KR20180022136A - Method for preparation of novel ligand compound and transition metal compound - Google Patents
Method for preparation of novel ligand compound and transition metal compound Download PDFInfo
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- KR20180022136A KR20180022136A KR1020160107067A KR20160107067A KR20180022136A KR 20180022136 A KR20180022136 A KR 20180022136A KR 1020160107067 A KR1020160107067 A KR 1020160107067A KR 20160107067 A KR20160107067 A KR 20160107067A KR 20180022136 A KR20180022136 A KR 20180022136A
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- South Korea
- Prior art keywords
- formula
- compound represented
- compound
- transition metal
- mmol
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 141
- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims description 22
- 239000003446 ligand Substances 0.000 title abstract description 18
- 238000002360 preparation method Methods 0.000 title description 15
- 239000000126 substance Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 claims description 4
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000001246 bromo group Chemical group Br* 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000002346 iodo group Chemical group I* 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 14
- 150000001336 alkenes Chemical class 0.000 abstract description 12
- 239000002685 polymerization catalyst Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 41
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 229920001577 copolymer Polymers 0.000 description 21
- 239000000203 mixture Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000012043 crude product Substances 0.000 description 16
- 239000012044 organic layer Substances 0.000 description 16
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 16
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- -1 trimethylsilylmethyl group Chemical group 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 8
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- KNLGRGALOHHVOL-UHFFFAOYSA-N hafnium(4+);methanidylbenzene Chemical compound [Hf+4].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 KNLGRGALOHHVOL-UHFFFAOYSA-N 0.000 description 8
- 239000004711 α-olefin Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- UBFFFAXMQZYDAN-UHFFFAOYSA-N 4-chloro-2-methyl-1,3-benzoxazole Chemical compound C1=CC=C2OC(C)=NC2=C1Cl UBFFFAXMQZYDAN-UHFFFAOYSA-N 0.000 description 5
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 4
- WVODSIBUYCZFCU-UHFFFAOYSA-N 4-chloro-2-methyl-1,3-benzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1Cl WVODSIBUYCZFCU-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 3
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 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 3
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 0 *C(*1)=Nc2c1c(*)c(*)c(*)c2Nc1c(*)c(*)c(*)c(*)c1* Chemical compound *C(*1)=Nc2c1c(*)c(*)c(*)c2Nc1c(*)c(*)c(*)c(*)c1* 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- OYBFKJFWVAZRMI-UHFFFAOYSA-N 2-bromo-4-chloro-1,3-benzothiazole Chemical compound ClC1=CC=CC2=C1N=C(Br)S2 OYBFKJFWVAZRMI-UHFFFAOYSA-N 0.000 description 2
- WSNKEJIFARPOSQ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(1-benzothiophen-2-ylmethyl)benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCC2=CC3=C(S2)C=CC=C3)C=CC=1 WSNKEJIFARPOSQ-UHFFFAOYSA-N 0.000 description 2
- GDSLUYKCPYECNN-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[(4-fluorophenyl)methyl]benzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NCC2=CC=C(C=C2)F)C=CC=1 GDSLUYKCPYECNN-UHFFFAOYSA-N 0.000 description 2
- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- DVZWQGLVEOWFOU-UHFFFAOYSA-N C[Hf]C Chemical compound C[Hf]C DVZWQGLVEOWFOU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- SAHIZENKTPRYSN-UHFFFAOYSA-N [2-[3-(phenoxymethyl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound O(C1=CC=CC=C1)CC=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 SAHIZENKTPRYSN-UHFFFAOYSA-N 0.000 description 2
- YKKPYMXANSSQCA-UHFFFAOYSA-N [3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxyphenyl]-(3-pyrazol-1-ylazetidin-1-yl)methanone Chemical compound N1(N=CC=C1)C1CN(C1)C(=O)C1=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F YKKPYMXANSSQCA-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DRNAQRXLOSUHBQ-UHFFFAOYSA-N cphos Chemical compound CN(C)C1=CC=CC(N(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 DRNAQRXLOSUHBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- KTMKRRPZPWUYKK-UHFFFAOYSA-N methylboronic acid Chemical compound CB(O)O KTMKRRPZPWUYKK-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- HUMMCEUVDBVXTQ-UHFFFAOYSA-N naphthalen-1-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC=CC2=C1 HUMMCEUVDBVXTQ-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 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
- 238000001291 vacuum drying Methods 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 1
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical group [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- 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
- DBQOUEWUAIHCNY-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)alumane Chemical compound Fc1c(F)c(F)c([AlH2])c(F)c1F DBQOUEWUAIHCNY-UHFFFAOYSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- CVSBJNAPWCWNMI-UHFFFAOYSA-N 12,13,23-trimethyl-21H-porphyrin Chemical compound CN1C2=C(C(=C1C=C1C=CC(C=C3C=CC(=CC=4C=CC(=C2)N4)N3)=N1)C)C CVSBJNAPWCWNMI-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- OJAHVYRKXZEVCR-UHFFFAOYSA-N 2-naphthalen-1-yl-1,3-benzothiazole Chemical compound C1=CC=C2C(C=3SC4=CC=CC=C4N=3)=CC=CC2=C1 OJAHVYRKXZEVCR-UHFFFAOYSA-N 0.000 description 1
- KAJMDIRNTNSOLE-UHFFFAOYSA-N 2-naphthalen-1-yl-1,3-benzoxazole Chemical compound C1=CC=C2C(C=3OC4=CC=CC=C4N=3)=CC=CC2=C1 KAJMDIRNTNSOLE-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
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- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
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- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
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Abstract
Description
본 발명은 신규한 리간드 화합물 및 상기 리간드 화합물을 포함하는 전이금속 화합물의 제조 방법에 관한 것이다.The present invention relates to a novel ligand compound and a process for producing a transition metal compound comprising the ligand compound.
기존의 폴리올레핀의 상업적 제조 과정에는 티타늄 또는 바나듐 화합물의 지글러-나타 촉매가 널리 사용되어 왔는데, 상기 지글러-나타 촉매는 높은 활성을 갖지만, 다활성점 촉매이기 때문에 생성 고분자의 분자량 분포가 넓으며 공단량체의 조성 분포가 균일하지 않아 원하는 물성 확보에 한계가 있었다.Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used for the commercial production of polyolefins. Although the Ziegler-Natta catalysts have high activity, they have a wide molecular weight distribution of the produced polymers because of their high activity, The uniformity of the composition is not uniform and there is a limit in ensuring desired physical properties.
이에 따라, 최근에는 티타늄, 지르코늄, 하프늄 등의 전이 금속과 사이클로펜타디엔 작용기를 포함하는 리간드가 결합된 메탈로센 촉매가 개발되어 널리 사용되고 있다. 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 리간드(예를 들어, 벤질 또는 트리메틸실릴메틸기(-CH2SiMe3))로 치환하는 경우 촉매 활성도 증가 등의 효과를 나타내는 예가 보고되었다.Accordingly, recently, a metallocene catalyst in which a transition metal such as titanium, zirconium, or hafnium and a ligand containing a cyclopentadiene functional group are bonded has been developed and widely used. 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 replaced 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.
Dow 사는 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 이루어지고 있다.Dow has disclosed in the early 1990's [Me 2 Si (Me 4 C 5 ) N t Bu] TiCl 2 (Constrained-Geometry Catalyst, CGC) in U.S. Patent No. 5,064,802 and the like that 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, as the various characteristics of CGC are gradually known during the polymerization reaction, efforts to synthesize the derivatives and use them as polymerization catalysts have been actively 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 시도된 바 있다. In another approach, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and some attempts have been made to polymerize them.
그러나, 이러한 모든 시도들 중에서 실제로 상업 공장에 적용되고 있는 촉매들은 몇몇에 불과한 수준으로, 보다 향상된 중합 성능을 나타내는 촉매에 대한 요구가 여전히 지속되고 있는 실정이다. However, among all of these attempts, there are only a few catalysts currently being applied to commercial plants, and there is still a demand for a catalyst exhibiting improved polymerization performance.
본 발명은 높은 촉매활성을 나타내며 고분자량의 올레핀계 중합체를 제조할 수 있는 신규한 리간드 화합물 및 이를 포함하는 전이금속 화합물의 제조 방법을 제공하기 위한 것이다. The present invention provides a novel ligand compound capable of producing a high molecular weight olefin polymer exhibiting high catalytic activity and a method for producing a transition metal compound containing the same.
하기 화학식 5로 표시되는 화합물과 하기 화학식 6으로 표시되는 화합물을 반응시키는 단계를 포함하는, 하기 화학식 1로 표시되는 화합물의 제조 방법을 제공한다:Reacting a compound represented by the following formula (5) with a compound represented by the following formula (6): < EMI ID =
[화학식 1][Chemical Formula 1]
[화학식 5][Chemical Formula 5]
[화학식 6][Chemical Formula 6]
상기 화학식 1, 5 및 6에서,In the above formulas (1), (5) and (6)
X는 O 또는 S이고,X is O or S,
Y는 할로겐이고,Y is halogen,
R1 내지 R9는 각각 독립적으로, 수소; C1-20 알킬; C3-20 사이클로알킬; C2-20 알케닐; C6-20 아릴; C7-20 알킬아릴; C7-20 아릴알킬; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 헤테로원자를 1개 이상 포함하는 C2-20 헤테로아릴이다.R 1 to R 9 are each independently hydrogen; C 1-20 alkyl; C 3-20 cycloalkyl; C 2-20 alkenyl; C 6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; Or C 2-20 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S.
본 발명의 제조 방법에 따라 제조된 화합물은 올레핀계 중합체 제조용 촉매로 이용될 수 있는 전이금속 화합물의 리간드로 사용될 수 있다. 보다 구체적으로, 상기 화학식 1로 표시되는 화합물은 벤즈옥사졸일기(X=O) 또는 벤조티아졸일기(X=S), 및 페닐기로 이치환된 아민계 화합물로서, 후술할 전이금속 화합물에서 아민의 질소 원자는 전이금속과 공유 결합되고, 벤즈옥사졸일기 또는 벤조티아졸일기의 질소 원자는 전이금속과 배위 결합된다. 상기의 신규 리간드 화합물을 이용하여 제조된 전이금속 화합물은 그 전자적 및 입체적 구조 등으로 인하여 올레핀계 중합체 제조 과정에서 높은 촉매 활성을 나타낼 수 있다. The compound prepared according to the production method of the present invention can be used as a ligand of a transition metal compound which can be used as a catalyst for producing an olefinic polymer. More specifically, the compound represented by Formula 1 is an amine compound disoriented with a benzoxazolyl group (X = O) or a benzothiazolyl group (X = S) and a phenyl group, The nitrogen atom is covalently bonded to the transition metal, and the nitrogen atom of the benzoxazolyl group or the benzothiazolyl group is coordinately bonded to the transition metal. The transition metal compound prepared using the novel ligand compound can exhibit a high catalytic activity in the production of olefinic polymer due to its electronic and steric structure.
특히, 상기 화학식 1로 표시되는 리간드 화합물을 이용하여 제조된 전이금속 화합물은 리간드 화합물의 구조적 특징으로 인하여 에틸렌 단량체와 알파-올레핀과의 공중합 반응에서 높은 활성을 나타내며 고분자량의 올레핀계 중합체를 제조할 수 있고, 최종 합성된 폴리올레핀 중 알파-올레핀의 공중합성이 향상될 수 있다.In particular, the transition metal compound prepared using the ligand compound represented by the above formula (1) exhibits high activity in the copolymerization reaction of the ethylene monomer and the alpha-olefin due to the structural characteristics of the ligand compound, and produces a high molecular weight olefin polymer And the copolymerization of the alpha-olefin in the final synthesized polyolefin can be improved.
구체적으로, 상기 화학식 5로 표시되는 화합물과 상기 화학식 6으로 표시되는 화합물의 반응은 C-N 커플링 반응으로 염기, 포스핀 리간드 및 팔라듐 촉매의 존재 하에서 진행될 수 있다. Specifically, the reaction between the compound represented by the formula (5) and the compound represented by the formula (6) can be carried out in the presence of a base, a phosphine ligand and a palladium catalyst in the C-N coupling reaction.
이때, 상기 팔라듐 촉매로는 트리스(디벤질리덴아세톤)디팔라듐(Pd2(dba)3), 비스(디벤질리덴아세톤)팔라듐(Pd(dba)2), 비스(트리(tert-부틸)포스핀))팔라듐(((tert-Bu)3P)2Pd), 테트라키스(트리페닐포스핀)팔라듐(Pd(PPh3)4), 팔라듐클로라이드(PdCl2), 또는 팔라듐아세테이트(Pd(OAc)2)가 사용될 수 있으나, 이에 한정되는 것은 아니다. At this time, as the palladium catalyst is tris (dibenzylideneacetone) dipalladium (Pd 2 (dba) 3), bis (dibenzylideneacetone) palladium (Pd (dba) 2), bis (tri (tert - butyl) phosphine Pd (PPh 3 ) 4 ), palladium chloride (PdCl 2 ), or palladium acetate (Pd (OAc))) palladium ((( tert- Bu) 3 P) 2 Pd), tetrakis (triphenylphosphine) palladium ) 2 ) may be used, but the present invention is not limited thereto.
또한, 상기 포스핀 리간드로는 프리페틸포스핀(PPh3), 1,1'-비스(디페닐포스피노)페로센(DPPF), 2-디시클로헥실포스피노-2',4',6'-트리이소프로필바이페닐(XPhos), 또는 2-디시클로헥실포스피노-2',6'-디메톡시바이페닐(SPhos), 2-(2-디시클로헥실포스파닐페닐)-N1,N1,N3,N3-테트라메틸-벤젠-1,3-디아민(CPhos)이 사용될 수 있으나, 이에 한정되는 것은 아니다. Examples of the phosphine ligand include PPh 3 , 1,1'-bis (diphenylphosphino) ferrocene (DPPF), 2-dicyclohexylphosphino-2 ', 4' (XPhos), or 2-dicyclohexylphosphino-2 ', 6'-dimethoxybiphenyl (SPhos), 2- (2-dicyclohexylphosphanylphenyl) -N1, N1, N3, N3-tetramethyl-benzene-1,3-diamine (CPhos) may be used, but are not limited thereto.
더욱 구체적으로, 상기 화학식 5로 표시되는 화합물과 상기 화학식 6으로 표시되는 화합물은 1:1 내지 1:3의 몰비로 사용될 수 있다. 예를 들어, 상기 화학식 5로 표시되는 화합물과 상기 화학식 6으로 표시되는 화합물은 1:1 내지 1:2, 1:1 내지 1:1.5, 또는 1:1 내지 1:1.2의 몰비로 사용될 수 있다. More specifically, the compound represented by Formula 5 and the compound represented by Formula 6 may be used in a molar ratio of 1: 1 to 1: 3. For example, the compound represented by Formula 5 and the compound represented by Formula 6 may be used in a molar ratio of 1: 1 to 1: 2, 1: 1 to 1: 1.5, or 1: 1 to 1: 1.2 .
또한, 상기 화학식 5로 표시되는 화합물과 상기 화학식 6으로 표시되는 화합물의 반응은 20 내지 150℃의 온도 범위에서 1 내지 72 시간 동안 진행될 수 있다. The reaction between the compound represented by the formula (5) and the compound represented by the formula (6) can be carried out at a temperature ranging from 20 to 150 ° C for 1 to 72 hours.
이때, 상기 화학식 5로 표시되는 화합물은, 하기 화학식 3으로 표시되는 화합물과 하기 화학식 4 또는 4'로 표시되는 화합물을 반응시켜 제조될 수 있다:The compound represented by Formula 5 may be prepared by reacting a compound represented by Formula 3 with a compound represented by Formula 4 or 4 '
[화학식 3](3)
[화학식 4][Chemical Formula 4]
[화학식 4'][Chemical Formula 4 ']
상기 화학식 3, 4 및 4'에서,In the above formulas (3), (4) and (4 '),
Z는 할로겐이고,Z is halogen,
X, Y 및 R6 내지 R9에 대한 설명은 상기 화학식 1, 5 및 6에서 정의한 바와 같다.X, Y and R 6 to R 9 are as defined in the above formulas (1), (5) and (6).
구체적으로, 상기 화학식 3로 표시되는 화합물과 상기 화학식 4 또는 4'로 표시되는 화합물의 반응은 Suzuki coupling 반응으로 팔라듐 촉매 하에서 진행될 수 있다.Specifically, the reaction between the compound represented by Formula 3 and the compound represented by Formula 4 or 4 'can be carried out in the Suzuki coupling reaction under palladium catalyst.
이때, 팔라듐 촉매로는 상술한 상기 화학식 5로 표시되는 화합물과 상기 화학식 6으로 표시되는 화합물의 반응에서 사용 가능한 것들을 사용할 수 있다. Here, as the palladium catalyst, those which can be used in the reaction of the compound represented by the above formula (5) and the compound represented by the above formula (6) can be used.
더욱 구체적으로, 상기 화학식 3로 표시되는 화합물과 상기 화학식 4 또는 4'로 표시되는 화합물은 1:1 내지 1:3의 몰비로 사용될 수 있다. 예를 들어, 상기 화학식 3로 표시되는 화합물과 상기 화학식 4 또는 4'로 표시되는 화합물은 1:1 내지 1:2, 1:1 내지 1:1.5, 1:1 내지 1:1.1, 또는 1:1 내지 1:1.05의 몰비로 사용될 수 있다. More specifically, the compound represented by Formula 3 and the compound represented by Formula 4 or 4 'may be used in a molar ratio of 1: 1 to 1: 3. For example, the compound represented by Formula 3 and the compound represented by Formula 4 or 4 'may be used in a ratio of 1: 1 to 1: 2, 1: 1 to 1: 1.5, 1: 1 to 1: 1 to 1: 1.05.
또한, 상기 화학식 3로 표시되는 화합물과 상기 화학식 4 또는 4'로 표시되는 화합물의 반응은 20 내지 150℃의 온도 범위에서 1 내지 72 시간 동안 진행될 수 있다. The reaction between the compound represented by Formula 3 and the compound represented by Formula 4 or 4 'may be conducted at a temperature ranging from 20 to 150 ° C for 1 to 72 hours.
그리고, 상기 화학식에서, Y 및 Z는 각각 독립적으로, 클로로, 브로모, 또는 아이오도일 수 있다. And, in the above formula, Y and Z may each independently be chloro, bromo, or iodo.
또한, R1 내지 R9는 각각 독립적으로, 수소, C1-10 알킬, 또는 C6-20 아릴일 수 있다.Also, R 1 to R 9 may each independently be hydrogen, C 1-10 alkyl, or C 6-20 aryl.
구체적으로, R1 내지 R9는 각각 독립적으로, 수소, 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, sec-부틸, tert-부틸, 페닐, 또는 나프틸일 수 있다. Specifically, R 1 to R 9 each independently may be hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, phenyl or naphthyl.
더욱 구체적으로, R1 내지 R9는 각각 독립적으로, 수소, 메틸, 이소프로필, 페닐, 또는 나프틸일 수 있다.More specifically, R 1 to R 9 each independently may be hydrogen, methyl, isopropyl, phenyl, or naphthyl.
예를 들어, R1 및 R5는 각각 독립적으로, 메틸 또는 이소프로필이고, R9는 메틸, 페닐, 또는 나프틸이고, R2 내지 R4 및 R6 내지 R8은 수소일 수 있다.For example, R 1 and R 5 are each independently methyl or isopropyl, R 9 is methyl, phenyl, or naphthyl, and R 2 to R 4 and R 6 to R 8 can be hydrogen.
이때, R1 및 R5는 서로 동일할 수 있다.Here, R 1 and R 5 may be the same as each other.
예를 들어, R1 및 R5는 메틸 또는 이소프로필일 수 있다.For example, R 1 and R 5 may be methyl or isopropyl.
상기 화학식 1로 표시되는 화합물은 하기 화학식 1A로 표시될 수 있다:The compound represented by Formula 1 may be represented by the following Formula 1A:
[화학식 1A]≪ EMI ID =
상기 화학식 1A에서,In the above formula (1A)
X, R1, R5 및 R9에 대한 설명은 상기 화학식 1에서 정의한 바와 같다.X, R 1 , R 5 and R 9 are as defined in the above formula (1).
또한, 상기 화학식 1로 표시되는 화합물의 대표적인 예는 하기 화합물 1-1 내지 1-12 중 하나일 수 있다:Representative examples of the compound represented by the formula (1) may be one of the following compounds 1-1 to 1-12:
일례로, 상기 화학식 1로 표시되는 화합물은 하기 반응식 1과 같은 방법으로 제조할 수 있으나, 이에 한정되는 것은 아니다. 상기 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다.For example, the compound represented by Formula 1 may be prepared according to the following Reaction Scheme 1, but is not limited thereto. The above production method can be more specific in the production example to be described later.
[반응식 1][Reaction Scheme 1]
상기 반응식 1에서, In the above Reaction Scheme 1,
Y 및 Z는 각각 독립적으로, 클로로, 브로모, 또는 아이오도이고, Y and Z are each independently chloro, bromo, or iodo,
X, R1 내지 R9에 대한 설명은 상기 화학식 1에서 정의한 바와 같다.X, R 1 to R 9 are the same as defined in the above formula (1).
한편, 본 발명은 하기 화학식 1로 표시되는 화합물과 하기 화학식 7로 표시되는 화합물을 반응시키거나, 또는 하기 화학식 1로 표시되는 화합물, 하기 화학식 8로 표시되는 화합물 및 하기 화학식 9로 표시되는 화합물을 반응시키는 단계를 포함하는, 하기 화학식 2로 표시되는 전이금속 화합물의 제조 방법을 제공한다:The present invention also relates to a process for preparing a compound represented by the following general formula (1) or (2) by reacting a compound represented by the following general formula (1) with a compound represented by the following general formula Reacting a compound represented by the following formula (2): < EMI ID =
[화학식 2](2)
[화학식 1][Chemical Formula 1]
[화학식 7](7)
M(R10)4 M (R 10 ) 4
[화학식 8][Chemical Formula 8]
MW4 MW 4
[화학식 9][Chemical Formula 9]
R10MgVR 10 MgV
상기 화학식 1, 2, 7, 8 및 9에서,In the above formulas (1), (2), (7), (8)
M은 4족의 전이금속이고,M is a transition metal of Group 4,
X는 O 또는 S이고,X is O or S,
R1 내지 R10은 각각 독립적으로, 수소; C1-20 알킬; C3-20 사이클로알킬; C2-20 알케닐; C6-20 아릴; C7-20 알킬아릴; C7-20 아릴알킬; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 헤테로원자를 1개 이상 포함하는 C2-20 헤테로아릴이고,R 1 to R 10 are each independently hydrogen; C 1-20 alkyl; C 3-20 cycloalkyl; C 2-20 alkenyl; C 6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; Or C 2-20 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,
V 및 W는 각각 독립적으로, 클로로, 브로모, 또는 아이오도이고,V and W are each independently chloro, bromo, or iodo,
n은 2 또는 3이다.n is 2 or 3;
여기서, →는 배위 결합을 의미하고, 점선은 결합의 존재 또는 부존재를 의미한다. 즉, n이 2일 경우, 상기 점선은 결합으로 존재하고, n이 3일 경우, 상기 점선은 결합이 존재하지 않음을 의미한다.Here, → denotes coordination bonding, and the dotted line denotes the presence or absence of bonding. That is, when n is 2, the dotted line is present as a bond, and when n is 3, the dotted line indicates that no bond exists.
상기 화학식 1로 표시되는 화합물과 상기 화학식 7로 표시되는 화합물의 반응, 및 상기 화학식 1로 표시되는 화합물, 상기 화학식 8로 표시되는 화합물 및 상기 화학식 9로 표시되는 화합물의 반응은 각각 상기 화합물들을 혼합한 후 교반을 통해 진행될 수 있다. 이후, 감압 하에서 건조하여 상기 화학식 1로 표시되는 리간드 화합물에 금속 원자가 결합한 착물 형태의 화학식 2로 표시되는 화합물이 얻어질 수 있다. The reaction between the compound represented by Formula 1 and the compound represented by Formula 7 and the reaction between the compound represented by Formula 1, the compound represented by Formula 8, and the compound represented by Formula 9, Followed by stirring. Thereafter, the compound is dried under reduced pressure to obtain a compound represented by the general formula (2) in the form of a complex in which a metal atom is bonded to the ligand compound represented by the general formula (1).
더욱 구체적으로, 상기 화학식 1로 표시되는 화합물과 상기 화학식 7로 표시되는 화합물은 1:1 내지 1:1.5의 몰비로 사용될 수 있다. 예를 들어, 상기 화학식 1로 표시되는 화합물과 상기 화학식 7로 표시되는 화합물은 1:1 내지 1:1.3, 1:1 내지 1:1.2, 1:1 내지 1:1.05, 또는 1:1 내지 1:1.02의 몰비로 사용될 수 있다. More specifically, the compound represented by Formula 1 and the compound represented by Formula 7 may be used in a molar ratio of 1: 1 to 1: 1.5. For example, the compound represented by Formula 1 and the compound represented by Formula 7 may be used in a ratio of 1: 1 to 1: 1.3, 1: 1 to 1: 1.2, 1: 1 to 1: 1.05, : 1.02. ≪ / RTI >
또한, 상기 화학식 1로 표시되는 화합물과 상기 화학식 7로 표시되는 화합물의 반응은 25 내지 100℃의 온도 범위에서 1 내지 12 시간 동안 진행될 수 있다.The reaction between the compound represented by the formula (1) and the compound represented by the formula (7) may be carried out at a temperature ranging from 25 to 100 ° C for 1 to 12 hours.
예를 들어, 상기 화학식 1로 표시되는 화합물, 상기 화학식 8로 표시되는 화합물 및 상기 화학식 9로 표시되는 화합물은 1:1:4 내지 1:1.5:5의 몰비로 사용될 수 있다.For example, the compound represented by Formula 1, the compound represented by Formula 8, and the compound represented by Formula 9 may be used in a molar ratio of 1: 1: 4 to 1: 1.5: 5.
또한, 상기 화학식 1로 표시되는 화합물, 상기 화학식 8로 표시되는 화합물 및 상기 화학식 9로 표시되는 화합물의 반응은 0 내지 100℃의 온도 범위에서 1 내지 72 시간 동안 진행될 수 있다.The reaction of the compound represented by the formula (1), the compound represented by the formula (8) and the compound represented by the formula (9) may be carried out at a temperature ranging from 0 to 100 ° C for 1 to 72 hours.
그리고, 상기 화학식에서, M은 Ti, Zr, 또는 Hf일 수 있다. 예를 들어, M은 Hf일 수 있다. In the above formula, M may be Ti, Zr, or Hf. For example, M may be Hf.
또한, R1 내지 R10은 각각 독립적으로, 수소, C1-10 알킬, C6-10 아릴, 또는 C6-10 아릴알킬일 수 있다.Furthermore, R 1 to R 10 may each independently be hydrogen, C 1-10 alkyl, C 6-10 aryl, or C 6-10 arylalkyl.
구체적으로, R1 내지 R10은 각각 독립적으로, 수소, 메틸, 에틸, 프로필, 이소프로필, 부틸, 이소부틸, sec-부틸, tert-부틸, 페닐, 나프틸, 벤질, 나프틸메틸일 수 있다. Specifically, each of R 1 to R 10 may independently be hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert- butyl, phenyl, naphthyl, benzyl or naphthylmethyl .
더욱 구체적으로, R1 내지 R10은 각각 독립적으로, 수소, 메틸, 이소프로필, 페닐, 나프틸, 또는 벤질일 수 있다.More specifically, R 1 to R 10 each independently may be hydrogen, methyl, isopropyl, phenyl, naphthyl, or benzyl.
예를 들어, R1 및 R5는 각각 독립적으로, 메틸 또는 이소프로필이고, R9는 메틸, 페닐, 또는 나프틸이고, R10은 벤질이고, R2 내지 R4 및 R6 내지 R8은 수소일 수 있다.For example, R 1 and R 5 are each independently methyl or isopropyl, R 9 is methyl, phenyl, or naphthyl, R 10 is benzyl, R 2 to R 4 and R 6 to R 8 are Hydrogen.
이때, R1 및 R5는 서로 동일할 수 있다.Here, R 1 and R 5 may be the same as each other.
예를 들어, R1 및 R5는 메틸 또는 이소프로필일 수 있다.For example, R 1 and R 5 may be methyl or isopropyl.
상기 화학식 2로 표시되는 화합물은 하기 화학식 2A로 표시될 수 있다:The compound represented by Formula 2 may be represented by Formula 2A below:
[화학식 2A](2A)
상기 화학식 2A에서,In the above formula (2A)
M, X, R1, R5, R9, R10 및 n에 대한 설명은 상기 화학식 2에서 정의한 바와 같다.M, X, R 1 , R 5 , R 9 , R 10 and n are as defined in the above formula (2).
또한, 상기 화학식 2로 표시되는 화합물의 대표적인 예는 하기 화합물 2-1 내지 2-12 중 하나일 수 있다:Representative examples of the compound represented by the formula (2) may be one of the following compounds 2-1 to 2-12:
일례로, 상기 화학식 2로 표시되는 화합물은 하기 반응식 2와 같은 방법으로 제조할 수 있으나, 이에 한정되는 것은 아니다. 상기 제조 방법은 후술할 제조예에서 보다 구체화될 수 있다. For example, the compound represented by Formula 2 may be prepared by the following reaction scheme 2, but is not limited thereto. The above production method can be more specific in the production example to be described later.
[반응식 2][Reaction Scheme 2]
상기 반응식 2에서,In the above Reaction Scheme 2,
M, X, V, W, R1 내지 R10 및 n에 대한 설명은 상기 화학식 2, 화학식 8 및 화학식 9에서 정의한 바와 같다.M, X, V, W, R 1 to R 10 and n are the same as defined in the above formulas (2), (8) and (9).
한편, 상술한 방법에 의해 제조된 전이금속 화합물을 포함하는 전이금속 촉매 조성물이 제공될 수 있다. 보다 구체적으로, 상기 전이금속 화합물은 단독으로 또는 상기 전이금속 화합물 이외에 조촉매를 추가로 포함하는 촉매 조성물 형태로, 올레핀계 중합체를 제조하기 위한 중합 반응의 촉매로 사용될 수 있다. 이때, 사용되는 조촉매로는 13족 금속을 포함하는 유기 금속 화합물로서, 일반적으로 전이금속 화합물의 촉매 하에 올레핀을 중합시킬 때 사용될 수 있는 것이라면 특별히 한정되지 않는다.On the other hand, a transition metal catalyst composition comprising the transition metal compound produced by the above-described method can be provided. More specifically, the transition metal compound may be used alone or in the form of a catalyst composition that further includes a cocatalyst in addition to the transition metal compound, as a catalyst for the polymerization reaction to produce the olefinic polymer. The co-catalyst used herein is not particularly limited as long as it is an organometallic compound containing a Group 13 metal and can be generally used in the polymerization of an olefin under the catalyst of a transition metal compound.
구체적으로, 상기 전이금속 촉매 조성물은 하기 화학식 10 내지 12으로 표시되는 화합물들로 이루어진 군으로부터 선택되는 어느 하나 이상의 조촉매를 더 포함할 수 있다:Specifically, the transition metal catalyst composition may further include at least one cocatalyst selected from the group consisting of compounds represented by
[화학식 10][Chemical formula 10]
-[Al(R21)-O]c- - [Al (R 21) -O ] c -
상기 화학식 10에서, In
R21은 각각 독립적으로 할로겐, C1-20 알킬 또는 C1-20 할로알킬이고, Each R < 21 > is independently halogen, C1-20 alkyl or C1-20 haloalkyl,
c는 2 이상의 정수이며,c is an integer of 2 or more,
[화학식 11](11)
D(R22)3 D (R 22) 3
상기 화학식 11에서,In Formula 11,
D는 알루미늄 또는 보론이고, D is aluminum or boron,
R22는 각각 독립적으로, 수소, 할로겐, C1-20 하이드로카빌 또는 할로겐으로 치환된 C1-20 하이드로카빌이고,R 22 are each independently, a substituted C 1-20 hydrocarbyl hydrogen, halogen, C 1-20 hydrocarbyl or a halogen,
[화학식 12][Chemical Formula 12]
[L-H]+[Q(E)4]- 또는 [L]+[Q(E)4]- [LH] + [Q (E ) 4] - or [L] + [Q (E ) 4] -
상기 화학식 12에서,In Formula 12,
L은 중성 또는 양이온성 루이스 염기이고, L is a neutral or cationic Lewis base,
[L-H]+는 브론스테드 산이며, [LH] + is Bronsted acid,
Q는 Br3+ 또는 Al3+이고, Q is Br < 3 + > or Al < 3+
E는 각각 독립적으로 C6-20 아릴 또는 C1-20 알킬이고, 여기서 상기 C6-20 아릴 또는 C1-20 알킬은 비치환되거나 또는 할로겐, C1-20 알킬, C1-20 알콕시 및 페녹시로 구성되는 군으로부터 선택되는 하나 이상의 치환기로 치환된다.Wherein each E is independently C 6-20 aryl or C 1-20 alkyl, wherein said C 6-20 aryl or C 1-20 alkyl is unsubstituted or substituted with one or more groups selected from halogen, C 1-20 alkyl, C 1-20 alkoxy and Lt; / RTI > is substituted by one or more substituents selected from the group consisting of phenoxy.
상기 화학식 10으로 표시되는 화합물로는, 예를 들어 개질메틸알루미녹산(MMAO), 메틸알루미녹산(MAO), 에틸알루미녹산, 이소부틸알루미녹산, 부틸알루미녹산 등이 될 수 있다.Examples of the compound represented by
상기 화학식 11로 표시되는 알킬 금속 화합물로는, 예를 들어 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 디메틸클로로알루미늄, 디메틸이소부틸알루미늄, 디메틸에틸알루미늄, 디에틸클로로알루미늄, 트리이소프로필알루미늄, 트리-s-부틸알루미늄, 트리씨클로펜틸알루미늄, 트리펜틸알루미늄, 트리이소펜틸알루미늄, 트리헥실알루미늄, 에틸디메틸알루미늄, 메틸디에틸알루미늄, 트리페닐알루미늄, 트리-p-톨릴알루미늄, 디메틸알루미늄메톡시드, 디메틸알루미늄에톡시드, 트리메틸보론, 트리에틸보론, 트리이소부틸보론, 트리프로필보론, 트리부틸보론 등일 수 있다.Examples of the alkyl metal compound represented by Formula 11 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethyl Tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, Dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like can be used.
상기 화학식 12으로 표시되는 화합물로는, 예를 들어 트리에틸암모니움테트라페닐보론, 트리부틸암모니움테트라페닐보론, 트리메틸암모니움테트라페닐보론, 트리프로필암모니움테트라페닐보론, 트리메틸암모니움테트라(p-톨릴)보론, 트리프로필암모니움테트라(p-톨릴)보론, 트리에틸암모니움테트라(o,p-디메틸페닐)보론, 트리메틸암모니움테트라(o,p-디메틸페닐)보론, 트리부틸암모니움테트라(p-트리플루오로메틸페닐)보론, 트리메틸암모니움테트라(p-트리플로로메틸페닐)보론, 트리부틸암모니움테트라펜타플루오로페닐보론, N,N-디에틸아닐리니움테트라페닐 보론, N,N-디에틸아닐리니움테트라페닐보론, N,N-디에틸아닐리니움테트라펜타플루오로페닐보론, 디에틸암모니움테트라펜타플루오로페닐보론, 트리페닐포스포늄테트라페닐보론, 트리메틸포스포늄테트라페닐보론, 트리에틸암모니움테트라페닐알루미늄, 트리부틸암모니움테트라페닐알루미늄, 트리메틸암모니움테트라페닐알루미늄, 트리프로필암모니움테트라페닐알루미늄, 트리메틸암모니움테트라(p-톨릴)알루미늄, 트리프로필암모니움테트라(p-톨릴)알루미늄, 트리에틸암모니움테트라(o,p-디메틸페닐)알루미늄, 트리부틸암모니움테트라(p-트리플루오로메틸페닐)알루미늄, 트리메틸암모니움테트라(p-트리플루오로메틸페닐)알루미늄,트리부틸암모니움테트라펜타플루오로페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라페닐알루미늄, N,N-디에틸아닐리니움테트라펜타플로로페닐알루미늄, 디에틸암모니움테트라펜타플루오로페닐알루미늄, 트리페닐포스포늄테트라페닐알루미늄, 트리메틸포스포늄테트라페닐알루미늄, 트리페닐카보니움테트라페닐보론, 트리페닐카보니움테트라페닐알루미늄, 트리페닐카보니움테트라(p-트리플로로메틸페닐)보론, 트리페닐카보니움테트라펜타플루오로페닐보론 등일 수 있다.Examples of the compound represented by Formula 12 include triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra (p (O, p-dimethylphenyl) boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, trimethylammoniumtetra (P-trifluoromethylphenyl) boron, tetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p -trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N , N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylporphyrin (P-tolyl) aluminum, tripropylammonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl ) Aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetra Tetrafluoro aluminum, pentafluorophenyl aluminum, diethylammonium tetrapentafluorophenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetra Phenyl aluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenyl aluminum, triphenylcarboniumtetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, etc. have.
보다 구체적으로, 상기 촉매 조성물은 조촉매로 메틸알루미녹산, 트리메틸알루미늄, 트리에틸알루미늄, 트리이소부틸알루미늄, 또는 메틸알룸옥산(MAO)을 사용할 수 있다. More specifically, the catalyst composition can use methyl aluminoxane, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, or methyl alumoxane (MAO) as a cocatalyst.
상기 조촉매의 사용 함량은 목적하는 촉매 조성물의 물성 또는 효과에 따라 적절하게 조절될 수 있다. The content of the cocatalyst can be appropriately controlled depending on the physical properties or effects of the desired catalyst composition.
상기 촉매 조성물은 상기 전이금속 화합물과 조촉매 화합물을 담체에 담지된 형태로 포함할 수 있다. 상기 화학식 2로 표시되는 전이 금속 화합물은 상술한 구조적 특징을 가져 담체에 안정적으로 담지될 수 있다. 또한, 이러한 전이 금속 화합물이 담지된 담지 촉매는 올레핀 중합에 높은 활성을 나타낼 수 있다. The catalyst composition may contain the transition metal compound and the cocatalyst compound in the form of being supported on a carrier. The transition metal compound represented by Formula 2 has the above-described structural characteristics and can be stably supported on the carrier. In addition, the supported catalyst carrying such a transition metal compound can exhibit high activity in olefin polymerization.
상기 담체로는 표면에 하이드록시기 또는 실록산기를 함유하는 담체를 사용할 수 있다. 구체적으로, 상기 담체로는 고온에서 건조하여 표면에 수분을 제거함으로써 반응성이 큰 하이드록시기 또는 실록산기를 함유하는 담체를 사용할 수 있다. 보다 구체적으로, 상기 담체로는 실리카, 알루미나, 마그네시아 또는 이들의 혼합물 등을 사용할 수 있다. 상기 담체는 고온에서 건조된 것일 수 있고, 이들은 통상적으로 Na2O, K2CO3, BaSO4 및 Mg(NO3)2 등의 산화물, 탄산염, 황산염, 질산염 성분을 포함할 수 있다.As the carrier, a carrier containing a hydroxyl group or a siloxane group on its surface can be used. Specifically, as the carrier, a carrier containing a hydroxyl group or a siloxane group having high reactivity by removing moisture on the surface by drying at a high temperature may be used. More specifically, examples of the carrier include silica, alumina, magnesia, and mixtures thereof. The carrier may be one which has been dried at elevated temperatures and these may typically comprise oxides, carbonates, sulphates and nitrate components such as Na2O, K2CO3, BaSO4 and Mg (NO3) 2.
한편, 상술한 제조 방법에 의해 제조된 전이금속 화합물을 포함하는 촉매 조성물의 존재 하에, 올레핀계 단량체를 중합 반응시키는 단계를 포함하는 올레핀계 중합체의 제조 방법이 제공될 수 있다.On the other hand, there can be provided a process for producing an olefin-based polymer comprising the step of polymerizing an olefin monomer in the presence of a catalyst composition comprising a transition metal compound produced by the above-mentioned production method.
상기 합성되는 올레핀계 중합체의 예가 특별히 제한되는 것은 아니나, 예를 들어 올레핀 단독 중합체, 올레핀 공중합체 또는 에틸렌/알파-올레핀 공중합체일 수 있다. 구체적으로 에틸렌/알파올레핀 공중합체일 수 있다. Examples of the olefin polymer to be synthesized are not particularly limited, but may be, for example, an olefin homopolymer, an olefin copolymer or an ethylene / alpha-olefin copolymer. Specifically, it may be an ethylene / alpha olefin copolymer.
상기 올레핀계 단량체의 구체적인 예로는 에틸렌, 알파-올레핀, 사이클릭 올레핀 등이 있으며, 이중 결합을 2개 이상 가지고 있는 다이엔 올레핀계 단량체 또는 트라이엔 올레핀계 단량체 등도 중합 가능하다. 상기 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, 노보넨, 노보나디엔, 에틸리덴노보넨, 페닐노보넨, 비닐노보넨, 디사이클로펜타디엔, 1,4-부타디엔, 1,5-펜타디엔, 1,6-헥사디엔, 스티렌, 알파-메틸스티렌, 디비닐벤젠, 3-클로로메틸스티렌 등이 있으며, 이들 단량체를 2 종 이상 혼합하여 공중합할 수도 있다.Specific examples of the olefin-based monomer include ethylene, alpha-olefin, cyclic olefin, and the like. Dioene olefin-based monomers or triene olefin-based monomers having two or more double bonds can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. These two or more monomers may be mixed and copolymerized.
상기 올레핀계 단량체의 중합 반응은 연속식 용행 중합 공정, 벌크 중합 공정, 현탁 중합 공정 또는 유화 중합 공정등으로 제한 없이 진행될 수 있으나, 예를 들어 단일 반응기에서 이루어지는 용액 공중합(solution polymerization) 반응 또는 담지 공중합 반응에 의할 수 있다. 상기 용액 공중합 반응은 상기 전이금속 촉매 조성물을 용매에 직접 녹여 용액 상태로 이루어지며, 상기 담지 공중합 반응은 상기 전이금속 촉매 조성물을 상술한 담체에 담지시켜 담지 촉매를 제조한 후, 상기 담지 촉매를 용매에 투입하여 슬러리 상태로 이루어 질 수 있다.The polymerization of the olefin monomer may be carried out without limitation, for example, a continuous polymerization process, a bulk polymerization process, a suspension polymerization process, or an emulsion polymerization process. For example, a solution polymerization reaction in a single reactor, Reaction can be done. The solution copolymerization reaction is carried out by dissolving the transition metal catalyst composition directly in a solvent in a solution state. The supported copolymerization reaction is carried out by preparing a supported catalyst by supporting the transition metal catalyst composition on the carrier, Into a slurry state.
상기 올레핀계 단량체의 중합 반응은 45 내지 200의 온도, 또는 60 내지 150 에서, 0.1 시간 내지 2.5 시간, 또는 0.1 시간 내지 1.3 시간 동안 이루어 질 수 있다. 또한, 압력은 1 bar 내지 50 bar, 또는 2 bar 내지 45 bar에서 진행될 수 있다. 구체적으로 상기 용액 공중합 반응은 1 bar 내지 50 bar의 압력, 60 내지 150의 온도에서 0.1 시간 내지 1 시간 동안 진행될 수 있고, 상기 담지 공중합 반응은 1 bar 내지 50 bar의 압력, 60 내지 90의 온도에서 0.5 시간 내지 2.5 시간 동안 진행될 수 있다.The polymerization of the olefin-based monomer may be carried out at a temperature of 45 to 200, or 60 to 150 for 0.1 to 2.5 hours, or 0.1 to 1.3 hours. Also, the pressure can be from 1 bar to 50 bar, or from 2 bar to 45 bar. Specifically, the solution copolymerization reaction may be conducted at a pressure of 1 bar to 50 bar, at a temperature of 60 to 150 for 0.1 hour to 1 hour, and the supported copolymerization reaction may be carried out at a pressure of 1 bar to 50 bar, For 0.5 to 2.5 hours.
상기 중합 반응에서 사용되는 반응기에는 별 다른 제한이 없으나, 예를 들어 연속 교반식 반응기(CSTR) 또는 연속 흐름식 반응기(PFR)를 사용할 수 있다. 상기 중합 반응에서 반응기는 2개 이상 직렬 혹은 병렬로 배열될 수 있고, 반응 혼합물로부터 용매 및 미반응 단량체를 연속적으로 분리하기 위한 분리기를 추가적으로 포함할 수 있다.There is no particular limitation on the reactor used in the polymerization reaction, but for example, a continuously stirred reactor (CSTR) or a continuous flow reactor (PFR) can be used. In the polymerization reaction, two or more reactors may be arranged in series or in parallel, and may further include a separator for continuously separating the solvent and unreacted monomers from the reaction mixture.
본 발명의 제조 방법에 의해 제조된 신규한 리간드 화합물 및 이를 포함하는 전이금속 화합물은, 높은 촉매 활성을 나타내며 고분자량의 올레핀계 중합체를 제조할 수 있어, 올레핀계 중합체의 제조에 있어 중합 반응의 촉매로 유용하게 사용될 수 있다. The novel ligand compound produced by the production method of the present invention and the transition metal compound containing the same can produce an olefin polymer having a high molecular weight and exhibiting a high catalytic activity, . ≪ / RTI >
도 1은 실시예 9에서 합성한 전이금속 화합물 2-1의 1H NMR spectrum을 나타낸 것이다.
도 2는 실시예 10에서 합성한 전이금속 화합물 2-7의 1H NMR spectrum을 나타낸 것이다.
도 3은 실시예 11에서 합성한 전이금속 화합물 2-3의 1H NMR spectrum을 나타낸 것이다.
도 4는 실시예 12에서 합성한 전이금속 화합물 2-9의 1H NMR spectrum을 나타낸 것이다.
도 5는 실시예 13에서 합성한 전이금속 화합물 2-4의 1H NMR spectrum을 나타낸 것이다.
도 6은 실시예 14에서 합성한 전이금속 화합물 2-10의 1H NMR spectrum을 나타낸 것이다.
도 7은 실시예 15에서 합성한 전이금속 화합물 2-6의 1H NMR spectrum을 나타낸 것이다.
도 8은 실시예 16에서 합성한 전이금속 화합물 2-12의 1H NMR spectrum을 나타낸 것이다.1 shows the 1 H NMR spectrum of the transition metal compound 2-1 synthesized in Example 9.
2 shows the 1 H NMR spectrum of the transition metal compound 2-7 synthesized in Example 10.
3 is a 1 H NMR spectrum of the transition metal compound 2-3 synthesized in Example 11.
4 shows the 1 H NMR spectrum of the transition metal compound 2-9 synthesized in Example 12.
5 shows the 1 H NMR spectrum of the transition metal compound 2-4 synthesized in Example 13.
6 shows the 1 H NMR spectrum of the transition metal compound 2-10 synthesized in Example 14.
7 shows the 1 H NMR spectrum of the transition metal compound 2-6 synthesized in Example 15.
8 is a 1 H NMR spectrum of the transition metal compound 2-12 synthesized in Example 16.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.
실시예 1: 화합물 1-1의 합성Example 1: Synthesis of Compound 1-1
단계 (a): 4-Step (a): 4- 클로로Chloro -2--2- 메틸벤조[d]옥사졸Methylbenzo [d] oxazole (4-(4- chlorochloro -2-methylbenzo[d]oxazole)의 제조-2-methylbenzo [d] oxazole)
잘 건조되고 Ar으로 치환된 250 mL Schlenk flask에 2-bromo-4-chlorobenzo[d]oxazole (1.86 g, 8 mmol), methylboronic acid(484 mg, 8.08 mmol), 2M Na2CO3 수용액(10 mL, 20 mmol), 무수 ethanol(20 mL), 무수 toluene(20 mL), Pd(PPh3)4(279 mg, 0.24 mmol)을 투입하였다. Degassing한 후 Ar으로 치환하고 80℃ 하에서 18 시간 동안 강하게 교반하였다. 일정 시간 후 상온으로 냉각시키고 유기층을 분리하였다. 물층은 dichloromethane(20 mL x 2회)으로 씻어주었다. 유기층을 모아 Silica gel pad를 통과시킨 후 농축하였다. Crude product를 column chromatography(n-hexane / ethyl acetate = 100 / 1)로 정제하여 4-클로로-2-메틸벤조[d]옥사졸을 얻었다. 수율 1.09 g (81%). 2-bromo-4-chlorobenzo [ d ] oxazole (1.86 g, 8 mmol), methylboronic acid (484 mg, 8.08 mmol) and a solution of 2M Na 2 CO 3 in water (10 mL) were added to a 250 mL Schlenk flask, , 20 mmol), anhydrous ethanol (20 mL), anhydrous toluene (20 mL) and Pd (PPh 3 ) 4 (279 mg, 0.24 mmol). After degassing, it was substituted with Ar and stirred vigorously at 80 DEG C for 18 hours. After a certain period of time, the mixture was cooled to room temperature and the organic layer was separated. The water layer was washed with dichloromethane (20 mL x 2). The organic layer was collected, passed through a Silica gel pad, and concentrated. The crude product was purified by column chromatography ( n- hexane / ethyl acetate = 100/1) to obtain 4-chloro-2-methylbenzo [d] oxazole. Yield 1.09 g (81%).
1H NMR (600 MHz, CDCl3, ppm): 7.43 (dd, J=8.0, 0.9 Hz, 1 H), 7.38 (dd, J=8.1, 0.9 Hz, 1 H), 7.14 (t, J=8.1 Hz, 1 H), 2.64 (s, 3 H). 1 H NMR (600 MHz, CDCl 3, ppm): 7.43 (dd, J = 8.0, 0.9 Hz, 1 H), 7.38 (dd, J = 8.1, 0.9 Hz, 1 H), 7.14 (t, J = 8.1 Hz, 1H), 2.64 (s, 3H).
단계 (b): 화합물 1-1의 제조Step (b): Preparation of compound 1-1
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 단계 (a)에서 제조한 4-클로로-2-메틸벤조[d]옥사졸(503 mg, 3 mmol), Pd2(dba)3(165 mg, 0.18 mmol), DPPF(200 mg, 0.36 mmol), sodium tert-butoxide(432 mg, 4.5 mmol), 무수 1,4-dioxane (15 mL), 2,6-dimethylaniline (406 μL, 3.3 mmol)을 투입하고 18 시간 동안 reflux하였다. 일정 시간 후 상온으로 냉각시키고 sat'd NH4Cl 수용액(15 mL)을 투입하여 반응을 종결시켰다. 유기층을 분리하여 silica gel pad를 통과시킨 후 농축하였다. Crude product를 ethanol 하에서 재결정하여 화합물 1-1을 얻었다. 수율 257 mg (34%). Chloro-2-methylbenzo [d] oxazole (503 mg, 3 mmol) and Pd 2 (dba) 3 (165 mg, , 0.18 mmol), DPPF (200 mg, 0.36 mmol), sodium tert- butoxide (432 mg, 4.5 mmol), anhydrous 1,4-dioxane (15 mL), and 2,6-dimethylaniline (406 μL, Were added and refluxed for 18 hours. After a certain period of time, the reaction mixture was cooled to room temperature and quenched by the addition of sat'd NH 4 Cl aqueous solution (15 mL). The organic layer was separated, passed through a silica gel pad, and concentrated. Crude product was recrystallized under ethanol to obtain Compound 1-1. Yield 257 mg (34%).
1H NMR (600 MHz, CDCl3, ppm): 7.15 (q, J=5.1 Hz, 3 H), 7.00 (t, J=8.1 Hz, 1 H), 6.86 (d, J=8.1 Hz, 1 H), 6.05 (br. s., 1 H), 6.00 (d, J=8.1 Hz, 1 H), 2.66 (s, 3 H), 2.25 (s, 6 H). 1 H NMR (600 MHz, CDCl 3, ppm): 7.15 (q, J = 5.1 Hz, 3 H), 7.00 (t, J = 8.1 Hz, 1 H), 6.86 (d, J = 8.1 Hz, 1 H ), 6.05 (br s, 1H), 6.00 (d, J = 8.1 Hz, 1H), 2.66 (s, 3H), 2.25 (s, 6H).
실시예 2: 화합물 1-7의 합성Example 2: Synthesis of Compound 1-7
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 1의 단계 (a)에서 제조한 4-클로로-2-메틸벤조[d]옥사졸 (503 mg, 3 mmol), Pd2(dba)3 (165 mg, 0.18 mmol), DPPF (200 mg, 0.36 mmol), sodium tert-butoxide(432 mg, 4.5 mmol), 무수 1,4-dioxane (15 mL), 2,6-diisopropylaniline (622 μL, 3.3 mmol)을 투입하고 18 시간 동안 reflux하였다. 일정 시간 후 상온으로 냉각시키고 sat'd NH4Cl 수용액(15 mL)을 투입하여 반응을 종결시켰다. 유기층을 분리하여 silica gel pad를 통과시킨 후 농축하였다. Crude product를 ethanol 하에서 재결정하여 화합물 1-7을 얻었다. 수율 315 mg (34%). Chloro-2-methylbenzo [d] oxazole (503 mg, 3 mmol) and Pd 2 (dba) prepared in step (a) of Example 1 were added to a 100 mL Schlenk flask which was well- 3 (165 mg, 0.18 mmol) , DPPF (200 mg, 0.36 mmol), sodium tert -butoxide (432 mg, 4.5 mmol), anhydrous 1,4-dioxane (15 mL), 2,6-diisopropylaniline (622 μL, 3.3 mmol) was added and refluxed for 18 hours. After a certain period of time, the reaction mixture was cooled to room temperature and quenched by the addition of sat'd NH 4 Cl aqueous solution (15 mL). The organic layer was separated, passed through a silica gel pad, and concentrated. Crude product was recrystallized under ethanol to obtain Compound 1-7. Yield 315 mg (34%).
1H NMR (600 MHz, CDCl3, ppm): 7.31 (t, J=7.6 Hz, 1 H), 7.22 (d, J=7.7 Hz, 2 H), 6.95 (t, J=8.1 Hz, 1 H), 6.79 (dd, J=8.1, 0.8 Hz, 1 H), 5.96 (s, 1 H), 5.94 (d, J=8.1 Hz, 1 H), 3.21 (spt, J=6.9 Hz, 2 H), 2.64 (s, 3 H), 1.12 (d, J=6.9 Hz, 13 H). 1 H NMR (600 MHz, CDCl 3 , ppm): 7.31 (t, J = 7.6 Hz, 1H), 7.22 J = 8.1 Hz, 1H), 3.21 (spt, J = 6.9 Hz, 2H), 6.79 (dd, J = 8.1, 0.8 Hz, 1H) , 2.64 (s, 3 H), 1.12 (d, J = 6.9 Hz, 13 H).
실시예 3: 화합물 1-3의 합성Example 3: Synthesis of Compound 1-3
단계 (a): 4-Step (a): 4- 클로로Chloro -2--2- (나프탈렌-1-일)벤조[d]옥사졸(4-chloro-2-(Naphthalen-l-yl) benzo [d] oxazole (4-chloro-2- (naphthalen-1-yl)benzo[d]oxazole)의 제조(naphthalen-1-yl) benzo [d] oxazole)
잘 건조되고 Ar으로 치환된 250 mL Schlenk flask에 2-bromo-4-chlorobenzo[d]oxazole(1.86 g, 8 mmol), 1-naphthylboronic acid(1.07 g, 8.08 mmol), 2M Na2CO3 수용액(10 mL, 20 mmol), 무수 ethanol(20 mL), 무수 toluene (20 mL), Pd(PPh3)4(279 mg, 0.24 mmol)을 투입하였다. Degassing한 후 Ar으로 치환하고 80℃ 하에서 18 시간 동안 강하게 교반하였다. 일정 시간 후 상온으로 냉각시키고 유기층을 분리하였다. 물층은 dichloromethane (20 mL x 2회)으로 씻어주었다. 유기층을 모아 Silica gel pad를 통과시킨 후 농축하였다. Crude product를 column chromatography (n-hexane / ethyl acetate = 100 / 1)로 정제하여 4-클로로-2-(나프탈렌-1-일)벤조[d]옥사졸을 얻었다. 수율 1.72 g (77%). A solution of 2-bromo-4-chlorobenzo [ d ] oxazole (1.86 g, 8 mmol), 1-naphthylboronic acid (1.07 g, 8.08 mmol) and 2M Na 2 CO 3 10 mL, 20 mmol), anhydrous ethanol (20 mL), anhydrous toluene (20 mL) and Pd (PPh 3 ) 4 (279 mg, 0.24 mmol). After degassing, it was substituted with Ar and stirred vigorously at 80 DEG C for 18 hours. After a certain period of time, the mixture was cooled to room temperature and the organic layer was separated. The water layer was washed with dichloromethane (20 mL x 2). The organic layer was collected, passed through a Silica gel pad, and concentrated. The crude product was purified by column chromatography ( n- hexane / ethyl acetate = 100/1) to obtain 4-chloro-2- (naphthalen-1-yl) benzo [ d ] oxazole. Yield 1.72 g (77%).
1H NMR (600 MHz, CDCl3, ppm): 9.48 (d, J=8.6 Hz, 1 H), 8.45 (dd, J=7.2, 0.9 Hz, 1 H), 8.05 (d, J=8.2 Hz, 1 H), 7.94 (d, J=8.2 Hz, 1 H), 7.74 (td, J=7.7, 1.1 Hz, 1 H), 7.53 - 7.66 (m, 4 H), 7.19 - 7.33 (m, 1 H). 1 H NMR (600 MHz, CDCl 3, ppm): 9.48 (d, J = 8.6 Hz, 1 H), 8.45 (dd, J = 7.2, 0.9 Hz, 1 H), 8.05 (d, J = 8.2 Hz, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.74 (td, J = 7.7,1.1 Hz, 1H), 7.53-7.66 (m, 4H), 7.19-7.33 ).
단계 (b): 화합물 1-3의 제조Step (b): Preparation of compound 1-3
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 단계 (a)에서 제조한 4-클로로-2-(나프탈렌-1-일)벤조[d]옥사졸(839 mg, 3 mmol), Pd2(dba)3(165 mg, 0.18 mmol), DPPF(200 mg, 0.36 mmol), sodium tert-butoxide(432 mg, 4.5 mmol), 무수 1,4-dioxane(15 mL), 2,6-dimethylaniline(406 μL, 3.3 mmol)을 투입하고 18 시간 동안 reflux하였다. 일정 시간 후 상온으로 냉각시키고 sat'd NH4Cl 수용액(15 mL)을 투입하여 반응을 종결시켰다. 유기층을 분리하여 silica gel pad를 통과시킨 후 농축하였다. Crude product를 ethanol 하에서 재결정하여 화합물 1-3을 얻었다. 수율 820 mg (75%). To a 100 mL Schlenk flask which was well dried and replaced with Ar was added 4-chloro-2- (naphthalen-1-yl) benzo [d] oxazole (839 mg, 3 mmol), Pd 2 dba) 3 (165 mg, 0.18 mmol), DPPF (200 mg, 0.36 mmol), sodium tert -butoxide (432 mg, 4.5 mmol), anhydrous 1,4-dioxane (15 mL), 2,6-dimethylaniline (406 mu L, 3.3 mmol) was added and refluxed for 18 hours. After a certain period of time, the reaction mixture was cooled to room temperature and quenched by the addition of sat'd NH 4 Cl aqueous solution (15 mL). The organic layer was separated, passed through a silica gel pad, and concentrated. Crude product was recrystallized under ethanol to obtain Compound 1-3. Yield 820 mg (75%).
1H NMR (600 MHz, CDCl3, ppm): 9.51 (d, J=8.6 Hz, 1 H), 8.45 (d, J=7.2 Hz, 1 H), 8.03 (d, J=8.2 Hz, 1 H), 7.96 (d, J=8.2 Hz, 1 H), 7.72 (t, J=7.7 Hz, 1 H), 7.62 (dt, J=11.4, 7.7 Hz, 2 H), 7.14 - 7.24 (m, 3 H), 7.13 (t, J=8.0 Hz, 1 H), 7.02 (d, J=8.0 Hz, 1 H), 6.31 (br. s., 1 H), 6.13 (d, J=8.0 Hz, 1 H), 2.34 (s, 6 H). 1 H NMR (600 MHz, CDCl 3, ppm): 9.51 (d, J = 8.6 Hz, 1 H), 8.45 (d, J = 7.2 Hz, 1 H), 8.03 (d, J = 8.2 Hz, 1 H ), 7.96 (d, J = 8.2 Hz, 1 H), 7.72 (t, J = 7.7 Hz, 1 H), 7.62 (dt, J = 11.4, 7.7 Hz, 2 H), 7.14 - 7.24 (m, 3 H), 7.13 (t, J = 8.0 Hz, 1 H), 7.02 (d, J = 8.0 Hz, 1 H), 6.31 (br. s., 1 H), 6.13 (d, J = 8.0 Hz, 1 H), 2.34 (s, 6 H).
실시예 4: 화합물 1-9의 합성Example 4: Synthesis of Compound 1-9
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 3의 단계 (a)에서 제조한 4-클로로-2-(나프탈렌-1-일)벤조[d]옥사졸(839 mg, 3 mmol), Pd2(dba)3(165 mg, 0.18 mmol), DPPF(200 mg, 0.36 mmol), sodium tert-butoxide(432 mg, 4.5 mmol), 무수 1,4-dioxane(15 mL), 2,6-diisopropylaniline(622 μL, 3.3 mmol)을 투입하고 18 시간 동안 reflux하였다. 일정 시간 후 상온으로 냉각시키고 sat'd NH4Cl 수용액(15 mL)을 투입하여 반응을 종결시켰다. 유기층을 분리하여 silica gel pad를 통과시킨 후 농축하였다. Crude product를 ethanol 하에서 재결정하여 화합물 1-9를 얻었다. 수율 707 mg (56%). (Naphthalen-1-yl) benzo [d] oxazole (839 mg, 3 mmol) prepared in step (a) of Example 3 was added to a 100 mL Schlenk flask which was well- , Pd 2 (dba) 3 ( 165 mg, 0.18 mmol), DPPF (200 mg, 0.36 mmol), sodium tert -butoxide (432 mg, 4.5 mmol), anhydrous 1,4-dioxane (15 mL), 2,6 -diisopropylaniline (622 μL, 3.3 mmol) was added and refluxed for 18 hours. After a certain period of time, the reaction mixture was cooled to room temperature and quenched by the addition of sat'd NH 4 Cl aqueous solution (15 mL). The organic layer was separated, passed through a silica gel pad, and concentrated. Crude product was recrystallized under ethanol to obtain Compound 1-9. Yield 707 mg (56%).
1H NMR (600 MHz, CDCl3, ppm): 9.49 (d, J=8.2 Hz, 1 H), 8.45 (dd, J=7.2, 1.2 Hz, 1 H), 8.04 (d, J=8.3 Hz, 1 H), 7.97 (d, J=8.2 Hz, 1 H), 7.69 - 7.78 (m, 1 H), 7.61 - 7.65 (m, 2 H), 7.35 - 7.41 (m, 1 H), 7.29 - 7.32 (m, 2 H), 7.11 (t, J=8.0 Hz, 1 H), 7.00 (dd, J=8.1, 0.7 Hz, 1 H), 6.29 (s, 1 H), 6.10 (d, J=8.0 Hz, 1 H), 3.36 (spt, J=6.9 Hz, 2 H), 1.22 (d, J=6.8 Hz, 12 H). 1 H NMR (600 MHz, CDCl 3, ppm): 9.49 (d, J = 8.2 Hz, 1 H), 8.45 (dd, J = 7.2, 1.2 Hz, 1 H), 8.04 (d, J = 8.3 Hz, (M, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.69-7.78 (m, 1H) (m, 2 H), 7.11 (t, J = 8.0 Hz, 1 H), 7.00 (dd, J = 8.1, 0.7 Hz, 1 H), 6.29 (s, 1 H), 6.10 (d, J = 8.0 Hz, 1 H), 3.36 (spt, J = 6.9 Hz, 2 H), 1.22 (d, J = 6.8 Hz, 12 H).
실시예 5: 화합물 1-4의 합성Example 5: Synthesis of Compound 1-4
단계 (a): 4-Step (a): 4- 클로로Chloro -2--2- 메틸벤조Methylbenzo [[ dd ]티아졸(4-] Thiazole (4- chlorochloro -2-methylbenzo[-2-methylbenzo [ dd ]thiazole)의 제조] thiazole
잘 건조되고 Ar으로 치환된 250 mL Schlenk flask에 2-bromo-4-chlorobenzo[d]thiazole (1.99 g, 8 mmol), methylboronic acid (484 mg, 8.08 mmol), 2M Na2CO3 수용액 (10 mL, 20 mmol), 무수 ethanol (20 mL), 무수 toluene (20 mL), Pd(PPh3)4(279 mg, 0.24 mmol)을 투입하였다. Degassing한 후 Ar으로 치환하고 80℃ 하에서 18 시간 동안 강하게 교반하였다. 일정 시간 후 상온으로 냉각시키고 유기층을 분리하였다. 물층은 dichloromethane(20 mL x 2회)으로 씻어주었다. 유기층을 모아 Silica gel pad를 통과시킨 후 농축하였다. Crude product를 column chromatography(n-hexane / ethyl acetate = 100 / 1)로 정제하여 4-클로로-2-메틸벤조[d]티아졸을 얻었다. 수율 1.41 g (96%). 2-bromo-4-chlorobenzo [ d ] thiazole (1.99 g, 8 mmol), methylboronic acid (484 mg, 8.08 mmol) and aqueous 2M Na 2 CO 3 solution (10 mL) were added to a 250 mL Schlenk flask, , 20 mmol), anhydrous ethanol (20 mL), anhydrous toluene (20 mL) and Pd (PPh 3 ) 4 (279 mg, 0.24 mmol). After degassing, it was substituted with Ar and stirred vigorously at 80 DEG C for 18 hours. After a certain period of time, the mixture was cooled to room temperature and the organic layer was separated. The water layer was washed with dichloromethane (20 mL x 2). The organic layer was collected, passed through a Silica gel pad, and concentrated. The crude product was purified by column chromatography ( n -hexane / ethyl acetate = 100/1) to obtain 4-chloro-2-methylbenzo [ d ] thiazole. Yield 1.41 g (96%).
1H NMR (600 MHz, CDCl3, ppm): 7.72 (dd, J=8.0, 1.0 Hz, 1 H), 7.60 (dd, J=7.7, 1.0 Hz, 1 H), 7.17 (t, J=7.9 Hz, 1 H), 2.85 (s, 3 H). 1 H NMR (600 MHz, CDCl 3, ppm): 7.72 (dd, J = 8.0, 1.0 Hz, 1 H), 7.60 (dd, J = 7.7, 1.0 Hz, 1 H), 7.17 (t, J = 7.9 Hz, 1H), 2.85 (s, 3H).
단계 (b): 화합물 1-4의 제조Step (b): Preparation of compounds 1-4
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 단계 (a)에서 제조한 4-클로로-2-메틸벤조[d]티아졸(551 mg, 3 mmol), Pd2(dba)3(165 mg, 0.18 mmol), DPPF(200 mg, 0.36 mmol), sodium tert-butoxide(432 mg, 4.5 mmol), 무수 1,4-dioxane(15 mL), 2,6-dimethylaniline(406 μL, 3.3 mmol)을 투입하고 18 시간 동안 reflux하였다. 일정 시간 후 상온으로 냉각시키고 sat'd NH4Cl 수용액(15 mL)을 투입하여 반응을 종결시켰다. 유기층을 분리하여 silica gel pad를 통과시킨 후 농축하였다. Crude product를 ethanol 하에서 재결정하여 화합물 1-4를 얻었다. 수율 668 mg (83%). Chloro-2-methylbenzo [ d ] thiazole (551 mg, 3 mmol) and Pd 2 (dba) 3 (165 mg, prepared as described in step (a)) in 100 mL Schlenk flask, , 0.18 mmol), DPPF (200 mg, 0.36 mmol), sodium tert- butoxide (432 mg, 4.5 mmol), anhydrous 1,4-dioxane (15 mL), and 2,6-dimethylaniline (406 μL, Were added and refluxed for 18 hours. After a certain period of time, the reaction mixture was cooled to room temperature and quenched by the addition of sat'd NH 4 Cl aqueous solution (15 mL). The organic layer was separated, passed through a silica gel pad, and concentrated. Crude product was recrystallized under ethanol to obtain Compound 1-4. Yield 668 mg (83%).
1H NMR (600 MHz, CDCl3, ppm): 7.13 - 7.20 (m, 4 H), 7.07 (t, J=7.9 Hz, 1 H), 6.57 (s, 1 H), 6.10 - 6.14 (m, 1 H), 2.87 (s, 3 H), 2.28 (s, 6 H). 1 H NMR (600 MHz, CDCl 3 , ppm): 7.13-7.20 (m, 4 H), 7.07 (t, J = 7.9 Hz, 1 H), 2.87 (s, 3 H), 2.28 (s, 6 H).
실시예 6: 화합물 1-10의 합성Example 6: Synthesis of Compound 1-10
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 5의 단계 (a)에서 제조한 4-클로로-2-메틸벤조[d]티아졸(551 mg, 3 mmol), Pd2(dba)3(165 mg, 0.18 mmol), DPPF(200 mg, 0.36 mmol), sodium tert-butoxide(432 mg, 4.5 mmol), 무수 1,4-dioxane(15 mL), 2,6-diisopropylaniline(622 μL, 3.3 mmol)을 투입하고 18 시간 동안 reflux하였다. 일정 시간 후 상온으로 냉각시키고 sat'd NH4Cl 수용액(15 mL)을 투입하여 반응을 종결시켰다. 유기층을 분리하여 silica gel pad를 통과시킨 후 농축하였다. Crude product를 ethanol 하에서 재결정하여 화합물 1-10을 얻었다. 수율 896 mg (92%). Chloro-2-methylbenzo [ d ] thiazole (551 mg, 3 mmol) and Pd 2 (dba) prepared in step (a) of Example 5 were added to a 100 mL Schlenk flask which was well- 3 (165 mg, 0.18 mmol) , DPPF (200 mg, 0.36 mmol), sodium tert -butoxide (432 mg, 4.5 mmol), anhydrous 1,4-dioxane (15 mL), 2,6-diisopropylaniline (622 μL, 3.3 mmol) was added and refluxed for 18 hours. After a certain period of time, the reaction mixture was cooled to room temperature and quenched by the addition of sat'd NH 4 Cl aqueous solution (15 mL). The organic layer was separated, passed through a silica gel pad, and concentrated. Crude product was recrystallized under ethanol to obtain compound 1-10. Yield 896 mg (92%).
1H NMR (600 MHz, CDCl3, ppm): 7.35 (t, J=7.7 Hz, 1 H), 7.27 (d, J=7.5 Hz, 2 H), 7.12 (d, J=7.9 Hz, 1 H), 7.05 (t, J=7.8 Hz, 1 H), 6.54 (s, 1 H), 6.09 (d, J=7.8 Hz, 1 H), 3.27 (dt, J=13.7, 6.8 Hz, 2 H), 2.88 (s, 3 H), 1.17 (d, J=5.7 Hz, 12 H). 1 H NMR (600 MHz, CDCl 3, ppm): 7.35 (t, J = 7.7 Hz, 1 H), 7.27 (d, J = 7.5 Hz, 2 H), 7.12 (d, J = 7.9 Hz, 1 H ), 7.05 (t, J = 7.8 Hz, 1 H), 6.54 (s, 1 H), 6.09 (d, J = 7.8 Hz, 1 H), 3.27 (dt, J = 13.7, 6.8 Hz, 2 H) , 2.88 (s, 3 H), 1.17 (d, J = 5.7 Hz, 12 H).
실시예 7: 화합물 1-6의 합성Example 7: Synthesis of Compound 1-6
단계 (a): 4-Step (a): 4- 클로로Chloro -2--2- (나프탈렌-1-일)벤조[(Naphthalen-1-yl) benzo [ dd ]티아졸] Thiazole (4-(4- chlorochloro -2-(naphthalen-1-yl)benzo[-2- (naphthalen-1-yl) benzo [ dd ]thiazole)의 제조] thiazole
잘 건조되고 Ar으로 치환된 250 mL Schlenk flask에 2-bromo-4-chlorobenzo[d]thiazole(2.48 g, 10 mmol), 1-naphthylboronic acid(1.34 g, 10.1 mmol), 2M Na2CO3 수용액(12.5 mL, 25 mmol), 무수 ethanol(25 mL), 무수 toluene(25 mL), Pd(PPh3)4(347 mg, 0.3 mmol)을 투입하였다. Degassing한 후 Ar으로 치환하고 80℃ 하에서 18 시간 동안 강하게 교반하였다. 일정 시간 후 상온으로 냉각시키고 유기층을 분리하였다. 물층은 dichloromethane (25 mL x 2회)으로 씻어주었다. 유기층을 모아 Silica gel pad를 통과시킨 후 농축하였다. Crude product를 column chromatography (n-hexane / ethyl acetate = 100 / 1)로 정제하여 4-클로로-2-(나프탈렌-1-일)벤조[d]티아졸을 얻었다. 수율 2.1 g (71%). A solution of 2-bromo-4-chlorobenzo [ d ] thiazole (2.48 g, 10 mmol), 1-naphthylboronic acid (1.34 g, 10.1 mmol) and 2M Na 2 CO 3 12.5 mL, 25 mmol), anhydrous ethanol (25 mL), anhydrous toluene (25 mL) and Pd (PPh 3 ) 4 (347 mg, 0.3 mmol). After degassing, it was substituted with Ar and stirred vigorously at 80 DEG C for 18 hours. After a certain period of time, the mixture was cooled to room temperature and the organic layer was separated. The water layer was washed with dichloromethane (25 mL x 2). The organic layer was collected, passed through a Silica gel pad, and concentrated. The crude product was purified by column chromatography ( n -hexane / ethyl acetate = 100/1) to obtain 4-chloro-2- (naphthalen-1-yl) benzo [ d ] thiazole. Yield 2.1 g (71%).
1H NMR (600 MHz, CDCl3, ppm): 9.48 (d, J=8.6 Hz, 1 H), 8.45 (dd, J=7.2, 0.9 Hz, 1 H), 8.05 (d, J=8.2 Hz, 1 H), 7.94 (d, J=8.2 Hz, 1 H), 7.74 (td, J=7.7, 1.1 Hz, 1 H), 7.53 - 7.66 (m, 4 H), 7.19 - 7.33 (m, 1 H). 1 H NMR (600 MHz, CDCl 3, ppm): 9.48 (d, J = 8.6 Hz, 1 H), 8.45 (dd, J = 7.2, 0.9 Hz, 1 H), 8.05 (d, J = 8.2 Hz, 1H), 7.94 (d, J = 8.2 Hz, 1H), 7.74 (td, J = 7.7,1.1 Hz, 1H), 7.53-7.66 (m, 4H), 7.19-7.33 ).
단계 (b): 화합물 1-6의 제조Step (b): Preparation of compound 1-6
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 단계 (a)에서 제조한 4-클로로-2-(나프탈렌-1-일)벤조[d]티아졸(887 mg, 3 mmol), Pd2(dba)3(165 mg, 0.18 mmol), DPPF(200 mg, 0.36 mmol), sodium tert-butoxide(432 mg, 4.5 mmol), 무수 1,4-dioxane(15 mL), 2,6-dimethylaniline(406 μL, 3.3 mmol)을 투입하고 18 시간 동안 reflux하였다. 일정 시간 후 상온으로 냉각시키고 sat'd NH4Cl 수용액(15 mL)을 투입하여 반응을 종결시켰다. 유기층을 분리하여 silica gel pad를 통과시킨 후 농축하였다. Crude product를 ethanol 하에서 재결정하여 화합물 1-6을 얻었다. 수율 594 mg (52%). To a 100 mL Schlenk flask that was well dried and replaced with Ar was added 4-chloro-2- (naphthalen-1-yl) benzo [ d ] thiazole (887 mg, 3 mmol), Pd 2 dba) 3 (165 mg, 0.18 mmol), DPPF (200 mg, 0.36 mmol), sodium tert -butoxide (432 mg, 4.5 mmol), anhydrous 1,4-dioxane (15 mL), 2,6-dimethylaniline (406 mu L, 3.3 mmol) was added and refluxed for 18 hours. After a certain period of time, the reaction mixture was cooled to room temperature and quenched by the addition of sat'd NH 4 Cl aqueous solution (15 mL). The organic layer was separated, passed through a silica gel pad, and concentrated. Crude product was recrystallized under ethanol to obtain compound 1-6. Yield 594 mg (52%).
1H NMR (600 MHz, CDCl3, ppm): 9.08 (d, J=8.5 Hz), 8.01 (t, J=6.6 Hz), 7.97 (d, J=8.0 Hz), 7.65 (t, J=7.6 Hz), 7.57 - 7.63 (m), 7.30 (d, J=7.9 Hz), 7.18 - 7.23 (m), 6.87 (s), 6.25 (d, J=7.8 Hz), 2.36 (s). 1 H NMR (600 MHz, CDCl 3, ppm): 9.08 (d, J = 8.5 Hz), 8.01 (t, J = 6.6 Hz), 7.97 (d, J = 8.0 Hz), 7.65 (t, J = 7.6 Hz), 7.57-7.63 (m), 7.30 (d, J = 7.9 Hz), 7.18-7.23 (m), 6.87 (s), 6.25 (d, J = 7.8 Hz), 2.36 (s).
실시예 8: 화합물 1-12의 합성Example 8: Synthesis of Compound 1-12
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 7의 단계 (a)에서 제조한 4-클로로-2-(나프탈렌-1-일)벤조[d]티아졸(887 mg, 3 mmol), Pd2(dba)3(165 mg, 0.18 mmol), DPPF(200 mg, 0.36 mmol), sodium tert-butoxide(432 mg, 4.5 mmol), 무수 1,4-dioxane(15 mL), 2,6-diisopropylaniline(622 μL, 3.3 mmol)을 투입하고 18 시간 동안 reflux하였다. 일정 시간 후 상온으로 냉각시키고 sat'd NH4Cl 수용액(15 mL)을 투입하여 반응을 종결시켰다. 유기층을 분리하여 silica gel pad를 통과시킨 후 농축하였다. Crude product를 ethanol 하에서 재결정하여 화합물 1-12를 얻었다. 수율 786 mg (60%). 2- (naphthalen-1-yl) benzo [ d ] thiazole (887 mg, 3 mmol) prepared in step (a) of Example 7 was added to a 100 mL Schlenk flask which was well- , Pd 2 (dba) 3 ( 165 mg, 0.18 mmol), DPPF (200 mg, 0.36 mmol), sodium tert -butoxide (432 mg, 4.5 mmol), anhydrous 1,4-dioxane (15 mL), 2,6 -diisopropylaniline (622 μL, 3.3 mmol) was added and refluxed for 18 hours. After a certain period of time, the reaction mixture was cooled to room temperature and quenched by the addition of sat'd NH 4 Cl aqueous solution (15 mL). The organic layer was separated, passed through a silica gel pad, and concentrated. Crude product was recrystallized from ethanol to obtain Compound 1-12. Yield 786 mg (60%).
1H NMR (600 MHz, CDCl3, ppm): 9.02 - 9.14 (m), 7.99 - 8.05 (m), 7.94 - 7.99 (m), 7.58 - 7.64 (m), 7.36 - 7.41 (m), 7.30 - 7.32 (m), 7.25 - 7.29 (m), 7.18 (t, J=7.9 Hz), 6.84 (s), 6.23 (dd, J=7.9, 0.8 Hz), 3.37 (spt, J=6.9 Hz), 1.24 (d, J=5.1 Hz). 1 H NMR (600 MHz, CDCl 3, ppm): 9.02 - 9.14 (m), 7.99 - 8.05 (m), 7.94 - 7.99 (m), 7.58 - 7.64 (m), 7.36 - 7.41 (m), 7.30 - J = 7.9, 0.8 Hz), 3.37 (s pt, J = 6.9 Hz), 1.24 (t, J = 7.9 Hz), 7.32 (m), 7.25-7.29 (d, J = 5.1 Hz).
실시예 9: 화합물 2-1의 합성Example 9: Synthesis of Compound 2-1
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 1에서 제조한 화합물 1-1(252 mg, 1 mmol), tetrabenzylhafnium(548 mg, 1.01 mmol), 무수 toluene(20 mL)을 투입하고 50℃ 하에서 3시간 동안 교반하였다. 일정 시간 후 진공 건조하여 얻은 crude product를 무수 n-hexane 하에서 재결정하여 화합물 2-1을 얻었다. 수율 478 mg (68%). (252 mg, 1 mmol), tetrabenzylhafnium (548 mg, 1.01 mmol) and anhydrous toluene (20 mL) were added to a 100 mL Schlenk flask which was well dried and replaced with Ar, C < / RTI > for 3 hours. The crude product obtained after vacuum drying after a certain period of time was recrystallized under anhydrous n- hexane to obtain Compound 2-1. Yield 478 mg (68%).
상기 실시예 9에서 합성한 화합물 2-1의 1H NMR spectrum(500 MHz, C6D6, ppm)을 도 1에 나타내었다. The 1 H NMR spectrum (500 MHz, C 6 D 6 , ppm) of the compound 2-1 synthesized in Example 9 is shown in FIG.
실시예 10: 화합물 2-7의 합성Example 10: Synthesis of Compound 2-7
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 2에서 제조한 화합물 1-7(308 mg, 1 mmol), tetrabenzylhafnium (548 mg, 1.01 mmol), 무수 toluene (20 mL)을 투입하고 50℃ 하에서 3시간 동안 교반하였다. 일정 시간 후 진공 건조하여 얻은 crude product를 무수 n-hexane 하에서 재결정하여 화합물 2-7을 얻었다. 수율 402 mg (53%). (308 mg, 1 mmol), tetrabenzylhafnium (548 mg, 1.01 mmol) and anhydrous toluene (20 mL) were added to a 100 mL Schlenk flask which was well dried and replaced with Ar, C < / RTI > for 3 hours. The crude product obtained after vacuum drying after a certain period of time was recrystallized under anhydrous n- hexane to obtain Compound 2-7. Yield 402 mg (53%).
상기 실시예 10에서 합성한 화합물 2-7의 1H NMR spectrum(500 MHz, C6D6, ppm)을 도 2에 나타내었다. The 1 H NMR spectrum (500 MHz, C 6 D 6 , ppm) of the compound 2-7 synthesized in Example 10 is shown in FIG.
실시예 11: 화합물 2-3의 합성Example 11: Synthesis of Compound 2-3
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 3에서 제조한 화합물 1-3(364 mg, 1 mmol), tetrabenzylhafnium(548 mg, 1.01 mmol), 무수 toluene(20 mL)을 투입하고 50℃ 하에서 3시간 동안 교반하였다. 일정 시간 후 진공 건조하여 화합물 2-3과 화합물 2-3'의 혼합물(2-3:2-3'=1:1)을 얻었다. 수율 611 mg (75%). (364 mg, 1 mmol), tetrabenzylhafnium (548 mg, 1.01 mmol) and anhydrous toluene (20 mL) were added to a 100 mL Schlenk flask which was well dried and substituted with Ar, C < / RTI > for 3 hours. After a certain period of time, it was vacuum-dried to obtain a mixture (2-3: 2-3 '= 1: 1) of compound 2-3 and compound 2-3'. Yield 611 mg (75%).
상기 실시예 11에서 합성한 화합물 2-3의 1H NMR spectrum(500 MHz, C6D6, ppm)을 도 3에 나타내었다. The 1 H NMR spectrum (500 MHz, C 6 D 6 , ppm) of the compound 2-3 synthesized in Example 11 is shown in FIG.
실시예 12: 화합물 2-9의 합성Example 12: Synthesis of Compound 2-9
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 4에서 제조한 화합물 1-9(421 mg, 1 mmol), tetrabenzylhafnium(548 mg, 1.01 mmol), 무수 toluene(20 mL)을 투입하고 50℃ 하에서 3시간 동안 교반하였다. 일정 시간 후 진공 건조하여 화합물 2-9와 화합물 2-9'의 혼합물(2-9:2-9'=1:1)을 얻었다. 수율 505 mg (58%). (421 mg, 1 mmol), tetrabenzylhafnium (548 mg, 1.01 mmol) and anhydrous toluene (20 mL) were added to a 100 mL Schlenk flask which was well dried and replaced with Ar, C < / RTI > for 3 hours. After a certain period of time, the mixture was vacuum-dried to obtain a mixture (2-9: 2-9 '= 1: 1) of the compound 2-9 and the compound 2-9'. Yield 505 mg (58%).
상기 실시예 12에서 합성한 화합물 2-9의 1H NMR spectrum(500 MHz, C6D6, ppm)을 도 4에 나타내었다. The 1 H NMR spectrum (500 MHz, C 6 D 6 , ppm) of the compound 2-9 synthesized in Example 12 is shown in FIG.
실시예 13: 화합물 2-4의 합성Example 13: Synthesis of compound 2-4
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 5에서 제조한 화합물 1-4(268 mg, 1 mmol), tetrabenzylhafnium(548 mg, 1.01 mmol), 무수 toluene(20 mL)을 투입하고 50℃ 하에서 3시간 동안 교반하였다. 일정 시간 후 진공 건조하여 얻은 crude product를 무수 n-hexane 하에서 재결정하여 화합물 2-4를 얻었다. 수율 439 mg (61%). (268 mg, 1 mmol), tetrabenzylhafnium (548 mg, 1.01 mmol) and toluene anhydride (20 mL) were added to a 100 mL Schlenk flask which was well dried and replaced with Ar, C < / RTI > for 3 hours. After a certain period of time, the crude product was vacuum dried and recrystallized under anhydrous n- hexane to obtain Compound 2-4. Yield 439 mg (61%).
상기 실시예 13에서 합성한 화합물 2-4의 1H NMR spectrum(500 MHz, C6D6, ppm)을 도 5에 나타내었다. The 1 H NMR spectrum (500 MHz, C 6 D 6 , ppm) of the compound 2-4 synthesized in Example 13 is shown in FIG.
실시예 14: 화합물 2-10의 합성Example 14: Synthesis of Compound 2-10
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 6에서 제조한 화합물 1-10(324 mg, 1 mmol), tetrabenzylhafnium(548 mg, 1.01 mmol), 무수 toluene(20 mL)을 투입하고 50℃ 하에서 3시간 동안 교반하였다. 일정 시간 후 진공 건조하여 얻은 crude product를 무수 n-hexane 하에서 재결정하여 화합물 2-10을 얻었다. 수율 457 mg (59%). (324 mg, 1 mmol), tetrabenzylhafnium (548 mg, 1.01 mmol) and anhydrous toluene (20 mL) were added to a 100 mL Schlenk flask which was well dried and replaced with Ar, C < / RTI > for 3 hours. After a certain period of time, the crude product was vacuum dried and recrystallized under anhydrous n- hexane to obtain Compound 2-10. Yield 457 mg (59%).
상기 실시예 14에서 합성한 화합물 2-10의 1H NMR spectrum(500 MHz, C6D6, ppm)을 도 6에 나타내었다. The 1 H NMR spectrum (500 MHz, C 6 D 6 , ppm) of Compound 2-10 synthesized in Example 14 is shown in FIG.
실시예 15: 화합물 2-6의 합성Example 15: Synthesis of compound 2-6
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 7에서 제조한 화합물 1-6(364 mg, 1 mmol), tetrabenzylhafnium(548 mg, 1.01 mmol), 무수 toluene(20 mL)을 투입하고 50℃ 하에서 3시간 동안 교반하였다. 일정 시간 후 진공 건조하여 화합물 2-6을 얻었다. 수율 739 mg (정량 수율). (364 mg, 1 mmol), tetrabenzylhafnium (548 mg, 1.01 mmol) and anhydrous toluene (20 mL) were added to a 100 mL Schlenk flask which was well dried and replaced with Ar, C < / RTI > for 3 hours. After a certain period of time, it was vacuum-dried to obtain Compound 2-6. Yield 739 mg (quantitative yield).
상기 실시예 15에서 합성한 화합물 2-6의 1H NMR spectrum(500 MHz, C6D6, ppm)을 도 7에 나타내었다. The 1 H NMR spectrum (500 MHz, C 6 D 6 , ppm) of the compound 2-6 synthesized in Example 15 is shown in FIG.
실시예 16: 화합물 2-12의 합성Example 16: Synthesis of Compound 2-12
잘 건조되고 Ar으로 치환된 100 mL Schlenk flask에 상기 실시예 8에서 제조한 화합물 1-12(421 mg, 1 mmol), tetrabenzylhafnium(548 mg, 1.01 mmol), 무수 toluene(20 mL)을 투입하고 50℃ 하에서 3시간 동안 교반하였다. 일정 시간 후 진공 건조하여 화합물 2-12를 얻었다. 수율 795 mg (정량 수율).(421 mg, 1 mmol), tetrabenzylhafnium (548 mg, 1.01 mmol) and anhydrous toluene (20 mL) were added to a 100 mL Schlenk flask which was well dried and replaced with Ar, C < / RTI > for 3 hours. After a certain period of time, it was vacuum-dried to obtain Compound 2-12. Yield 795 mg (quantitative yield).
상기 실시예 16에서 합성한 화합물 2-12의 1H NMR spectrum(500 MHz, C6D6, ppm)을 도 8에 나타내었다. The 1 H NMR spectrum (500 MHz, C 6 D 6 , ppm) of the compound 2-12 synthesized in Example 16 is shown in FIG.
비교예Comparative Example 1: [ One: [ NN -2,6--2,6- 비스(1-메틸에틸)페닐Bis (1-methylethyl) phenyl ]-α-[2-(1-] - &alpha; - [2- (1- 메틸에틸Methyl ethyl )-페닐]-6-(1-) -Phenyl] -6- (1- 나프탈레닐Naphthalenyl -κC-KC 22 )-2-피리딘메탄아미나토(2-)-κN) -2-pyridine Methanaminato (2 -) - 虜 N 1One ,κN, κN 22 ]디메틸하프늄 ([] Dimethyl hafnium ([ NN -2,6-bis(1-methylethyl)phenyl]-α-[2-(1-methylethyl)-phenyl]-6-(1-naphthalenyl-κC-2,6-bis (1-methylethyl) phenyl] -? - [2- (1-methylethyl) -phenyl] -6- (1-naphthalenyl- 22 )-2-pyridinemethanaminato(2-)-κN) -2-pyridinemethanaminato (2 -) - N 1One ,κN, κN 22 ]dimethylhafnium)의 제조] dimethylhafnium)
문헌 'Organometallics, 2011, 30, 3318-3329'에 기재된 방법에 따라 하기 화학식으로 표시되는 표제의 화합물 D1을 제조하였다.The title compound D1 represented by the following formula was prepared according to the method described in the literature " Organometallics, 2011, 30, 3318-3329 ".
[화합물 D1][Compound D1]
실시예 17: 에틸렌/1-옥텐 공중합체의 제조Example 17: Preparation of ethylene / 1-octene copolymer
약 100℃ 하의 2L 오토클레이브 반응기에 무수 n-헥산(1 L), 1-옥텐(230 mL), 트리이소부틸알루미늄 용액(1.0 M in n-hexane, 0.3 mL)을 가한 후, 반응기 내부 압력을 10 psi 이하가 되도록 vent하였다. 반응기의 온도를 120°C로 예열한 후 에틸렌을 500 psi로 주입하였다. 디메틸아닐리늄 테트라키스(펜타플루오로페닐) 보레이트 조촉매 용액(2 x 10-3 M in toluene, 3 mL)을 촉매 저장탱크에 넣은 후 고압의 아르곤 압력을 가하여 반응기에 넣고, 트리이소부틸알루미늄 화합물로 처리된 상기 실시예 9의 전이금속 화합물 촉매 용액(2 x 10-3 M in toluene, 1 mL)을 반응기에 넣은 후 약 30 bar의 고압 아르곤 압력을 가하여 중합 반응을 개시하였다. 중합 반응은 10분간 진행하였다. 반응열은 반응기 내부의 냉각 코일을 통해 제거하여 중합 온도를 최대한 일정하게 유지하였다. 중합 반응을 10분 간 진행한 후, 남은 가스를 빼내고 고분자 용액을 반응기의 하부로 배출시키고 과량의 에탄올을 가하여 냉각시켜 침전을 유도하였다. 얻어진 고분자를 에탄올 및 아세톤으로 각각 2 내지 3회 세척한 후, 90℃ 진공 오븐에서 12시간 이상 건조한 후 물성을 측정하였다.After adding anhydrous n -hexane (1 L), 1-octene (230 mL) and triisobutylaluminum solution (1.0 M in n -hexane, 0.3 mL) to a 2 L autoclave reactor at about 100 ° C, And vented to below 10 psi. The reactor temperature was preheated to 120 ° C and ethylene was injected at 500 psi. A solution of dimethylanilinium tetrakis (pentafluorophenyl) borate co-catalyst (2 x 10-3 M in toluene, 3 mL) was placed in a catalyst storage tank, and a high-pressure argon pressure was applied to the reactor. Triisobutyl aluminum compound (2 x 10 -3 M in toluene, 1 mL) of the above-mentioned Example 9, which had been treated with a high-pressure argon gas, was introduced into the reactor, and a high-pressure argon pressure of about 30 bar was applied to initiate the polymerization reaction. The polymerization reaction was carried out for 10 minutes. The reaction heat was removed through a cooling coil inside the reactor to keep the polymerization temperature at a maximum. After the polymerization reaction was carried out for 10 minutes, the remaining gas was discharged and the polymer solution was discharged to the lower part of the reactor, and excessive ethanol was added to cool the solution to induce precipitation. The obtained polymer was washed with ethanol and acetone two to three times, respectively, and then dried in a vacuum oven at 90 캜 for more than 12 hours, and the physical properties thereof were measured.
실시예 18: 에틸렌/1-옥텐 공중합체의 제조Example 18: Preparation of ethylene / 1-octene copolymer
상기 실시예 17에서 실시예 9에서 제조한 전이금속 화합물 대신에 실시예 10에서 제조한 전이금속 화합물을 사용하는 것을 제외하고는, 상기 실시예 17과 동일한 방법으로 에틸렌/1-옥텐 공중합체를 제조하였다. An ethylene / 1-octene copolymer was prepared in the same manner as in Example 17, except that the transition metal compound prepared in Example 10 was used instead of the transition metal compound prepared in Example 9 in Example 17 Respectively.
실시예 19: 에틸렌/1-옥텐 공중합체의 제조Example 19: Preparation of ethylene / 1-octene copolymer
상기 실시예 17에서 실시예 9에서 제조한 전이금속 화합물 대신에 실시예 11에서 제조한 전이금속 화합물을 사용하는 것을 제외하고는, 상기 실시예 17과 동일한 방법으로 에틸렌/1-옥텐 공중합체를 제조하였다. An ethylene / 1-octene copolymer was prepared in the same manner as in Example 17, except that the transition metal compound prepared in Example 11 was used instead of the transition metal compound prepared in Example 9 in Example 17 Respectively.
실시예 20: 에틸렌/1-옥텐 공중합체의 제조Example 20: Preparation of ethylene / 1-octene copolymer
상기 실시예 17에서 실시예 9에서 제조한 전이금속 화합물 대신에 실시예 12에서 제조한 전이금속 화합물을 사용하는 것을 제외하고는, 상기 실시예 17과 동일한 방법으로 에틸렌/1-옥텐 공중합체를 제조하였다. An ethylene / 1-octene copolymer was prepared in the same manner as in Example 17, except that the transition metal compound prepared in Example 12 was used instead of the transition metal compound prepared in Example 9 in Example 17 Respectively.
실시예 21: 에틸렌/1-옥텐 공중합체의 제조Example 21: Preparation of ethylene / 1-octene copolymer
상기 실시예 17에서 실시예 9에서 제조한 전이금속 화합물 대신에 실시예 13에서 제조한 전이금속 화합물을 사용하는 것을 제외하고는, 상기 실시예 17과 동일한 방법으로 에틸렌/1-옥텐 공중합체를 제조하였다. An ethylene / 1-octene copolymer was prepared in the same manner as in Example 17, except that the transition metal compound prepared in Example 13 was used instead of the transition metal compound prepared in Example 9 in Example 17 Respectively.
실시예 22: 에틸렌/1-옥텐 공중합체의 제조Example 22: Preparation of ethylene / 1-octene copolymer
상기 실시예 17에서 실시예 9에서 제조한 전이금속 화합물 대신에 실시예 14에서 제조한 전이금속 화합물을 사용하는 것을 제외하고는, 상기 실시예 17과 동일한 방법으로 에틸렌/1-옥텐 공중합체를 제조하였다. An ethylene / 1-octene copolymer was prepared in the same manner as in Example 17, except that the transition metal compound prepared in Example 14 was used instead of the transition metal compound prepared in Example 9 in Example 17 Respectively.
실시예 23: 에틸렌/1-옥텐 공중합체의 제조Example 23: Preparation of ethylene / 1-octene copolymer
상기 실시예 17에서 실시예 9에서 제조한 전이금속 화합물 대신에 실시예 15에서 제조한 전이금속 화합물을 사용하는 것을 제외하고는, 상기 실시예 17과 동일한 방법으로 에틸렌/1-옥텐 공중합체를 제조하였다.The procedure of Example 17 was repeated except that the transition metal compound prepared in Example 15 was used instead of the transition metal compound prepared in Example 9 to prepare an ethylene / 1-octene copolymer Respectively.
실시예 24: 에틸렌/1-옥텐 공중합체의 제조Example 24: Preparation of ethylene / 1-octene copolymer
상기 실시예 17에서 실시예 9에서 제조한 전이금속 화합물 대신에 실시예 16에서 제조한 전이금속 화합물을 사용하는 것을 제외하고는, 상기 실시예 17과 동일한 방법으로 에틸렌/1-옥텐 공중합체를 제조하였다.An ethylene / 1-octene copolymer was prepared in the same manner as in Example 17, except that the transition metal compound prepared in Example 16 was used instead of the transition metal compound prepared in Example 9 in Example 17 Respectively.
비교예 2: 에틸렌/1-옥텐 공중합체의 제조Comparative Example 2: Preparation of ethylene / 1-octene copolymer
상기 실시예 17에서 실시예 9에서 제조한 전이금속 화합물 대신에 비교예 1에서 제조한 전이금속 화합물을 사용하는 것을 제외하고는, 상기 실시예 17과 동일한 방법으로 에틸렌/1-옥텐 공중합체를 제조하였다.An ethylene / 1-octene copolymer was prepared in the same manner as in Example 17, except that the transition metal compound prepared in Comparative Example 1 was used instead of the transition metal compound prepared in Example 17 in Example 17 Respectively.
실험예: 에틸렌/1-옥텐 공중합체의 물성 측정Experimental Example: Measurement of physical properties of ethylene / 1-octene copolymer
상기 실시예 18 내지 24 및 비교예 2에서 제조한 에틸렌/1-옥텐 공중합체에 대해 중량, 밀도, 용융지수 및 용융온도를 측정하였다.The weight, density, melt index and melting temperature of the ethylene / 1-octene copolymer prepared in Examples 18 to 24 and Comparative Example 2 were measured.
이때, 중합체의 밀도(density)는 190℃ 프레스 몰드(press mold)로 두께 3 mm, 반지름 2 mm시트를 제작하고, 10℃/min으로 냉각하여 메틀러(Mettler) 저울에서 측정하였고,At this time, the density of the polymer was measured on a Mettler scale by making a sheet having a thickness of 3 mm and a radius of 2 mm with a 190 占 폚 press mold, cooling at 10 占 폚 / min,
중합체의 용융지수(melt index, MI)는 ASTM D-1238(190℃, 2.16 kg 하중)로 측정하였으며, The melt index (MI) of the polymer was determined by ASTM D-1238 (190 占 폚, 2.16 kg load)
중합체의 용융온도(Tm)는 TA사의 Q100을 사용하여 측정하였으며, 측정값은 중합체의 열적 이력(thermal history)을 없애기 위해 분당 10℃로 승온시킨 두 번째 용융(melting)을 통해 얻었다.The melting temperature (Tm) of the polymer was measured using Q100 from TA, and the measured values were obtained through a second melting step of raising the temperature to 10 ° C per minute to eliminate the thermal history of the polymer.
또한, 상기 실시예 18 내지 24 및 비교예 2에서의 에틸렌/1-옥텐 공중합체 제조 시 사용된 촉매 활성도를 측정하였다. 이때, 촉매 활성도는 제조한 중합체 총 수득량에 대한 전이금속 화합물의 투입 몰수 및 중합 시간을 이용하여 계산되었다. In addition, the catalyst activity used in the production of the ethylene / 1-octene copolymer in Examples 18 to 24 and Comparative Example 2 was measured. At this time, the catalytic activity was calculated by using the mole number of the transition metal compound and the polymerization time with respect to the total amount of polymer produced.
상기 실시예 18 내지 24 및 비교예 2에 대해 상기와 같은 방법으로 물성을 측정한 후 그 결과를 하기 표 1에 나타내었다.The properties of Examples 18 to 24 and Comparative Example 2 were measured in the same manner as described above, and the results are shown in Table 1 below.
(전이금속 화합물)catalyst
(Transition metal compound)
(단위:
g)Polymer weight
(unit:
g)
(단위: g/cc)density
(Unit: g / cc)
(단위: g/10min)Melt Index
(Unit: g / 10 min)
(단위:
℃)Melting temperature
(unit:
° C)
(단위:
kg·mmol-1hr-1)Catalytic activity
(unit:
kg · mmol -1 hr -1 )
2-7compound
2-7
2-3compound
2-3
2-9compound
2-9
2-4compound
2-4
2-10compound
2-10
2-6compound
2-6
2-12compound
2-12
D1compound
D1
상기 표 1에 나타난 바와 같이, 본 발명에 따른 전이금속 화합물은 올리핀계 중합체를 제조하는데 있어 중합 반응 촉매로 사용될 수 있음을 확인할 수 있었다. 또한, 실시예에 따른 전이금속 화합물은 비교예에 따른 전이금속 화합물에 비하여 고분자량의 올레핀계 공중합체를 제조할 수 있음을 알 수 있다. As shown in Table 1, it was confirmed that the transition metal compound according to the present invention can be used as a polymerization catalyst in the preparation of an olefin-based polymer. It is also understood that the olefin-based copolymer having a higher molecular weight than the transition metal compound according to the comparative example can be produced by the transition metal compound according to the embodiment.
Claims (14)
[화학식 1]
[화학식 5]
[화학식 6]
상기 화학식 1, 5 및 6에서,
X는 O 또는 S이고,
Y는 할로겐이고,
R1 내지 R9는 각각 독립적으로, 수소; C1-20 알킬; C3-20 사이클로알킬; C2-20 알케닐; C6-20 아릴; C7-20 알킬아릴; C7-20 아릴알킬; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 헤테로원자를 1개 이상 포함하는 C2-20 헤테로아릴이다.
Reacting a compound represented by the following formula (5) with a compound represented by the following formula (6): < EMI ID =
[Chemical Formula 1]
[Chemical Formula 5]
[Chemical Formula 6]
In the above formulas (1), (5) and (6)
X is O or S,
Y is halogen,
R 1 to R 9 are each independently hydrogen; C 1-20 alkyl; C 3-20 cycloalkyl; C 2-20 alkenyl; C 6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; Or C 2-20 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S.
상기 화학식 5로 표시되는 화합물과 상기 화학식 6으로 표시되는 화합물은 1:1 내지 1:3의 몰비로 사용되는, 제조 방법.
The method according to claim 1,
Wherein the compound represented by Formula 5 and the compound represented by Formula 6 are used in a molar ratio of 1: 1 to 1: 3.
상기 반응은 20 내지 150℃의 온도 범위에서 1 내지 72 시간 동안 진행되는, 제조 방법.
The method according to claim 1,
Wherein the reaction is carried out at a temperature ranging from 20 to 150 DEG C for 1 to 72 hours.
R1 내지 R9는 각각 독립적으로, 수소, 메틸, 이소프로필, 페닐, 또는 나프틸인, 제조 방법.
The method according to claim 1,
R 1 to R 9 are each independently hydrogen, methyl, isopropyl, phenyl, or naphthyl.
R1 및 R5는 각각 독립적으로, 메틸 또는 이소프로필이고,
R9는 메틸, 페닐, 또는 나프틸이고,
R2 내지 R4 및 R6 내지 R8은 수소인, 제조 방법.
5. The method of claim 4,
R 1 and R 5 are each independently methyl or isopropyl,
R 9 is methyl, phenyl, or naphthyl,
R 2 to R 4 and R 6 to R 8 are hydrogen.
상기 화학식 5로 표시되는 화합물은, 하기 화학식 3으로 표시되는 화합물과 하기 화학식 4 또는 4'로 표시되는 화합물을 반응시켜 제조되는, 제조 방법:
[화학식 3]
[화학식 4]
[화학식 4']
상기 화학식 3, 4 및 4'에서,
Z는 할로겐이고,
X, Y 및 R6 내지 R9에 대한 설명은 제1항에서 정의한 바와 같다.
The method according to claim 1,
The compound represented by Formula 5 is prepared by reacting a compound represented by Formula 3 with a compound represented by Formula 4 or 4 '
(3)
[Chemical Formula 4]
[Chemical Formula 4 ']
In the above formulas (3), (4) and (4 '),
Z is halogen,
X, Y and R 6 to R 9 are the same as defined in claim 1.
상기 화학식 1로 표시되는 화합물은 하기 화합물 1-1 내지 1-12 중 하나인, 제조 방법:
The method according to claim 1,
Wherein the compound represented by Formula 1 is one of the following Compounds 1-1 to 1-12,
[화학식 2]
[화학식 1]
[화학식 7]
M(R10)4
[화학식 8]
MW4
[화학식 9]
R10MgV
상기 화학식 1, 2, 7, 8 및 9에서,
M은 4족의 전이금속이고,
X는 O 또는 S이고,
R1 내지 R10은 각각 독립적으로, 수소; C1-20 알킬; C3-20 사이클로알킬; C2-20 알케닐; C6-20 아릴; C7-20 알킬아릴; C7-20 아릴알킬; 또는 N, O 및 S로 구성되는 군으로부터 선택되는 헤테로원자를 1개 이상 포함하는 C2-20 헤테로아릴이고,
V 및 W는 각각 독립적으로, 클로로, 브로모, 또는 아이오도이고,
n은 2 또는 3이다.
Reacting a compound represented by the following formula (1) with a compound represented by the following formula (7), or reacting a compound represented by the following formula (1), a compound represented by the following formula (8) A process for producing a transition metal compound represented by the following formula (2):
(2)
[Chemical Formula 1]
(7)
M (R 10 ) 4
[Chemical Formula 8]
MW 4
[Chemical Formula 9]
R 10 MgV
In the above formulas (1), (2), (7), (8)
M is a transition metal of Group 4,
X is O or S,
R 1 to R 10 are each independently hydrogen; C 1-20 alkyl; C 3-20 cycloalkyl; C 2-20 alkenyl; C 6-20 aryl; C7-20 alkylaryl; C7-20 arylalkyl; Or C 2-20 heteroaryl containing one or more heteroatoms selected from the group consisting of N, O and S,
V and W are each independently chloro, bromo, or iodo,
n is 2 or 3;
상기 화학식 1로 표시되는 화합물과 상기 화학식 7로 표시되는 화합물은 1:1 내지 1:1.5의 몰비로 사용되고
상기 화학식 1로 표시되는 화합물, 상기 화학식 8로 표시되는 화합물 및 상기 화학식 9로 표시되는 화합물은 1:1:4 내지 1:1.5:5의 몰비로 사용되는, 제조 방법.
9. The method of claim 8,
The compound represented by Formula 1 and the compound represented by Formula 7 are used in a molar ratio of 1: 1 to 1: 1.5
Wherein the compound represented by Formula 1, the compound represented by Formula 8, and the compound represented by Formula 9 are used in a molar ratio of 1: 1: 4 to 1: 1.5: 5.
상기 화학식 1로 표시되는 화합물과 상기 화학식 7로 표시되는 화합물의 반응은 25 내지 100℃의 온도 범위에서 1 내지 12 시간 동안 진행되고,
상기 화학식 1로 표시되는 화합물, 상기 화학식 8로 표시되는 화합물 및 상기 화학식 9로 표시되는 화합물의 반응은 0 내지 100℃의 온도 범위에서 1 내지 72 시간 동안 진행되는, 제조 방법.
9. The method of claim 8,
The reaction between the compound represented by the formula (1) and the compound represented by the formula (7) is carried out at a temperature ranging from 25 to 100 ° C for 1 to 12 hours,
Wherein the reaction of the compound represented by the formula (1), the compound represented by the formula (8) and the compound represented by the formula (9) is carried out at a temperature ranging from 0 to 100 ° C for 1 to 72 hours.
M은 Ti, Zr, 또는 Hf인, 제조 방법.
9. The method of claim 8,
And M is Ti, Zr, or Hf.
R1 내지 R10은 각각 독립적으로, 수소, 메틸, 이소프로필, 페닐, 나프틸, 또는 벤질인, 제조 방법.
9. The method of claim 8,
R 1 to R 10 are each independently hydrogen, methyl, isopropyl, phenyl, naphthyl or benzyl.
R1 및 R5는 각각 독립적으로, 메틸 또는 이소프로필이고,
R9는 메틸, 페닐, 또는 나프틸이고,
R10은 벤질이고,
R2 내지 R4 및 R6 내지 R8은 수소인, 제조 방법.
9. The method of claim 8,
R 1 and R 5 are each independently methyl or isopropyl,
R 9 is methyl, phenyl, or naphthyl,
R < 10 > is benzyl,
R 2 to R 4 and R 6 to R 8 are hydrogen.
상기 화학식 2로 표시되는 전이금속 화합물은 하기 화합물 2-1 내지 2-12 중 하나인, 제조 방법:
9. The method of claim 8,
Wherein the transition metal compound represented by Formula 2 is one of the following compounds 2-1 to 2-12,
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