 개의 시그마 클로라이드 리간드를 갖는 메탈로센 화합물은 알루미녹산을 활성화제로 사용한다. 이러한 메탈로센 화합물의 클로라이드기를 다른 리간드로(예를 들어, 벤질 또는 트리메틸실릴메틸기(-CH2SiMe3)) 치환하는 경우 촉매 활성도 증가 등의 효과를 나타내는 예가 보고되었다.Metallocene catalysts for olefin polymerization have been developed for a long time. The metallocene compound is generally activated by using aluminoxane, borane, borate or other activator. For example, a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. When the chloride group of such a metallocene compound is substituted with another ligand (for example, benzyl or trimethylsilylmethyl group (-CH 2 SiMe 3 )), there has been reported an example in which the catalytic activity is increased.
유럽특허 EP 1462464는 클로라이드, 벤질, 트리메틸실릴메틸기를 갖는 하프늄 메탈로센 화합물을 이용한 중합 실시예가 개시되어 있다. 또한 중심 금속과 결합한 알킬 리간드에 따라 활성화 종의 생성 에너지 등이 달라지는 결과도 보고된 바 있다(J. Am. Chem. Soc. 2000, 122, 10358). 한국특허 제 820542호에는 퀴놀린계 리간드를 갖는 올레핀 중합용 촉매를 개시되어 있으며, 본 특허는 메틸기 외의 실리콘, 게르마늄 원자를 포함하는 리빙 그룹을 갖는 촉매에 관한 것이다.European Patent EP 1462464 discloses a polymerization example using a hafnium metallocene compound having a chloride, benzyl, trimethylsilylmethyl group. Also, it has been reported that the production energy of the activated species varies depending on the alkyl ligand bound to the center metal (J. Am. Chem. Soc. 2000, 122, 10358). Korean Patent No. 820542 discloses a catalyst for the polymerization of olefins having a quinoline ligand, and this patent relates to a catalyst having a living group containing silicon and germanium atoms other than the methyl group.
Dow 사가 1990년대 초반 [Me2Si(Me4C5)NtBu]TiCl2 (Constrained-Geometry Catalyst, CGC)를 미국특허 제5,064,802호 등에서 개시하였는데, 에틸렌과 알파-올레핀의 공중합 반응에서 CGC가 기존까지 알려진 메탈로센 촉매들에 비해 우수한 측면을 크게 다음과 같이 두 가지로 요약할 수 있다: (1) 높은 중합 온도에서도 높은 활성도를 나타내면서 고분자량의 중합체를 생성하며, (2) 1-헥센 및 1-옥텐과 같은 입체적 장애가 큰 알파-올레핀의 공중합성도 매우 뛰어나다는 점이다. 그 외에도 중합 반응 시, CGC 의 여러 가지 특성들이 점차 알려지면서 이의 유도체를 합성하여 중합 촉매로 사용하고자 하는 노력이 학계 및 산업계에서 활발히 이루어졌다.Dow has disclosed in the early 1990s [Me 2 Si (Me 4 C 5 ) N t Bu] TiCl 2 (Constrained-Geometry Catalyst, CGC) in U.S. Patent No. 5,064,802. In the copolymerization reaction of ethylene and alpha-olefin, CGC (1) high molecular weight polymers with high activity at high polymerization temperatures, and (2) 1-hexene (1-hexene) And 1-octene are also excellent in the copolymerization of alpha-olefins with large steric hindrance. In addition, various characteristics of CGC were gradually known during the polymerization reaction, and efforts to synthesize the derivative and use it as a polymerization catalyst have actively been made in academia and industry.
그 중 하나의 접근 방법으로 실리콘 브릿지 대신에 다른 다양한 브릿지 및 질소 치환체가 도입된 금속 화합물의 합성과 이를 이용한 중합이 시도되었다. 최근까지 알려진 대표적인 금속 화합물들은 CGC 구조의 실리콘 브릿지 대신에 포스포러스, 에틸렌 또는 프로필렌, 메틸리덴 및 메틸렌 브릿지가 각각 도입되어 있으나, 에틸렌 중합 또는 에틸렌과 알파올레핀의 공중합에의 적용시에 CGC 대비하여 중합 활성도나 공중합 성능 등의 측면에서 뛰어난 결과들을 나타내지 못하였다.One approach is to synthesize and incorporate a variety of metal compounds into which various bridges and nitrogen substituents have been introduced instead of silicon bridges. Representative metal compounds that have been known up to now include phosphorus, ethylene or propylene, methylidene and methylene bridges instead of CGC-structured silicon bridges. However, when applied to ethylene polymerization or copolymerization of ethylene and alpha olefins, But did not show excellent results in terms of activity or copolymerization performance.
다른 접근 방법으로는 상기 CGC의 아미도 리간드 대신에 옥시도 리간드로 구성된 화합물들 많이 합성되었으며, 이를 이용한 중합도 일부 시도되었다. As another approach, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and some polymerization using the compounds was attempted.
그러나, 이러한 모든 시도들 중에서 실제로 상업 공장에 적용되고 있는 촉매들은 몇몇에 불과한 수준이다. However, among all these attempts, only a few catalysts have actually been applied to commercial plants.
상기와 같은 문제점을 해결하기 위하여, 본 발명은 신규한 리간드 화합물, 및 상기 리간드 화합물을 포함하는 전이금속 화합물을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention aims to provide a novel ligand compound and a transition metal compound containing the ligand compound.
상기한 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 리간드 화합물을 제공한다.In order to achieve the above object, the present invention provides a ligand compound represented by the following general formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In Formula 1,
m은 1 내지 2의 정수이고,m is an integer of 1 to 2,
R1, R2 및 R3은 동일하거나 상이하고 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아릴알킬기 또는 실릴기이며, 2개 이상의 R1, R2 또는 R3은 탄소수 1 내지 20의 알킬기 또는 탄소수 6 내지 20의 아릴기를 포함하는 알킬리딘기에 의해 서로 연결되어 고리를 형성할 수 있고, 단 R2가 수소인 경우는 제외하며;R 1 , R 2 and R 3 are the same or different and are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group or silyl group having 7 to 20 carbon atoms, and two or more R 1 , R 2 or R 3 are connected to each other by an alkylidine group including an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring; Except where R 2 is hydrogen;
R4, R5 및 R6은 동일하거나 상이하고 각각 독립적으로 수소, 할로겐기, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 1 내지 20의 알콕시기, 탄소수 6 내지 20의 아릴옥시기, 탄소수 1 내지 20의 알킬 아미노기 또는 탄소수 6 내지 20의 아릴 아미노기이며, 2개 이상의 R4, R5 또는 R6가 서로 연결되어 지방족 또는 방향족 고리를 형성할 수 있다.R 4 , R 5 and R 6 are the same or different and are each independently hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms An oxy group, an alkyl amino group having 1 to 20 carbon atoms or an aryl amino group having 6 to 20 carbon atoms, and two or more R 4 , R 5 or R 6 may be linked to each other to form an aliphatic or aromatic ring.
또한, 본 발명은 하기 화학식 2로 표시되는 전이금속 화합물을 제공한다.The present invention also provides a transition metal compound represented by the following formula (2).
[화학식 2](2)
M은 4족의 전이금속이고;M is a transition metal of Group 4;
K는 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아 알킬기, 탄소수 1 내지 20의 알킬아미노기, 탄소수 6 내지 20의 아릴 아미노기 및 탄소수 1 내지 20의 알킬리덴기로 이루어진 군에서 선택된 1종이고;K is a halogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, alkyl of 1 to 20 carbon atoms An amino group, an aryl amino group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms;
n은 2 내지 3의 정수이며; n is an integer from 2 to 3;
m, R1, R2, R3, R4, R5 및 R6는 상기 화학식 1에서 정의한 바와 같다.m, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same as defined in
본 발명의 신규한 리간드 화합물 및 이를 포함하는 전이금속 화합물은 올레핀계 중합체의 제조에 있어 중합 반응의 촉매로 유용하게 사용될 수 있다.The novel ligand compounds of the present invention and transition metal compounds containing them can be usefully used as catalysts for the polymerization reaction in the production of olefinic polymers.
도 1은 실시예 1의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 2은 실시예 2의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 3은 실시예 3의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 4는 실시예 4의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 5는 실시예 5의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 6은 실시예 6의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 7은 실시예 7의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 8은 실시예 8의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 9는 실시예 9의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 10은 실시예 10의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 11은 실시예 11의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 12는 실시예 12의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 13은 실시예 13의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 14는 실시예 14의 리간드 화합물의 NMR spectrum을 나타낸 것이다.
도 15는 실시예 15의 전이금속 화합물의 NMR spectrum을 나타낸 것이다.
도 16은 실시예 16의 전이금속 화합물의 NMR spectrum을 나타낸 것이다.
도 17은 실시예 17의 전이금속 화합물의 NMR spectrum을 나타낸 것이다.
도 18은 실시예 18의 전이금속 화합물의 NMR spectrum을 나타낸 것이다.
도 19는 실시예 19의 전이금속 화합물의 NMR spectrum을 나타낸 것이다.
도 20은 실시예 20의 전이금속 화합물의 NMR spectrum을 나타낸 것이다.
도 21은 실시예 21의 전이금속 화합물의 NMR spectrum을 나타낸 것이다.
도 22는 실시예 22의 전이금속 화합물의 NMR spectrum을 나타낸 것이다.
도 23은 실시예 23의 전이금속 화합물의 NMR spectrum을 나타낸 것이다.
도 24는 실시예 24의 전이금속 화합물의 NMR spectrum을 나타낸 것이다.Figure 1 shows an NMR spectrum of the ligand compound of Example 1.
Figure 2 shows the NMR spectrum of the ligand compound of Example 2.
3 shows an NMR spectrum of a ligand compound of Example 3.
4 shows an NMR spectrum of a ligand compound of Example 4.
Figure 5 shows the NMR spectrum of the ligand compound of Example 5.
Figure 6 shows the NMR spectrum of the ligand compound of Example 6.
7 shows an NMR spectrum of a ligand compound of Example 7.
8 shows an NMR spectrum of a ligand compound of Example 8.
9 shows an NMR spectrum of a ligand compound of Example 9.
10 shows an NMR spectrum of a ligand compound of Example 10.
11 shows an NMR spectrum of a ligand compound of Example 11.
12 shows an NMR spectrum of a ligand compound of Example 12.
FIG. 13 shows an NMR spectrum of a ligand compound of Example 13. FIG.
14 shows an NMR spectrum of a ligand compound of Example 14.
15 shows an NMR spectrum of a transition metal compound of Example 15.
16 shows an NMR spectrum of a transition metal compound of Example 16.
17 shows an NMR spectrum of a transition metal compound of Example 17.
18 shows an NMR spectrum of a transition metal compound of Example 18.
19 shows an NMR spectrum of a transition metal compound of Example 19.
20 shows an NMR spectrum of a transition metal compound of Example 20.
21 shows an NMR spectrum of a transition metal compound of Example 21.
22 shows an NMR spectrum of a transition metal compound of Example 22.
FIG. 23 shows an NMR spectrum of a transition metal compound of Example 23. FIG.
24 shows an NMR spectrum of a transition metal compound of Example 24.
본 명세서에서 사용되는 용어는 단지 예시적인 실시예들을 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도는 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서, "포함하다", "구비하다" 또는 "가지다" 등의 용어는 실시된 특징, 숫자, 단계, 구성 요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 구성 요소, 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바, 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
이하, 본 발명을 상세하게 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명의 리간드 화합물은 하기 화학식 1로 표시될 수 있다.Ligand compound of the present invention may be represented by the formula (1).
[화학식 1][Formula 1]
상기 화학식 1에서,In
m은 1 내지 2의 정수이고,m is an integer of 1 to 2,
R1, R2 및 R3은 동일하거나 상이하고 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아릴알킬기 또는 실릴기이며, 2개 이상의 R1, R2 또는 R3은 탄소수 1 내지 20의 알킬기 또는 탄소수 6 내지 20의 아릴기를 포함하는 알킬리딘기에 의해 서로 연결되어 고리를 형성할 수 있고, 단 R2가 수소인 경우는 제외하며;R 1 , R 2 and R 3 are the same or different and are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group or silyl group having 7 to 20 carbon atoms, and two or more R 1 , R 2 or R 3 are connected to each other by an alkylidine group including an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring; Where R 2 Except for hydrogen;
R4, R5 및 R6은 동일하거나 상이하고 각각 독립적으로 수소, 할로겐기, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 1 내지 20의 알콕시기, 탄소수 6 내지 20의 아릴옥시기, 탄소수 1 내지 20의 알킬 아미노기 또는 탄소수 6 내지 20의 아릴 아미노기이며, 2개 이상의 R4, R5 또는 R6가 서로 연결되어 지방족 또는 방향족 고리를 형성할 수 있다.R 4 , R 5 and R 6 are the same or different and are each independently hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms An oxy group, an alkyl amino group having 1 to 20 carbon atoms or an aryl amino group having 6 to 20 carbon atoms, and two or more R 4 , R 5 or R 6 may be linked to each other to form an aliphatic or aromatic ring.
상기 화학식 1 에서 정의된 각 치환기에 대하여 상세히 설명하면 다음과 같다.Each of the substituents defined in
상기 알킬기는 직쇄 또는 분지쇄의 알킬기를 포함한다.The alkyl group includes a straight or branched chain alkyl group.
상기 알케닐기는 직쇄 또는 분지쇄의 알케닐기를 포함한다.The alkenyl group includes a straight or branched alkenyl group.
본 발명의 일 실시예에 따르면, 상기 실릴기는 트리메틸실릴, 트리에틸실릴, 트리프로필실릴, 트리부틸실릴, 트리헥실실릴, 트리이소프로필실릴, 트리이소부틸실릴, 트리에톡시실릴, 트리페닐실릴, 트리스(트리메틸실릴)실릴 등이 있으나, 이들 예로만 한정되는 것은 아니다.According to an embodiment of the present invention, the silyl group is trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, Tris (trimethylsilyl) silyl and the like, but are not limited to these examples.
본 발명의 일 실시예에 따르면, 상기 아릴기는 탄소수 6 내지 20인 것이 바람직하며, 구체적으로 페닐, 나프틸, 안트라세닐, 피리딜, 디메틸아닐리닐, 아니솔릴 등이 있으나, 이들 예로만 한정되는 것은 아니다.According to one embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto. no.
상기 알킬아릴기는 상기 알킬기에 의하여 치환된 아릴기를 의미한다.The alkylaryl group means an aryl group substituted by the alkyl group.
상기 아릴알킬기는 상기 아릴기에 의하여 치환된 알킬기를 의미한다.The arylalkyl group means an alkyl group substituted by the aryl group.
상기 할로겐기는 플루오린기, 염소기, 브롬기 또는 요오드기를 의미한다.The halogen group means a fluorine group, a chlorine group, a bromine group or an iodine group.
상기 알킬 아미노기는 상기 알킬기에 의하여 치환된 아미노기를 의미하며, 디메틸아미노기, 디에틸아미노기 등이 있으나, 이들 예로만 한정된 것은 아니다.The alkyl amino group means an amino group substituted by the alkyl group, and there are a dimethylamino group, a diethylamino group, and the like, but is not limited thereto.
상기 아릴 아미노기는 상기 아릴기에 의하여 치환된 아미노기를 의미하며, 디페닐아미노기 등이 있으나, 이들 예로만 한정된 것은 아니다.The aryl amino group means an amino group substituted by the aryl group, and there are diphenylamino groups and the like, but are not limited thereto.
본 발명의 일 실시예에 따르면, 상기 아릴기는 탄소수 6 내지 20인 것이 바람직하며, 구체적으로 페닐, 나프틸, 안트라세닐, 피리딜, 디메틸아닐리닐, 아니솔릴 등이 있으나, 이들 예로만 한정되는 것은 아니다.According to one embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto. no.
상기 화학식 1로 표시되는 리간드 화합물은 하기 구조식 중 하나로 표시될 수 있으나, 이에 한정되는 것은 아니다.The ligand compound represented by
또한 상기 화학식 1로 표시되는 화합물의 일반적인 제조방법은 다음과 같지만, 이에 한정되는 것은 아니다. In addition, the general method for preparing a compound represented by
상기 방법에 따라 제조된 화학식 1로 표시되는 화합물은, 금속과 킬레이트를 형성할 수 있는 리간드 화합물일 수 있다. The compound represented by
본 발명의 일 실시예에 따르면, 상기 화학식 1로 표시되는 리간드 화합물은 하기 화학식 1a 로 표시되는 화합물일 수 있다.According to one embodiment of the present invention, the ligand compound represented by
[화학식 1a] [Formula 1a]
상기 화학식 1a로 표시되는 리간드 화합물은 예를 들어, 하기 반응식 1과 같은 방법으로 합성할 수 있으나 본 발명이 이에 한정되는 것은 아니다.The ligand compound represented by Formula 1a may be synthesized, for example, by the same method as in
[반응식 1][Reaction Scheme 1]
본 발명의 전이금속 화합물은 상기 화학식 1로 표시되는 화합물을 리간드로 하여 4족 전이금속이 배위 결합된 형태이며, 하기 화학식 2로 표시될 수 있다.The transition metal compound of the present invention is a compound in which a compound represented by the formula (1) is a ligand and a transition metal of a group 4 transition metal is coordinately bonded and can be represented by the following formula (2).
[화학식 2](2)
상기 화학식 2에서, In
M은 4족의 전이금속이고;M is a transition metal of Group 4;
K는 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아릴알킬기, 탄소수 1 내지 20의 알킬아미노기, 탄소수 6 내지 20의 아릴 아미노기 및 탄소수 1 내지 20의 알킬리덴기로 이루어진 군에서 선택된 1종이고;K is halogen, alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group having 7 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, alkyl having 1 to 20 carbon atoms An amino group, an aryl amino group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms;
n은 2 내지 3의 정수이며;n is an integer from 2 to 3;
m, R1, R2, R3, R4, R5 및 R6는 상기 화학식 1에서 정의한 바와 같다.m, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same as defined in
본 발명의 일 실시예에 따르면, 상기 M에 해당하는 4족의 전이금속으로는 Ti, Zr, Hf 등이 있을 수 있으나, 이에 한정되는 것은 아니다.According to an embodiment of the present invention, the transition metal of Group 4 corresponding to M may be Ti, Zr, Hf or the like, but is not limited thereto.
또한 본 발명의 일 실시예에 따르면, 상기 화학식 2로 표시되는 전이금속 화합물은 하기 구조식 중 하나로 표시될 수 있으나, 이에 한정되는 것은 아니다.According to an embodiment of the present invention, the transition metal compound represented by
상기 구조식에서, Me는 메틸기(methyl), Bn은 벤질기(benzyl)를 가리킨다. In the above structural formula, Me represents a methyl group and Bn represents a benzyl group.
본 발명의 일 실시예에 따르면, 상기 화학식 2로 표시되는 전이금속 화합물은 하기 화학식 2a 로 표시되는 화합물일 수 있다.According to an embodiment of the present invention, the transition metal compound represented by
[화학식 2a](2a)
상기 화학식 2a로 표시되는 전이금속 화합물은 예를 들어, 하기 반응식 2와 같은 방법으로 합성할 수 있으나 이에 한정되는 것은 아니다.The transition metal compound represented by Chemical Formula 2a may be synthesized, for example, by the same method as in
[반응식 2][Reaction Scheme 2]
본 발명에 따른 신규한 구조의 리간드 화합물 및 이를 포함하는 전이금속 화합물은 올레핀계 중합체를 제조하는데 있어 중합 반응의 촉매로 사용될 수 있다. The ligand compound of the novel structure and the transition metal compound including the same according to the present invention can be used as a catalyst for the polymerization reaction in preparing the olefin polymer.
보다 구체적으로, 본 발명에 따른 전이금속 화합물은 단독으로 또는 상기 전이금속 화합물 이외에 하기 화학식 3, 화학식 4 또는 화학식 5로 표시되는 조촉매 화합물 중 1종 이상을 추가로 포함하는 조성물 형태로, 중합 반응의 촉매로 사용될 수 있다.More specifically, the transition metal compound according to the present invention alone or in addition to the transition metal compound in the form of a composition further comprising one or more of the promoter compounds represented by the following formula (3), (4) or (5), the polymerization reaction It can be used as a catalyst.
[화학식 3](3)
-[Al(R7)-O]n--[Al (R7) -O] n-
상기 화학식 3에서,In Formula 3,
R7은 서로 동일하거나 다를 수 있으며, 각각 독립적으로 할로겐; 탄소수 1 내지 20의 탄화수소; 또는 할로겐으로 치환된 탄소수 1 내지 20의 탄화수소이고;R7 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
n은 2 이상의 정수이며;n is an integer of 2 or more;
[화학식 4][Chemical Formula 4]
J(R7)3 J (R7) 3
상기 화학식 4에서,In Chemical Formula 4,
R7은 상기 화학식 3에서 정의된 바와 같고;R7 is as defined in Formula 3 above;
J는 알루미늄 또는 보론이며;J is aluminum or boron;
[화학식 5][Chemical Formula 5]
[E-H]+[ZA4]- 또는 [E]+[ZA4]- [EH] + [ZA 4] - or [E] + [ZA 4] -
상기 화학식 5에서,In Formula 5,
E는 중성 또는 양이온성 루이스 염기이고;E is a neutral or cationic Lewis base;
H는 수소 원자이며;H is a hydrogen atom;
Z는 13족 원소이고;Z is a
A는 서로 동일하거나 다를 수 있으며, 각각 독립적으로 1 이상의 수소 원자가 할로겐, 탄소수 1 내지 20의 탄화수소, 알콕시 또는 페녹시로 치환 또는 비치환된 탄소수 6 내지 20의 아릴기 또는 탄소수 1 내지 20의 알킬기이다.A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .
상기 화학식 3으로 표시되는 화합물의 예로는 메틸알루미녹산, 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산 등이 있으며, 더욱 바람직한 화합물은 메틸알루미녹산이다.Examples of the compound represented by the general formula (3) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.
상기 화학식 4로 표시되는 화합물의 예로는 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 트리이소프로필알루미늄, 트리-s-부틸알루미늄, 트리사이클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 트리옥틸알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론, 트리부틸보론 등이 포함되며, 더욱 바람직한 화합물은 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄 중에서 선택된다.Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
상기 화학식 5로 표시되는 화합물의 예로는 트리에틸암모니움테트라페닐보론, 트리부틸암모니움테트라페닐보론, 트리메틸암모니움테트라페닐보론, 트리프로필암모니움테트라페닐보론, 트리메틸암모니움테트라(p-톨릴)보론, 트리메틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리메틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리부틸암모니움테트라펜타플로로페닐보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라펜타플로로페닐보론, 디에틸암모니움테트라펜타플로로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리메틸포스포늄테트라페닐보론, 트리에틸암모니움테트라페닐알루미늄, 트리부틸암모니움테트라페닐알루미늄, 트리메틸암모니움테트라페닐알루미늄, 트리프로필암모니움테트라페닐알루미늄, 트리메틸암모니움테트라(p-톨릴)알루미늄, 트리프로필암모니움테트라(p-톨릴)알루미늄, 트리에틸암모니움테트라(o,p-디메틸페닐)알루미늄, 트리부틸암모니움테트라(p-트리플로로메틸페닐)알루미늄, 트리메틸암모니움테트라(p-트리플로로메틸페닐)알루미늄, 트리부틸암모니움테트라펜타플로로페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라펜타플로로페닐알루미늄, 디에틸암모니움테트라펜타테트라페닐알루미늄, 트리페닐포스포늄테트라페닐알루미늄, 트리메틸포스포늄테트라페닐알루미늄, 트리프로필암모니움테트라(p-톨릴)보론, 트리에틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리페닐카보니움테트라(p-트리플로로메틸페닐)보론, 트리페닐카보니움테트라펜타플로로페닐보론 등이 있다.Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra (p- Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.
바람직하게는 알룸옥산을 사용할 수 있으며, 더 바람직하게는 알킬알룸옥산인 메틸알룸옥산(MAO)이다.Preferably, alumoxane can be used, more preferably methylalumoxane (MAO) which is alkylalumoxane.
상기 촉매 조성물은, 첫 번째 방법으로서 1) 상기 화학식 2로 표시되는 전이금속 화합물과 상기 화학식 3 또는 화학식 4로 표시되는 화합물을 접촉시켜 혼합물을 얻는 단계; 및 2) 상기 혼합물에 상기 화학식 5로 표시되는 화합물을 첨가하는 단계를 포함하는 방법으로 제조될 수 있다.The catalyst composition may include the steps of 1) contacting a transition metal compound represented by
또한, 상기 촉매 조성물은, 두 번째 방법으로서 상기 화학식 2로 표시되는 전이금속 화합물과 상기 화학식 3으로 표시되는 화합물을 접촉시키는 방법으로 제조될 수 있다.In addition, the catalyst composition may be prepared by a method of contacting the transition metal compound represented by
상기 촉매 조성물의 제조방법 중에서 첫 번째 방법의 경우에, 상기 화학식 2로 표시되는 전이금속 화합물/상기 화학식 3 또는 화학식 4로 표시되는 화합물의 몰 비율은 1/5,000 내지 1/2이 바람직하고, 더욱 바람직하게는 1/1,000 내지 ~ 1/10 이고, 가장 바람직하게는 1/500 내지 1/20이다. 상기 화학식 2로 표시되는 전이금속 화합물/상기 화학식 3 또는 화학식 4로 표시되는 화합물의 몰 비율이 1/2을 초과하는 경우에는 알킬화제의 양이 매우 작아 금속 화합물의 알킬화가 완전히 진행되지 못하는 문제가 있고, 몰 비율이 1/5,000 미만인 경우에는 금속 화합물의 알킬화는 이루어지지만, 남아있는 과량의 알킬화제와 상기 화학식 5의 활성화제 간의 부반응으로 인하여 알킬화된 금속 화합물의 활성화가 완전히 이루어지지 못하는 문제가 있다. 또한, 상기 화학식 2로 표시되는 전이금속 화합물/상기 화학식 5로 표시되는 화합물의 몰 비율은 1/25 내지 1이 바람직하고, 더욱 바람직하게는 1/10 내지 1이고, 가장 바람직하게는 1/5 내지 1이다. 상기 화학식 2로 표시되는 전이금속 화합물/상기 화학식 5로 표시되는 화합물의 몰 비율이 1을 초과하는 경우에는 활성화제의 양이 상대적으로 적어 금속 화합물의 활성화가 완전히 이루어지지 못해 생성되는 촉매 조성물의 활성도가 떨어지는 문제가 있고, 몰 비율이 1/25 미만인 경우에는 금속 화합물의 활성화가 완전히 이루어지지만, 남아 있는 과량의 활성화제로 촉매 조성물의 단가가 경제적이지 못하거나 생성되는 고분자의 순도가 떨어지는 문제가 있다.In the case of the first method of the method for preparing the catalyst composition, the molar ratio of the transition metal compound represented by the formula (2) / compound represented by the formula (3) or formula (4) is preferably 1 / 5,000 to 1/2, more Preferably it is 1 / 1,000-1/10, Most preferably, it is 1/500-1/20. When the molar ratio of the transition metal compound represented by the formula (2) / compound represented by the formula (3) or formula (4) is more than 1/2, the amount of the alkylating agent is so small that there is a problem that alkylation of the metal compound does not proceed completely. In the case where the molar ratio is less than 1 / 5,000, alkylation of the metal compound is performed, but there is a problem that activation of the alkylated metal compound is not completely performed due to a side reaction between the remaining excess alkylating agent and the activator of Formula 5. In addition, the molar ratio of the transition metal compound represented by
상기 촉매 조성물의 제조방법 중에서 두 번째 방법의 경우에, 상기 화학식 2로 표시되는 전이금속 화합물/화학식 3으로 표시되는 화합물의 몰 비율은 1/10,000 내지 1/10 이 바람직하며, 더욱 바람직하게는 1/5,000 내지 1/100이고, 가장 바람직하게는 1/3,000 내지 1/500이다. 상기 몰 비율이 1/10 을 초과하는 경우에는 활성화제의 양이 상대적으로 적어 금속 화합물의 활성화가 완전히 이루어지지 못해 생성되는 촉매 조성물의 활성도가 떨어지는 문제가 있고, 1/10,000 미만인 경우에는 금속 화합물의 활성화가 완전히 이루어지지만, 남아 있는 과량의 활성화제로 촉매 조성물의 단가가 경제적이지 못하거나 생성되는 고분자의 순도가 떨어지는 문제가 있다.In the case of the second method of the preparation method of the catalyst composition, the molar ratio of the transition metal compound represented by
상기 촉매 조성물의 제조시에 반응 용매로서 펜탄, 헥산, 헵탄 등과 같은 탄화수소계 용매, 또는 벤젠, 톨루엔 등과 같은 방향족계 용매가 사용될 수 있다.In preparing the catalyst composition, a hydrocarbon solvent such as pentane, hexane, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used.
또한, 상기 촉매 조성물은 상기 전이금속 화합물과 조촉매 화합물을 담체에 담지된 형태로 포함할 수 있다.In addition, the catalyst composition may include the transition metal compound and the cocatalyst compound in a form supported on a carrier.
또한, 상기 전이금속 화합물을 포함하는 촉매 조성물의 존재 하에 올레핀계 단량체를 중합하는 중합 반응은 하나의 연속식 슬러리 중합 반응기, 루프 슬러리 반응기, 기상 반응기 또는 용액 반응기 등을 이용하여, 용액 중합 공정, 슬러리 공정 또는 기상 공정에 의해 수행될 수 있다. 또한 하나의 올레핀 단량체로 호모중합하거나 또는 2종 이상의 단량체로 공중합하여 진행할 수 있다.In addition, the polymerization reaction for polymerizing the olefin monomer in the presence of the catalyst composition comprising the transition metal compound is a solution polymerization process, a slurry using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor or solution reactor, etc. It may be carried out by a process or a gas phase process. It can also proceed by homopolymerization with one olefin monomer or copolymerization with two or more monomers.
상기 폴리올레핀의 중합은 약 25 내지 약 500℃의 온도 및 약 1 내지 약 100 kgf/cm2에서 반응시켜 수행할 수 있다. 구체적으로, 상기 폴리올레핀의 중합은 약 25 내지 약 500℃, 바람직하게는 약 25 내지 200℃, 보다 바람직하게는 약 50 내지 100℃의 온도에서 수행할 수 있다. 또한 반응 압력은 약 1 내지 약 100 kgf/cm2, 바람직하게는 약 1 내지 약50 kgf/cm2, 보다 바람직하게는 약 5 내지 약 40 kgf/cm2에서 수행할 수 있다. The polymerization of the polyolefin may be carried out by reacting at a temperature of about 25 to about 500 ℃ and about 1 to about 100 kgf / cm 2 . Specifically, the polymerization of the polyolefin may be carried out at a temperature of about 25 to about 500 ℃, preferably about 25 to 200 ℃, more preferably about 50 to 100 ℃. The reaction pressure can also be carried out at about 1 to about 100 kgf / cm 2 , preferably at about 1 to about 50 kgf / cm 2 , more preferably at about 5 to about 40 kgf / cm 2 .
본 발명에 따라 제조되는 폴리올레핀에 있어서, 상기 올레핀계 단량체의 구체적인 예로는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센, 1-헥사데센, 1-아이토센 등이 있으며, 이들을 2종 이상 혼합하여 공중합한 공중합체일 수 있다.In the polyolefin prepared according to the present invention, specific examples of the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- itocene and the like, may be a copolymer copolymerized by mixing two or more thereof.
상기 폴리올레핀은 프로필렌 중합체일 수 있으나, 이에만 한정되는 것은 아니다.The polyolefin may be a propylene polymer, but is not limited thereto.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 기재한다. 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 본 발명의 범위를 한정하고자 하는 것은 아니다.
Hereinafter, preferred embodiments of the present invention will be described to facilitate understanding of the present invention. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.
<실시예><Examples>
<리간드 화합물의 합성>Synthesis of Ligand Compound
실시예Example 1 One
((
EE
)-N-((1,2,3,4-) -N-((1,2,3,4-
TetrahydroTetratrahydro
-2--2-
phenylquinolinphenylquinolin
-8--8-
ylyl
) () (
phenylphenyl
) )
methylene메틸렌
)-2,6-diisopropylbenzenamine의 제조Preparation of) -2,6-diisopropylbenzenamine
실시예Example 1-1 1-1
PhenylPhenyl (2-(2- phenylphenyl -1,2,3,4--1,2,3,4- tetrahydroquinolintetrahydroquinolin -8--8- ylyl )methanone 의 제조Preparation of methanone
250ml 2-neck 둥근 바닥 플라스크에 수냉식 응축기(water-cooled condenser)를 연결한 후 2-phenyl 1,2,3,4-tetrahydroquinoline (10g, 48mmol)을 넣고 정제 톨루엔(toluene) 48mL를 가하여 녹였다. 이 용액을 0℃로 식힌 후, BCl3 (53mL, 53mmol, 1M solution in methylene chloride)를 가하고 교반시켰다. 벤조니트릴(benzonitrile) (10mL, 96mmol)과 AlCl3(6.4g, 48mmol)을 가하고 110℃에서 밤새 환류(reflux)하였다. 이후 110℃에서 진공 건조하여 용매를 제거하고 상온으로 식힌 후 4N HCl 100mL를 넣고 80℃에서 1시간 동안 교반하였다. A water-cooled condenser was connected to a 250 ml 2-neck round bottom flask, and 2-
상온으로 식힌 후 메틸렌 클로라이드(methylene chloride)로 반응물을 녹인 후 유기층을 모았다. 모아진 유기층을 분별 깔때기(separatory funnel)로 옮기고 물을 가한 후 1N KOH를 가하여 물층의 pH가 9~10이 되도록 조절하였다. 추출 후 모은 유기층은 brine으로 세정하고 Na2SO4로 건조한 후 여과하고 농축하여 노란색 고체의 조 생성물(crude product)을 얻었다. 이를 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정한 후 이를 여과하여 노란색 결정인 phenyl(2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl)methanone을 수득하였다. (수득률 94%)
After cooling to room temperature, the reactants were dissolved with methylene chloride, and the organic layers were collected. The collected organic layers were transferred to a separatory funnel, water was added, and 1N KOH was added to adjust the pH of the water layer to 9-10. The extracted organic layer was extracted with brine, dried over Na 2 SO 4 , filtered and concentrated to give a crude product as a yellow solid. It was dissolved in a small amount of methylene chloride, and recrystallized by adding an excess of methanol. The resultant was filtered to obtain phenyl (2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl) methanone as yellow crystals. (94% yield)
실시예Example 1-2 1-2
(( EE )-N-((1,2,3,4-) -N-((1,2,3,4- TetrahydroTetratrahydro -2--2- phenylquinolinphenylquinolin -8--8- ylyl ) () ( phenylphenyl ) ) methylene메틸렌 )-2,6-diisopropylbenzenamine의 제조Preparation of) -2,6-diisopropylbenzenamine
100ml 2-neck 둥근 바닥 플라스크(rbf)에 수냉식 응축기(water-cooled condenser)를 연결한 후 실시예 1-1의 phenyl(2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl)methanone (10g, 48mmol)을 넣고 정제 톨루엔(toluene) 21mL를 가하여 녹였다. 여기에, 2,6-diisopropylaniline (2.9mL, 32mmol)을 가하고 상온에서 10분간 교반하였다. 이후 TiCl4 (6.4mL, 6.4mmol, 1M solution in toluene)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 1일 동안 reflux하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르(diethyl ether) 50mL를 가하여 충분히 교반한 후 celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물을 소량의 메틸렌 클로라이드(methylene chloride)에 녹이고 과량의 메탄올(methanol)을 가하여 재결정하였다. 이를 여과하여 노란색 결정의 (E)-N-((1,2,3,4-Tetrahydro-2-phenylquinolin-8-yl) (phenyl) methylene)-2,6-diisopropylbenzenamine를 수득하였다. (수득율 88%)Phenyl (2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl) methanone of Example 1-1 after connecting a water-cooled condenser to a 100 ml 2-neck round bottom flask (rbf) (10 g, 48 mmol) was added and 21 mL of purified toluene was added thereto and dissolved. 2,6-diisopropylaniline (2.9 mL, 32 mmol) was added thereto, and the mixture was stirred at room temperature for 10 minutes. Then TiCl 4 (6.4mL, 6.4mmol, 1M solution in toluene) was added and stirred at room temperature for 1 hour and reflux at 110 ℃ for 1 day. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding an excess of methanol. This was filtered to give ( E ) -N-((1,2,3,4-Tetrahydro-2-phenylquinolin-8-yl) (phenyl) methylene) -2,6-diisopropylbenzenamine as yellow crystals. (88% yield)
상기 실시예 1에서 합성된 리간드 화합물의 NMR spectrum을 도 1에 나타내었다.
An NMR spectrum of the ligand compound synthesized in Example 1 is shown in FIG. 1.
실시예Example 2 2
(( EE )-) - NN -((1,2,3,4--((1,2,3,4- tetrahydrotetrahydro -2--2- phenylquinolinphenylquinolin -8-yl)(phenyl)methylene)benzenamine의 제조Preparation of -8-yl) (phenyl) methylene) benzenamine
100ml 2-neck 둥근 바닥 플라스크에 수냉식 응축기를 연결한 후 실시예 1-1의 phenyl(2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl)methanone 2 g (6.4 mmol)을 넣고 정제 톨루엔 21 mL를 가하여 녹였다. 이에 aniline 2.9 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 4.8 mL (1 M solution in toluene, 4.8 mmol, 0.75 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 2.2 g (5.6 mmol, 88 % 수율)의 노란색 고체인 결과물을 얻었다.Connect a water-cooled condenser to a 100 ml 2-neck round bottom flask, add 2 g (6.4 mmol) of phenyl (2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl) methanone of Example 1-1 21 mL of toluene was added and dissolved. 2.9 mL (32 mmol, 5 equivalents) of aniline was added thereto, and the mixture was stirred at room temperature for 10 minutes. After that, 4.8 mL of TiCl 4 solution (1 M solution in toluene, 4.8 mmol, 0.75 equiv) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 2.2 g (5.6 mmol, 88% yield) of a yellow solid.
상기 실시예 2에서 합성된 리간드 화합물의 NMR spectrum을 도 2에 나타내었다.
An NMR spectrum of the ligand compound synthesized in Example 2 is shown in FIG. 2.
실시예Example 3 3
(( EE )-) - NN -((1,2,3,4--((1,2,3,4- tetrahydrotetrahydro -2--2- phenylquinolinphenylquinolin -8--8- ylyl )() ( phenylphenyl )) methylene메틸렌 )-2,6-dimethylbenzenamine의 제조Preparation of) -2,6-dimethylbenzenamine
100ml 2-neck 둥근 바닥 플라스크)에 수냉식 응축기를 연결한 후 실시예 1-1의 phenyl(2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl)methanone 2 g (6.4 mmol)을 넣고 정제 톨루엔 21 mL를 가하여 녹인다. 이에 2,6-dimethylaniline 3.3 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 Celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 2.1 g (5.2 mmol, 81 % 수율)의 노란색 고체인 결과물을 얻었다.Connect a water-cooled condenser to a 100 ml 2-neck round bottom flask), and add 2 g (6.4 mmol) of phenyl (2-phenyl-1,2,3,4-tetrahydroquinolin-8-yl) methanone of Example 1-1. Add 21 mL of purified toluene to dissolve. 3.3 mL (32 mmol, 5 equivalents) of 2,6-dimethylaniline was added thereto, followed by stirring at room temperature for 10 minutes. After that, 6.4 mL of TiCl 4 solution (1 M solution in toluene, 6.4 mmol, 1 equivalent) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with Celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding ê * amount of methanol. This was filtered to give 2.1 g (5.2 mmol, 81% yield) of a yellow solid.
상기 실시예 3에서 합성된 리간드 화합물의 NMR spectrum을 도 3에 나타내었다.
An NMR spectrum of the ligand compound synthesized in Example 3 is shown in FIG. 3.
실시예Example 4 4
(( EE )-) - NN -((1,2,3,4--((1,2,3,4- tetrahydrotetrahydro -2-(1--2- (1- naphthylnaphthyl )) quinolinquinolin -8-yl)(phenyl)methylene)-2,6-dimethyl-benzenamine의 제조Preparation of -8-yl) (phenyl) methylene) -2,6-dimethyl-benzenamine
실시예Example 4-1 4-1
(2-((2-( NaphthalenNaphthalen -1--One- ylyl )-1,2,3,4-) -1,2,3,4- tetrahydroquinolintetrahydroquinolin -8--8- ylyl )() ( phenylphenyl )) methanone메탄one 의 제조Manufacturing
250 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기를 연결한 후 2-(naphthen-1-yl)-1,2,3,4-tetrahydroquinoline 12 g (48 mmol)를 넣고 정제 toluene 48 mL를 가하여 녹였다. 이 용액을 0℃로 식힌 후 BCl3 53 mL (1 M solution in methylene chloride, 53 mmol, 1 당량)를 가하고 교반시켰다. 벤조니트릴 10 mL (96 mmol, 2 당량)와 AlCl3 6.4 g (48 mmol, 1 당량)을 가하고 110 ℃에서 밤새 환류하였다. 반응이 끝나면 110 ℃에서 진공 건조하여 용매를 제거하고 상온으로 식힌 후 4 N HCl (100 mL)을 넣고 80 ℃에서 1시간 동안 교반하였다. A water-cooled condenser was connected to a 250 mL 2-neck round bottom flask, and 12 g (48 mmol) of 2- (naphthen-1-yl) -1,2,3,4-tetrahydroquinoline was added and dissolved by adding 48 mL of purified toluene. After the solution was cooled to 0 ° C., 53 mL of BCl 3 (1 M solution in methylene chloride, 53 mmol, 1 equivalent) was added thereto, followed by stirring. 10 mL (96 mmol, 2 equiv) of benzonitrile and 6.4 g (48 mmol, 1 equiv) of AlCl 3 were added and refluxed at 110 ° C. overnight. After the reaction was dried in vacuo at 110 ℃ to remove the solvent, cooled to room temperature, 4 N HCl (100 mL) was added and stirred at 80 ℃ for 1 hour.
상온으로 식힌 후 메틸렌 클로라이드로 반응물을 녹인 후 유기층을 모았다. 모아진 유기층을 분별 깔때기로 옮기고 물을 가한 후 1N KOH를 가하여 물층의 pH가 9~10이 되도록 조절하였다. 추출 후 모은 유기층은 brine으로 씻고, Na2SO4로 건조한 후 여과하고 농축하여 노란색 고체의 조 생성물을 얻었다. 이를 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정한 후 이를 여과하여 15.7 g (43 mmol, 90 % 수율)의 노란색 고체인 결과물을 얻었다.After cooling to room temperature, the reactant was dissolved with methylene chloride, and then the organic layer was collected. The collected organic layers were transferred to a separatory funnel, and water was added thereto, followed by addition of 1N KOH to adjust the pH of the water layer to 9-10. The extracted organic layer was extracted with brine, dried over Na 2 SO 4 , filtered and concentrated to give a crude product as a yellow solid. It was dissolved in a small amount of methylene chloride and recrystallized by adding an excess of methanol. The resultant was filtered to give 15.7 g (43 mmol, 90% yield) of a yellow solid.
실시예Example 4-2 4-2
(( EE )-) - NN -((1,2,3,4--((1,2,3,4- tetrahydrotetrahydro -2-(1--2- (1- naphthylnaphthyl )) quinolinquinolin -8-yl)(phenyl)methylene)-2,6-dimethyl-benzenamine의 제조Preparation of -8-yl) (phenyl) methylene) -2,6-dimethyl-benzenamine
100 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기를 연결한 후 실시예 4-1의 (2-(naphthalen-1-yl)-1,2,3,4-tetrahydroquinolin-8-yl)(phenyl)methanone 2.3 g (6.4 mmol)을 넣고 정제 톨루엔21 mL를 가하여 녹였다. 이에 2,6-dimethylaniline 3.3 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 Celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 2.5 g (5.4 mmol, 85 % 수율)의 노란색 고체인 결과물을 얻었다.The water-cooled condenser was connected to a 100 mL 2-neck round bottom flask, followed by (2- (naphthalen-1-yl) -1,2,3,4-tetrahydroquinolin-8-yl) (phenyl) methanone of Example 4-1. 2.3 g (6.4 mmol) was added thereto and dissolved in 21 mL of purified toluene. 3.3 mL (32 mmol, 5 equivalents) of 2,6-dimethylaniline was added thereto, followed by stirring at room temperature for 10 minutes. After that, 6.4 mL of TiCl 4 solution (1 M solution in toluene, 6.4 mmol, 1 equivalent) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with Celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 2.5 g (5.4 mmol, 85% yield) of a yellow solid.
상기 실시예 4에서 합성된 리간드 화합물의 NMR spectrum을 도 4에 나타내었다.
An NMR spectrum of the ligand compound synthesized in Example 4 is shown in FIG. 4.
실시예Example 5 5
(( EE )-) - NN -((1,2,3,4--((1,2,3,4- tetrahydrotetrahydro -2-(1--2- (1- naphthylnaphthyl )) quinolinquinolin -8-yl)(phenyl)methylene)-2,6-diisopropyl-benzenamine의 제조Preparation of -8-yl) (phenyl) methylene) -2,6-diisopropyl-benzenamine
100 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기를 연결한 후 실시예 4-1의 (2-(naphthalen-1-yl)-1,2,3,4-tetrahydroquinolin-8-yl)(phenyl)methanone 2.3 g (6.4 mmol)을 넣고 정제 톨루엔 21 mL를 가하여 녹인다. 이에 2,6-diisopropylaniline 3.9 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 당량)을 가하고 상온에서 1시간 동안 교반한 후 110 ℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 Celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 1.7 g (3.3 mmol, 51 % 수율)의 노란색 고체인 결과물을 얻었다.The water-cooled condenser was connected to a 100 mL 2-neck round bottom flask, followed by (2- (naphthalen-1-yl) -1,2,3,4-tetrahydroquinolin-8-yl) (phenyl) methanone of Example 4-1. 2.3 g (6.4 mmol) was added and dissolved in 21 mL of purified toluene. 3.9 mL (32 mmol, 5 equivalents) of 2,6-diisopropylaniline was added thereto, followed by stirring for 10 minutes at room temperature. After that, 6.4 mL of TiCl 4 solution (1 M solution in toluene, 6.4 mmol, 1 equivalent) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with Celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 1.7 g (3.3 mmol, 51% yield) of a yellow solid.
상기 실시예 5에서 합성된 리간드 화합물의 NMR spectrum을 도 5에 나타내었다.
An NMR spectrum of the ligand compound synthesized in Example 5 is shown in FIG. 5.
실시예Example 6 6
(( EE )-) - NN -(- ( PhenylPhenyl (2-(2- phenylindolinphenylindolin -7--7- ylyl )methylene)methylene) benzenaminebenzenamine 의 제조Manufacturing
실시예Example 6-1 6-1
PhenylPhenyl (2-(2- phenylindolinphenylindolin -7--7- ylyl )methanone의 제조Preparation of methanone
250 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기를 연결한 후 2-phenylindoline 9.4 g (48 mmol)를 넣고 정제 톨루엔48 mL를 가하여 녹였다. 이 용액을 0℃로 식힌 후 BCl3 53 mL (1 M solution in methylene chloride, 53 mmol, 1 당량)를 가하고 교반시켰다. 벤조니트릴10 mL (96 mmol, 2 당량)와 AlCl3 6.4 g (48 mmol, 1 당량)을 가하고 110 ℃에서 밤새 환류하였다. 반응이 끝나면 110℃에서 진공 건조하여 용매를 제거하고 상온으로 식힌 후 4 N HCl (100 mL)을 넣고 80℃에서 1시간 동안 교반하였다. 상온으로 식힌 후 메틸렌 클로라이드로 반응물을 녹인 후 유기층을 모았다. 모아진 유기층을 분별 깔때기로 옮기고 물을 가한 후 1N KOH를 가하여 물층의 pH가 9~10이 되도록 조절하였다. 추출 후 모은 유기층은 brine으로 세정하고 Na2SO4로 건조한 후 여과하고 농축하여 노란색 고체의 조 생성물을 얻었다. 이를 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정한 후 이를 여과하여 14 g (정량 수율)의 노란색 고체인 결과물을 얻었다.After connecting a water-cooled condenser to a 250 mL 2-neck round bottom flask, 9.4 g (48 mmol) of 2-phenylindoline was added, and 48 mL of purified toluene was added to dissolve it. After the solution was cooled to 0 ° C., 53 mL of BCl 3 (1 M solution in methylene chloride, 53 mmol, 1 equivalent) was added thereto, followed by stirring. 10 mL (96 mmol, 2 equiv) of benzonitrile and 6.4 g (48 mmol, 1 equiv) of AlCl 3 were added and refluxed at 110 ° C. overnight. After the reaction was dried in vacuo at 110 ℃ to remove the solvent, cooled to room temperature, 4 N HCl (100 mL) was added and stirred at 80 ℃ for 1 hour. After cooling to room temperature, the reactant was dissolved with methylene chloride, and then the organic layer was collected. The collected organic layers were transferred to a separatory funnel, and water was added thereto, followed by addition of 1N KOH to adjust the pH of the water layer to 9-10. The organic layer collected after extraction was washed with brine, dried over Na 2 SO 4 , filtered and concentrated to give a crude product as a yellow solid. It was dissolved in a small amount of methylene chloride and recrystallized by adding an excess of methanol, which was then filtered to give 14 g (quantitative yield) of a yellow solid.
실시예Example 6-2 6-2
(( EE )-) - NN -(- ( PhenylPhenyl (2-(2- phenylindolinphenylindolin -7--7- ylyl )methylene)methylene) benzenaminebenzenamine 의 제조Manufacturing
100 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기에 연결한 후 실시예6-1의 phenyl(2-phenylindolin-7-yl)methanone 1.9 g (6.4 mmol)을 넣고 정제 톨루엔 21 mL를 가하여 녹였다. 이에 aniline 2.9 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 4.8 mL (1 M solution in toluene, 4.8 mmol, 0.75 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 2.1 g (5.6mmol, 88 % 수율)의 노란색 고체인 결과물을 얻었다.A 100 mL 2-neck round bottom flask was connected to a water-cooled condenser, and then 1.9 g (6.4 mmol) of phenyl (2-phenylindolin-7-yl) methanone of Example 6-1 was added thereto and dissolved in 21 mL of purified toluene. 2.9 mL (32 mmol, 5 equivalents) of aniline was added thereto, and the mixture was stirred at room temperature for 10 minutes. After that, 4.8 mL of TiCl 4 solution (1 M solution in toluene, 4.8 mmol, 0.75 equiv) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 2.1 g (5.6 mmol, 88% yield) of a yellow solid.
상기 실시예 6에서 합성된 리간드 화합물의 NMR spectrum을 도 6에 나타내었다.
An NMR spectrum of the ligand compound synthesized in Example 6 is shown in FIG. 6.
실시예Example 7 7
(( EE )-) - NN -(- ( PhenylPhenyl (2-(2- phenylindolinphenylindolin -7--7- ylyl )methylene)-2,6-methylene) -2,6- dimethylbenzenaminedimethylbenzenamine 의 제조Manufacturing
100 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기에 연결한 후 실시예6-1의 phenyl(2-phenylindolin-7-yl)methanone 1.9 g (6.4 mmol)을 넣고 정제 톨루엔21 mL를 가하여 녹였다. 이에 2,6-dimethylaniline 3.3 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 교반하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 2.0 g (5.1 mmol, 79 % 수율)의 노란색 고체인 결과물을 얻었다.A 100 mL 2-neck round bottom flask was connected to a water-cooled condenser, and then 1.9 g (6.4 mmol) of phenyl (2-phenylindolin-7-yl) methanone of Example 6-1 was added and dissolved in 21 mL of purified toluene. 3.3 mL (32 mmol, 5 equivalents) of 2,6-dimethylaniline was added thereto, followed by stirring at room temperature for 10 minutes. After that, 6.4 mL of TiCl 4 solution (1 M solution in toluene, 6.4 mmol, 1 equivalent) was added thereto, stirred at room temperature for 1 hour, and then stirred at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 2.0 g (5.1 mmol, 79% yield) of a yellow solid.
상기 실시예 7에서 합성된 리간드 화합물의 NMR spectrum을 도 7에 나타내었다.
An NMR spectrum of the ligand compound synthesized in Example 7 is shown in FIG. 7.
실시예Example 8 8
(( EE )-) - NN -(- ( phenylphenyl (2-(2- phenylindolinphenylindolin -7--7- ylyl )methylene)-2,6-diisopropylbenzenamine의 제조Preparation of methylene) -2,6-diisopropylbenzenamine
100 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기에 연결한 후 실시예6-1의 phenyl(2-phenylindolin-7-yl)methanone 1.9 g (6.4 mmol)을 넣고 정제 톨루엔21 mL를 가하여 녹였다. 이에 2,6-diisopropylaniline 3.9 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 교반하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 1.6 g (3.5 mmol, 55 % 수율)의 노란색 고체인 결과물을 얻었다.A 100 mL 2-neck round bottom flask was connected to a water-cooled condenser, and then 1.9 g (6.4 mmol) of phenyl (2-phenylindolin-7-yl) methanone of Example 6-1 was added and dissolved in 21 mL of purified toluene. 3.9 mL (32 mmol, 5 equivalents) of 2,6-diisopropylaniline was added thereto, followed by stirring for 10 minutes at room temperature. After that, 6.4 mL of TiCl 4 solution (1 M solution in toluene, 6.4 mmol, 1 equivalent) was added thereto, stirred at room temperature for 1 hour, and then stirred at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 1.6 g (3.5 mmol, 55% yield) of a yellow solid.
상기 실시예 8에서 합성된 리간드 화합물의 NMR spectrum을 도 8에 나타내었다.
The NMR spectrum of the ligand compound synthesized in Example 8 is shown in FIG. 8.
실시예Example 9 9
(( EE )-) - NN -(- ( PhenylPhenyl (( indolinindolin -7--7- ylyl )methylene)methylene) benzenaminebenzenamine 의 제조Manufacturing
실시예Example 9-1 9-1
IndolinIndolin -7--7- ylyl (( phenylphenyl )methanone의 제조Preparation of methanone
250 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기에 연결한 후 indoline 5.7 g (48 mmol)를 넣고 정제 톨루엔48 mL를 가하여 녹였다. 이 용액을 0℃로 식힌 후 BCl3 53 mL (1 M solution in methylene chloride, 53 mmol, 1 당량)를 가하고 교반시켰다. 벤조니트릴10 mL (96 mmol, 2 당량)와 AlCl3 6.4 g (48 mmol, 1 당량)을 가하고 110℃에서 밤새 환류하였. 반응이 끝나면 110℃에서 진공 건조하여 용매를 제거하고 상온으로 식힌 후 4 N HCl (100 mL)을 넣고 80℃에서 1시간 동안 교반하였다. 3026After connecting to a water-cooled condenser in a 250 mL 2-neck round bottom flask, 5.7 g (48 mmol) of indoline was added, and 48 mL of purified toluene was added to dissolve it. After the solution was cooled to 0 ° C., 53 mL of BCl 3 (1 M solution in methylene chloride, 53 mmol, 1 equivalent) was added thereto, followed by stirring. 10 mL (96 mmol, 2 equiv) of benzonitrile and 6.4 g (48 mmol, 1 equiv) of AlCl 3 were added and refluxed at 110 ° C. overnight. After the reaction was dried in vacuo at 110 ℃ to remove the solvent, cooled to room temperature, 4 N HCl (100 mL) was added and stirred at 80 ℃ for 1 hour. 3026
상온으로 식힌 후 메틸렌 클로라이드로 반응물을 녹인 후 유기층을 모았다. 모아진 유기층을 분별 깔때기로 옮기고 물을 가한 후 1N KOH를 가하여 물층의 pH가 9~10이 되도록 조절하였다. 추출 후 모은 유기층은 brine으로 씻고, Na2SO4로 건조한 후 여과하고 농축하여 노란색 고체의 조 생성물을 얻었다. 이를 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정한 후 이를 여과하여 11 g (정량 수율)의 노란색 고체인 결과물을 얻었다.After cooling to room temperature, the reactant was dissolved with methylene chloride, and then the organic layer was collected. The collected organic layers were transferred to a separatory funnel, and water was added thereto, followed by addition of 1N KOH to adjust the pH of the water layer to 9-10. The extracted organic layer was extracted with brine, dried over Na 2 SO 4 , filtered and concentrated to give a crude product as a yellow solid. It was dissolved in a small amount of methylene chloride and recrystallized by adding an excess of methanol, which was then filtered to give 11 g (quantitative yield) of a yellow solid.
실시예Example 9-2 9-2
(( EE )-) - NN -(- ( PhenylPhenyl (( indolinindolin -7--7- ylyl )methylene)methylene) benzenaminebenzenamine 의 제조Manufacturing
100 mL 2-neck 둥근 바닥 플라스크)에 수냉식 응축기를 연결한 후 실시예9-1의 indolin-7-yl(phenyl)methanone 1.4 g (6.4 mmol)을 넣고 정제 톨루엔21 mL를 가하여 녹였다. 이에 aniline 2.9 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 4.8 mL (1 M solution in toluene, 4.8 mmol, 0.75 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 Celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 1.9 g (6.2mmol, 97 % 수율)의 노란색 고체인 결과물을 얻었다.100 mL 2-neck round bottom flask) was connected to a water-cooled condenser, and 1.4 g (6.4 mmol) of indolin-7-yl (phenyl) methanone of Example 9-1 was added and dissolved in 21 mL of purified toluene. 2.9 mL (32 mmol, 5 equivalents) of aniline was added thereto, and the mixture was stirred at room temperature for 10 minutes. After that, 4.8 mL of TiCl 4 solution (1 M solution in toluene, 4.8 mmol, 0.75 equiv) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with Celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 1.9 g (6.2 mmol, 97% yield) of a yellow solid.
상기 실시예 9에서 합성된 리간드 화합물의 NMR spectrum을 도 9에 나타내었다.
NMR spectrum of the ligand compound synthesized in Example 9 is shown in FIG. 9.
실시예Example 10 10
(( EE )-) - NN -(- ( PhenylPhenyl (( indolinindolin -7--7- ylyl )methylene)-2,6-methylene) -2,6- dimethylbenzenaminedimethylbenzenamine 의 제조Manufacturing
100 mL 2-neck 둥근 바닥 플라스크)에 수냉식 응축기를 연결한 후 실시예9-1의 indolin-7-yl(phenyl)methanone 1.4 g (6.4 mmol)을 넣고 정제 톨루엔21 mL를 가하여 녹였다. 이에 2,6-dimethylaniline 3.3 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 Celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 1.9 g (5.8 mmol, 91 % 수율)의 노란색 고체인 결과물을 얻었다.100 mL 2-neck round bottom flask) was connected to a water-cooled condenser, and 1.4 g (6.4 mmol) of indolin-7-yl (phenyl) methanone of Example 9-1 was added and dissolved in 21 mL of purified toluene. 3.3 mL (32 mmol, 5 equivalents) of 2,6-dimethylaniline was added thereto, followed by stirring at room temperature for 10 minutes. After that, 6.4 mL of TiCl 4 solution (1 M solution in toluene, 6.4 mmol, 1 equivalent) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with Celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 1.9 g (5.8 mmol, 91% yield) of a yellow solid.
상기 실시예 10에서 합성된 리간드 화합물의 NMR spectrum을 도 10에 나타내었다.
The NMR spectrum of the ligand compound synthesized in Example 10 is shown in FIG. 10.
실시예Example 11 11
(( EE )-) - NN -(- ( PhenylPhenyl (1,2,3,4-(1,2,3,4- tetrahydroquinolintetrahydroquinolin -7--7- ylyl )methylene)methylene) benzenaminebenzenamine 의 제조Manufacturing
실시예Example 11-1 11-1
PhenylPhenyl (1,2,3,4-(1,2,3,4- tetrahydroquinolintetrahydroquinolin -8--8- ylyl )methanone의 제조 Preparation of methanone
250 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기를 연결한 후 1,2,3,4-tetrahydroquinoline 6.4 g (48 mmol)를 넣고 정제 톨루엔48 mL를 가하여 녹였다. 이 용액을 0℃로 식힌 후 BCl3 53 mL (1 M solution in methylene chloride, 53 mmol, 1 당량)를 가하고 교반시켰다. 벤조니트릴10 mL (96 mmol, 2 당량)와 AlCl3 6.4 g (48 mmol, 1 당량)을 가하고 110℃에서 밤새 환류하였다. 반응이 끝나면 110 ℃에서 진공 건조하여 용매를 제거하고 상온으로 식힌 후 4 N HCl (100 mL)을 넣고 80 ℃에서 1시간 동안 교반하였다. A water-cooled condenser was connected to a 250 mL 2-neck round bottom flask, and 6.4 g (48 mmol) of 1,2,3,4-tetrahydroquinoline were added and dissolved by adding 48 mL of purified toluene. After the solution was cooled to 0 ° C., 53 mL of BCl 3 (1 M solution in methylene chloride, 53 mmol, 1 equivalent) was added thereto, followed by stirring. 10 mL (96 mmol, 2 equiv) of benzonitrile and 6.4 g (48 mmol, 1 equiv) of AlCl 3 were added and refluxed at 110 ° C. overnight. After the reaction was dried in vacuo at 110 ℃ to remove the solvent, cooled to room temperature, 4 N HCl (100 mL) was added and stirred at 80 ℃ for 1 hour.
상온으로 식힌 후 메틸렌 클로라이드로 반응물을 녹인 후 유기층을 모았다. 모아진 유기층을 분별 깔때기로 옮기고 물을 가한 후 1N KOH를 가하여 물층의 pH가 9~10이 되도록 조절하였다. 추출 후 모은 유기층은 brine으로 씻고, Na2SO4로 건조한 후 여과하고 농축하여 노란색 고체의 조 생성물을 얻었다. 이를 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정한 후 이를 여과하여11.4 g (정량 수율)의 노란색 고체인 결과물을 얻었다.After cooling to room temperature, the reactant was dissolved with methylene chloride, and then the organic layer was collected. The collected organic layers were transferred to a separatory funnel, and water was added thereto, followed by addition of 1N KOH to adjust the pH of the water layer to 9-10. The extracted organic layer was extracted with brine, dried over Na 2 SO 4 , filtered and concentrated to give a crude product as a yellow solid. It was dissolved in a small amount of methylene chloride and recrystallized by adding an excess of methanol, which was then filtered to give 11.4 g (quantitative yield) of a yellow solid.
실시예Example 11-2 11-2
(( EE )-) - NN -(- ( PhenylPhenyl (1,2,3,4-(1,2,3,4- tetrahydroquinolintetrahydroquinolin -7--7- ylyl )methylene)methylene) benzenaminebenzenamine 의 제조 Manufacturing
100 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기를 연결한 후 실시예11-1의 phenyl(1,2,3,4-tetrahydroquinolin-8-yl)methanone 1.5 g (6.4 mmol)을 넣고 정제 톨루엔21 mL를 가하여 녹였다. 이에 aniline 2.9 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 4.8 mL (1 M solution in toluene, 4.8 mmol, 0.75 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 Celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 1.9 g (6.1mmol, 95 % 수율)의 노란색 고체인 결과물을 얻었다.Connect a water-cooled condenser to a 100 mL 2-neck round bottom flask, add 1.5 g (6.4 mmol) of phenyl (1,2,3,4-tetrahydroquinolin-8-yl) methanone in Example 11-1, and add 21 mL of purified toluene. Was dissolved by addition. 2.9 mL (32 mmol, 5 equivalents) of aniline was added thereto, and the mixture was stirred at room temperature for 10 minutes. After that, 4.8 mL of TiCl 4 solution (1 M solution in toluene, 4.8 mmol, 0.75 equiv) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with Celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 1.9 g (6.1 mmol, 95% yield) of a yellow solid.
상기 실시예 11에서 합성된 리간드 화합물의 NMR spectrum을 도 11에 나타내었다.
An NMR spectrum of the ligand compound synthesized in Example 11 is shown in FIG. 11.
실시예Example 12 12
(( EE )-) - NN -(- ( PhenylPhenyl (1,2,3,4-(1,2,3,4- tetrahydroquinolintetrahydroquinolin -7--7- ylyl )methylene)-2,6-dimethylbenzenamine의 제조Preparation of methylene) -2,6-dimethylbenzenamine
100 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기를 연결한 후 실시예11-1의 phenyl(1,2,3,4-tetrahydroquinolin-8-yl)methanone 1.5 g (6.4 mmol)을 넣고 정제 톨루엔21 mL를 가하여 녹였다. 이에 2,6-dimethylaniline 3.3 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 Celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 2.1 g (6.1 mmol, 95 % 수율)의 노란색 고체인 결과물을 얻었다.Connect a water-cooled condenser to a 100 mL 2-neck round bottom flask, add 1.5 g (6.4 mmol) of phenyl (1,2,3,4-tetrahydroquinolin-8-yl) methanone in Example 11-1, and add 21 mL of purified toluene. Was dissolved by addition. 3.3 mL (32 mmol, 5 equivalents) of 2,6-dimethylaniline was added thereto, followed by stirring at room temperature for 10 minutes. After that, 6.4 mL of TiCl 4 solution (1 M solution in toluene, 6.4 mmol, 1 equivalent) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with Celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 2.1 g (6.1 mmol, 95% yield) of a yellow solid.
상기 실시예 12에서 합성된 리간드 화합물의 NMR spectrum을 도 12에 나타내었다.
An NMR spectrum of the ligand compound synthesized in Example 12 is shown in FIG. 12.
실시예Example 13 13
(( EE )-) - NN -(- ( phenylphenyl (1,2,3,4-(1,2,3,4- tetrahydroquinolintetrahydroquinolin -7--7- ylyl )methylene)-2,6-diisopropylbenzenamine의 제조Preparation of methylene) -2,6-diisopropylbenzenamine
100 mL 2-neck 둥근 바닥 플라스크에 수냉식 응축기를 연결한 후 실시예 11-1의 phenyl(1,2,3,4-tetrahydroquinolin-8-yl)methanone 1.5 g (6.4 mmol)을 넣고 정제 톨루엔21 mL를 가하여 녹였다. 이에 2,6-diisopropylaniline 3.9 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 6.4 mL (1 M solution in toluene, 6.4 mmol, 1 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 Celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 1.7 g (4.2 mmol, 66 % 수율)의 노란색 고체인 결과물을 얻었다.Connect a water-cooled condenser to a 100 mL 2-neck round bottom flask, add 1.5 g (6.4 mmol) of phenyl (1,2,3,4-tetrahydroquinolin-8-yl) methanone from Example 11-1, and add 21 mL of purified toluene. Was dissolved by addition. 3.9 mL (32 mmol, 5 equivalents) of 2,6-diisopropylaniline was added thereto, followed by stirring for 10 minutes at room temperature. After that, 6.4 mL of TiCl 4 solution (1 M solution in toluene, 6.4 mmol, 1 equivalent) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with Celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 1.7 g (4.2 mmol, 66% yield) of a yellow solid.
상기 실시예 13에서 합성된 리간드 화합물의 NMR spectrum을 도 13에 나타내었다.
NMR spectrum of the ligand compound synthesized in Example 13 is shown in FIG. 13.
실시예Example 14 14
(( EE )-) - NN -(Phenyl(2--(Phenyl (2- tt -- butylbutyl -1,2,3,4--1,2,3,4- tetrahydroquinolintetrahydroquinolin -7-yl)methylene)benzenamine의 제조Preparation of -7-yl) methylene) benzenamine
실시예Example 14-1 14-1
(2-(2- terttert -- ButylButyl -1,2,3,4--1,2,3,4- tetrahydroquinolintetrahydroquinolin -8--8- ylyl )() ( phenylphenyl )) methanone메탄one 의 제조 Manufacturing
250 mL 2-neck 둥근 바닥 플라스크)에 수냉식 응축기를 연결한 후 2-tert-butyl-1,2,3,4-tetrahydroquinoline 9.1 g (48 mmol)를 넣고 정제 톨루엔48 mL를 가하여 녹였다. 이 용액을 0℃로 식힌 후 BCl3 53 mL (1 M solution in methylene chloride, 53 mmol, 1 당량)를 가하고 교반시켰다. 벤조니트릴 10 mL (96 mmol, 2 당량)와 AlCl3 6.4 g (48 mmol, 1 당량)을 가하고 110℃에서 밤새 환류하였다. 반응이 끝나면 110℃에서 진공 건조하여 용매를 제거하고 상온으로 식힌 후 4 N HCl (100 mL)을 넣고 80℃에서 1시간 동안 교반하였다. 250 mL 2-neck round bottom flask) was connected to a water-cooled condenser, and then 9.1 g (48 mmol) of 2- tert- butyl-1,2,3,4-tetrahydroquinoline were added and dissolved in 48 mL of purified toluene. After the solution was cooled to 0 ° C., 53 mL of BCl 3 (1 M solution in methylene chloride, 53 mmol, 1 equivalent) was added thereto, followed by stirring. 10 mL (96 mmol, 2 equiv) of benzonitrile and 6.4 g (48 mmol, 1 equiv) of AlCl 3 were added and refluxed at 110 ° C. overnight. After the reaction was dried in vacuo at 110 ℃ to remove the solvent, cooled to room temperature, 4 N HCl (100 mL) was added and stirred at 80 ℃ for 1 hour.
상온으로 식힌 후 메틸렌 클로라이드로 반응물을 녹인 후 유기층을 모았다. 모아진 유기층을 분별 깔때기로 옮기고 물을 가한 후 1N KOH를 가하여 물층의 pH가 9~10이 되도록 조절하였다. 추출 후 모은 유기층은 brine으로 씻고, Na2SO4로 건조한 후 여과하고 농축하여 노란색 고체의 조 생성물을 얻었다. 이를 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정한 후 이를 여과하여 9.3 g (31.7 mmol, 66 % 수율)의 노란색 고체인 결과물을 얻었다.After cooling to room temperature, the reactant was dissolved with methylene chloride, and then the organic layer was collected. The collected organic layers were transferred to a separatory funnel, and water was added thereto, followed by addition of 1N KOH to adjust the pH of the water layer to 9-10. The extracted organic layer was extracted with brine, dried over Na 2 SO 4 , filtered and concentrated to give a crude product as a yellow solid. This was dissolved in a small amount of methylene chloride, and recrystallized by adding an excess of methanol, which was filtered to give 9.3 g (31.7 mmol, 66% yield) of a yellow solid.
실시예Example 14-2 14-2
(( EE )-) - NN -(Phenyl(2--(Phenyl (2- tt -- butylbutyl -1,2,3,4--1,2,3,4- tetrahydroquinolintetrahydroquinolin -7-yl)methylene)benzenamine의 제조Preparation of -7-yl) methylene) benzenamine
100 mL 2-neck 둥근 바닥 플라스크)에 수냉식 응축기를 연결한 후 실시예 14-1의 (2-tert-butyl-1,2,3,4-tetrahydroquinolin-8-yl)(phenyl)methanone 1.9 g (6.4 mmol)을 넣고 정제 톨루엔21 mL를 가하여 녹였다. 이에 aniline 2.9 mL (32 mmol, 5 당량)를 가하고 상온에서 10 분간 교반하였다. 이 후 TiCl4 용액 4.8 mL (1 M solution in toluene, 4.8 mmol, 0.75 당량)을 가하고 상온에서 1시간 동안 교반한 후 110℃에서 밤새 환류하였다. 반응이 종결되면 상온으로 식히고 디에틸 에테르 50 mL를 가하여 충분히 교반한 후 Celite pad가 깔린 글래스 필터로 여과하였다. 여과액을 농축하여 얻은 조 생성물은 소량의 메틸렌 클로라이드로 녹이고 과량의 메탄올을 가하여 재결정하였다. 이를 여과하여 1.6 g (4.4mmol, 69 % 수율)의 노란색 고체인 결과물을 얻었다.To a 100 mL 2-neck round bottom flask) 1.9 g (6.4 mmol) of (2- tert- butyl-1,2,3,4-tetrahydroquinolin-8-yl) (phenyl) methanone of Example 14-1 was added thereto, and 21 mL of purified toluene was added thereto and dissolved. 2.9 mL (32 mmol, 5 equivalents) of aniline was added thereto, and the mixture was stirred at room temperature for 10 minutes. After that, 4.8 mL of TiCl 4 solution (1 M solution in toluene, 4.8 mmol, 0.75 equiv) was added thereto, stirred at room temperature for 1 hour, and refluxed at 110 ° C. overnight. After the reaction was completed, the mixture was cooled to room temperature, 50 mL of diethyl ether was added thereto, the mixture was sufficiently stirred, and filtered through a glass filter coated with Celite pad. The crude product obtained by concentrating the filtrate was dissolved in a small amount of methylene chloride and recrystallized by adding excess methanol. This was filtered to give 1.6 g (4.4 mmol, 69% yield) of a yellow solid.
상기 실시예 14에서 합성된 리간드 화합물의 NMR spectrum을 도 14에 나타내었다.
An NMR spectrum of the ligand compound synthesized in Example 14 is shown in FIG. 14.
<전이금속 화합물의 합성>Synthesis of Transition Metal Compound
실시예Example 15 15
글러브 박스(glove box) 내에서 1-neck 둥근 바닥 플라스크에 실시예 1의 리간드 화합물(2mmol)과 정제 톨루엔 10mL를 가하여 녹인 후, n-부틸리튬(n-butyllithium) 용액 (0.88mL, 2.2mmolm 2.5M solution in n-hexane)을 가하고 상온에서 1시간 동안 교반하였다. 반응 용액에 HfCl4 (673mg, 2.1mmol)을 넣은 후 air-cooled condenser에 연결하고 100℃에서 2시간 동안 교반하였다. 이후 상온으로 식히고 메틸 마그네슘 브로마이드(methyl magnesium bromide) 용액(2mL, 6mmolm 3M solution in diethyl ether)을 가한 후 상온에서 1일 동안 교반하였다. 반응이 종결하면 100℃에서 진공 건조한 후 50℃로 식히고 정제 n-헥산(n-hexane) 20mL를 가한 후 2시간 동안 교반하여 결과물을 추출하였다. 이를 4G 글래스 필터로 여과하고 여과액을 진공 건조하여 노란색 고체의 결과물을 수득하였다. In a glove box, a 1-neck round bottom flask was added to dissolve the ligand compound of Example 1 (2 mmol) and 10 mL of purified toluene, followed by n-butyllithium solution (0.88 mL, 2.2 mmol 2.5). M solution in n-hexane) was added and stirred at room temperature for 1 hour. HfCl 4 (673mg, 2.1mmol) was added to the reaction solution, which was then connected to an air-cooled condenser and stirred at 100 ° C. for 2 hours. After cooling to room temperature, methyl magnesium bromide solution (2mL, 6mmolm 3M solution in diethyl ether) was added and stirred at room temperature for 1 day. After the reaction was completed, the resultant was dried under vacuum at 100 ° C., cooled to 50 ° C., 20 mL of purified n-hexane was added, and stirred for 2 hours. It was filtered through a 4G glass filter and the filtrate was dried in vacuo to yield the result as a yellow solid.
상기 실시예 15에서 합성된 전이금속 화합물의 NMR spectrum을 도 15에 나타내었다.
An NMR spectrum of the transition metal compound synthesized in Example 15 is shown in FIG. 15.
실시예Example 16 16
글러브 박스 내에서 1-neck 둥근 바닥 플라스크에 실시예 2의 리간드 화합물 (2 mmol)과 Hf(NMe2)4 745 mg (2.1 mmol, 1.05 당량)을 넣고 정제 톨루엔6 mL을 가하여 녹인 후 air-cooled condenser를 연결하고 일정 온도에서 일정 시간 동안 교반하였다. 반응 종결 후 온도를 100℃로 올리고 진공 건조하여 주황색 고체를 정량 수율로 얻었다.In a glove box, 745 mg (2.1 mmol, 1.05 eq) of the ligand compound of Example 2 and Hf (NMe 2 ) 4 were added to a 1-neck round bottom flask, and 6 mL of purified toluene was added thereto, followed by air-cooling. The condenser was connected and stirred for a certain time at a certain temperature. After completion of the reaction, the temperature was raised to 100 ° C. and vacuum dried to give an orange solid in quantitative yield.
상기 실시예 16에서 합성된 전이금속 화합물의 NMR spectrum을 도 16에 나타내었다.
The NMR spectrum of the transition metal compound synthesized in Example 16 is shown in FIG. 16.
실시예Example 17 17
실시예 2의 리간드 화합물 대신 실시예 6의 리간드 화합물을 사용한 것을 제외하고는 실시예 16과 동일한 방법으로 전이금속 화합물을 제조하였으며, 주황색 고체를 정량 수율로 얻었다.A transition metal compound was prepared in the same manner as in Example 16, except that the ligand compound of Example 6 was used instead of the ligand compound of Example 2, and an orange solid was obtained in a quantitative yield.
상기 실시예 17에서 합성된 전이금속 화합물의 NMR spectrum을 도 17에 나타내었다.
The NMR spectrum of the transition metal compound synthesized in Example 17 is shown in FIG. 17.
실시예Example 18 18
글러브 박스 내에서 1-neck 둥근 바닥 플라스크에 실시예 7의 리간드 화합물 (1 mmol)과 Hf(CH2Ph)4 600 mg (1.1 mmol, 1.1 당량)을 넣고 정제 n-hexane 2.5 mL을 가하여 녹인 후 상온에서 1일간 교반하였다. 반응 종결 후 진공 건조하여 주황색 고체를 정량 수율로 얻었다.In a 1-neck round bottom flask in a glove box, 600 mg (1.1 mmol, 1.1 equiv) of the ligand compound (1 mmol) and Hf (CH 2 Ph) 4 of Example 7 were added and dissolved in 2.5 mL of purified n- hexane. Stirred at room temperature for 1 day. After completion of the reaction and dried under vacuum to give an orange solid in quantitative yield.
상기 실시예 18에서 합성된 전이금속 화합물의 NMR spectrum을 도 18에 나타내었다.
An NMR spectrum of the transition metal compound synthesized in Example 18 is shown in FIG. 18.
실시에 1919 on implementation
실시예 1의 리간드 화합물 대신 실시예 8의 리간드 화합물을 사용한 것을 제외하고는 실시예 15와 동일한 방법으로 전이금속 화합물을 제조하였으며, 주황색 고체를 정량 수율로 얻었다.A transition metal compound was prepared in the same manner as in Example 15, except that the ligand compound of Example 8 was used instead of the ligand compound of Example 1, and an orange solid was obtained in a quantitative yield.
상기 실시예 19에서 합성된 전이금속 화합물의 NMR spectrum을 도 19에 나타내었다.
NMR spectrum of the transition metal compound synthesized in Example 19 is shown in FIG. 19.
실시예Example 20 20
실시예 2의 리간드 화합물 대신 실시예 9의 리간드 화합물을 사용한 것을 제외하고는 실시예 16과 동일한 방법으로 전이금속 화합물을 제조하였으며, 주황색 고체를 정량 수율로 얻었다.A transition metal compound was prepared in the same manner as in Example 16, except that the ligand compound of Example 9 was used instead of the ligand compound of Example 2, and an orange solid was obtained in a quantitative yield.
상기 실시예 20에서 합성된 전이금속 화합물의 NMR spectrum을 도 20에 나타내었다.
An NMR spectrum of the transition metal compound synthesized in Example 20 is shown in FIG. 20.
실시예Example 21 21
실시예 2의 리간드 화합물 대신 실시예 10의 리간드 화합물을 사용한 것을 제외하고는 실시예 16과 동일한 방법으로 전이금속 화합물을 제조하였으며, 주황색 고체를 정량 수율로 얻었다.A transition metal compound was prepared in the same manner as in Example 16, except that the ligand compound of Example 10 was used instead of the ligand compound of Example 2, and an orange solid was obtained in a quantitative yield.
상기 실시예 21에서 합성된 전이금속 화합물의 NMR spectrum을 도 21에 나타내었다.
An NMR spectrum of the transition metal compound synthesized in Example 21 is shown in FIG. 21.
실시예Example 22 22
실시예 2의 리간드 화합물 대신 실시예 11의 리간드 화합물을 사용한 것을 제외하고는 실시예 16과 동일한 방법으로 전이금속 화합물을 제조하였으며, 주황색 고체를 정량 수율로 얻었다.A transition metal compound was prepared in the same manner as in Example 16, except that the ligand compound of Example 11 was used instead of the ligand compound of Example 2, and an orange solid was obtained in a quantitative yield.
상기 실시예 22에서 합성된 전이금속 화합물의 NMR spectrum을 도 22에 나타내었다.
An NMR spectrum of the transition metal compound synthesized in Example 22 is shown in FIG. 22.
실시예Example 23 23
실시예 2의 리간드 화합물 대신 실시예 12의 리간드 화합물을 사용한 것을 제외하고는 실시예 16과 동일한 방법으로 전이금속 화합물을 제조하였으며, 주황색 고체를 정량 수율로 얻었다.A transition metal compound was prepared in the same manner as in Example 16, except that the ligand compound of Example 12 was used instead of the ligand compound of Example 2, and an orange solid was obtained in a quantitative yield.
상기 실시예 23에서 합성된 전이금속 화합물의 NMR spectrum을 도 23에 나타내었다.
An NMR spectrum of the transition metal compound synthesized in Example 23 is shown in FIG. 23.
실시예Example 24 24
실시예 1의 리간드 화합물 대신 실시예 13의 리간드 화합물을 사용한 것을 제외하고는 실시예 15와 동일한 방법으로 전이금속 화합물을 제조하였으며, 주황색 고체를 정량 수율로 얻었다.A transition metal compound was prepared in the same manner as in Example 15 except that the ligand compound of Example 13 was used instead of the ligand compound of Example 1, and an orange solid was obtained in a quantitative yield.
상기 실시예 24에서 합성된 전이금속 화합물의 NMR spectrum을 도 24에 나타내었다.
An NMR spectrum of the transition metal compound synthesized in Example 24 is shown in FIG. 24.
비교예Comparative Example 1 One
TribenzylTribenzyl (( EE )-(8-(((2-)-(8-(((2- methylcyclohexylmethylcyclohexyl )) iminoimino )) methylmethyl )-3,4-) -3,4- dihydroquinolindihydroquinolin -1(-One( 2H2H )-) - ylyl )) zirconiumzirconium
Tribenzyl (E)-(8-(((2-methylcyclohexyl)imino)methyl)-3,4-dihydroquinolin-1(2H)-yl)zirconium 화합물은 PCT/KR2010/004842의 실시예 4에 따라 합성하였다.
Tribenzyl ( E )-(8-(((2-methylcyclohexyl) imino) methyl) -3,4-dihydroquinolin-1 ( 2H ) -yl) zirconium compound was synthesized according to Example 4 of PCT / KR2010 / 004842.
프로필렌 단독 중합체의 제조Preparation of propylene homopolymer
실시예Example 25 25
300mL 미니클레이브 반응기에 톨루엔 용매(200mL)를 가한 후, 반응기의 온도를 70℃로 예열하였다. 5 ｘ 10-3 M의 디메틸아닐리늄 테트라키스(펜타플로로페닐) 보레이트 조촉매 2mL를 트리이소부틸알루미늄 화합물로 처리된 상기 실시예 15의 전이금속 화합물(2ｘ10-3M, 1mL)를 순서대로 반응기에 넣었다. 프로필렌(5 bar)을 연속 주입하면서 중합 반응을 시작하였다. 중합 반응을 10분간 진행한 후, 남은 가스를 빼내고 고분자 용액을 과량의 에탄올이 있는 비커에 부어 침전을 유도하였다. 얻어진 고분자를 에탄올 및 아세톤으로 각각 2 내지 3회 세척한 후, 80℃ 진공 오븐에서 12시간 이상 건조하였다.
Toluene solvent (200 mL) was added to a 300 mL miniclave reactor, and then the temperature of the reactor was preheated to 70 ° C. The transition metal compound of Example 15 (2x10 -3 M, 1 mL) in which 2 mL of 5'10 -3 M dimethylanilinium tetrakis (pentafluorophenyl) borate cocatalyst was treated with a triisobutylaluminum compound was sequentially Into the reactor. The polymerization reaction was started with continuous injection of propylene (5 bar). After 10 minutes of polymerization, the remaining gas was removed and the polymer solution was poured into a beaker with excess ethanol to induce precipitation. The obtained polymer was washed two to three times with ethanol and acetone, and then dried in an 80 ° C. vacuum oven for at least 12 hours.
실시예Example 26 26
상기 실시예 16의 전이금속 화합물을 이용한 것을 제외하고는 상기 실시예 25와 동일한 방법으로 올레핀계 중합체를 제조하였다.
An olefin polymer was prepared in the same manner as in Example 25, except that the transition metal compound of Example 16 was used.
실시예Example 27 27
상기 실시예 17의 전이금속 화합물을 이용한 것을 제외하고는 상기 실시예 25와 동일한 방법으로 올레핀계 중합체를 제조하였다.
An olefin polymer was prepared in the same manner as in Example 25, except that the transition metal compound of Example 17 was used.
실시예Example 28 28
상기 실시예 18의 전이금속 화합물을 이용한 것을 제외하고는 상기 실시예 25와 동일한 방법으로 올레핀계 중합체를 제조하였다.
An olefin polymer was prepared in the same manner as in Example 25, except that the transition metal compound of Example 18 was used.
실시예Example 29 29
상기 실시예 19의 전이금속 화합물을 이용한 것을 제외하고는 상기 실시예 25와 동일한 방법으로 올레핀계 중합체를 제조하였다.
An olefin polymer was prepared in the same manner as in Example 25, except that the transition metal compound of Example 19 was used.
실시예Example 30 30
상기 실시예 20의 전이금속 화합물을 이용한 것을 제외하고는 상기 실시예 25와 동일한 방법으로 올레핀계 중합체를 제조하였다.
An olefin polymer was prepared in the same manner as in Example 25, except that the transition metal compound of Example 20 was used.
실시예Example 31 31
상기 실시예 21의 전이금속 화합물을 이용한 것을 제외하고는 상기 실시예 25와 동일한 방법으로 올레핀계 중합체를 제조하였다.
An olefin polymer was prepared in the same manner as in Example 25, except that the transition metal compound of Example 21 was used.
실시예Example 32 32
상기 실시예 22의 전이금속 화합물을 이용한 것을 제외하고는 상기 실시예 25와 동일한 방법으로 올레핀계 중합체를 제조하였다.
An olefin polymer was prepared in the same manner as in Example 25, except that the transition metal compound of Example 22 was used.
실시예Example 33 33
상기 실시예 23의 전이금속 화합물을 이용한 것을 제외하고는 상기 실시예 25와 동일한 방법으로 올레핀계 중합체를 제조하였다.
An olefin polymer was prepared in the same manner as in Example 25, except that the transition metal compound of Example 23 was used.
실시예Example 34 34
상기 실시예 24의 전이금속 화합물을 이용한 것을 제외하고는 상기 실시예 25와 동일한 방법으로 올레핀계 중합체를 제조하였다.
An olefin polymer was prepared in the same manner as in Example 25, except that the transition metal compound of Example 24 was used.
비교예Comparative Example 2 2
상기 비교예 1의 전이금속 화합물을 이용한 것을 제외하고는 상기 실시예 25와 동일한 방법으로 올레핀계 중합체를 제조하였다.
An olefin polymer was prepared in the same manner as in Example 25, except that the transition metal compound of Comparative Example 1 was used.
중합체의 녹는점(Tm)은 TA사의 Q100을 사용하여 측정하였다. 측정값은 중합체의 thermal history를 없애기 위해 분당 10℃로 승온시킨 두 번째 melting을 통해 얻었다.The melting point (Tm) of the polymer was measured using TA Q100. The measured values were obtained through a second melting up to 10 ° C. per minute to eliminate the thermal history of the polymer.
상기 실시예 26 및 비교예 2에서 수득된 중합체에 대해 상기와 같은 방법으로 물성을 측정한 후 그 결과를 하기 표 2에 나타내었다.The physical properties of the polymers obtained in Example 26 and Comparative Example 2 were measured in the same manner as described above, and the results are shown in Table 2 below.
(단위: kg/mol hr)Catalytic activity
(Unit: kg / mol hr)
(단위: ℃)Melting point
(Unit: ℃)
Claims (5)
[화학식 1]
상기 화학식 1에서,
m은 1 내지 2의 정수이고;
R1, R2 및 R3은 동일하거나 상이하고 각각 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아릴알킬기 또는 실릴기이며, 2개 이상의 R1, R2 또는 R3은 탄소수 1 내지 20의 알킬기 또는 탄소수 6 내지 20의 아릴기를 포함하는 알킬리딘기에 의해 서로 연결되어 고리를 형성할 수 있고, 단 R2가 수소인 경우는 제외하며;
R4, R5 및 R6은 동일하거나 상이하고 각각 독립적으로 수소, 할로겐기, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 20의 아릴기, 탄소수 1 내지 20의 알콕시기, 탄소수 6 내지 20의 아릴옥시기, 탄소수 1 내지 20의 알킬 아미노기 또는 탄소수 6 내지 20의 아릴 아미노기이며, 2개 이상의 R4, R5 또는 R6가 서로 연결되어 지방족 또는 방향족 고리를 형성할 수 있다.
A ligand compound represented by the following formula (1):
[Chemical Formula 1]
In Formula 1,
m is an integer from 1 to 2;
R 1 , R 2 and R 3 are the same or different and are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, An arylalkyl group or silyl group having 7 to 20 carbon atoms, and two or more R 1 , R 2 or R 3 are connected to each other by an alkylidine group including an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring; Except where R 2 is hydrogen;
R 4 , R 5 and R 6 are the same or different and are each independently hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl having 6 to 20 carbon atoms An oxy group, an alkyl amino group having 1 to 20 carbon atoms or an aryl amino group having 6 to 20 carbon atoms, and two or more R 4 , R 5 or R 6 may be linked to each other to form an aliphatic or aromatic ring.
The compound of claim 1, wherein the compound represented by Formula 1 is a ligand compound represented by one of the following formulas:
[화학식 2]
M은 4족의 전이금속이고;
K는 할로겐, 탄소수 1 내지 20의 알킬기, 탄소수 2 내지 20의 알케닐기, 탄소수 6 내지 20의 아릴기, 탄소수 7 내지 20의 알킬아릴기, 탄소수 7 내지 20의 아 알킬기, 탄소수 1 내지 20의 알킬아미노기, 탄소수 6 내지 20의 아릴 아미노기 및 탄소수 1 내지 20의 알킬리덴기로 이루어진 군에서 선택된 1종이고;
n은 2 내지 3의 정수이며;
m, R1, R2, R3, R4, R5 및 R6는 상기 화학식 1에서 정의한 바와 같다.
A transition metal compound represented by the following formula (2):
(2)
M is a transition metal of Group 4;
K is a halogen, an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, alkyl of 1 to 20 carbon atoms An amino group, an aryl amino group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms;
n is an integer from 2 to 3;
m, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same as defined in Chemical Formula 1.
The transition metal compound of claim 3, wherein M is selected from the group consisting of Ti, Zr, and Hf.
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| CN105440212A (en) * | 2014-09-30 | 2016-03-30 | 中国石油化工股份有限公司 | Preparation method for butadiene styrene rubber and butadiene styrene rubber |
| KR20170095036A (en) * | 2016-02-12 | 2017-08-22 | 주식회사 엘지화학 | Method of preparing novel ligand compound and transition metal compound |
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| EP0131921A2 (en) * | 1983-07-13 | 1985-01-23 | Shionogi & Co., Ltd. | Ortho-(mono-substituted amino)phenylimines and production thereof |
| KR20110009942A (en) * | 2009-07-23 | 2011-01-31 | 주식회사 엘지화학 | New post metallocene catalysts for olefin polymerization |
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| EP0131921A2 (en) * | 1983-07-13 | 1985-01-23 | Shionogi & Co., Ltd. | Ortho-(mono-substituted amino)phenylimines and production thereof |
| KR20110009942A (en) * | 2009-07-23 | 2011-01-31 | 주식회사 엘지화학 | New post metallocene catalysts for olefin polymerization |
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| CN105440212A (en) * | 2014-09-30 | 2016-03-30 | 中国石油化工股份有限公司 | Preparation method for butadiene styrene rubber and butadiene styrene rubber |
| KR20170095036A (en) * | 2016-02-12 | 2017-08-22 | 주식회사 엘지화학 | Method of preparing novel ligand compound and transition metal compound |
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