JP2022539506A - チアゾールまたはイミダゾールを有するオレフィン重合触媒 - Google Patents
チアゾールまたはイミダゾールを有するオレフィン重合触媒 Download PDFInfo
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- 150000001336 alkenes Chemical class 0.000 title claims description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 16
- 239000002685 polymerization catalyst Substances 0.000 title description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 title description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title 3
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 13
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- 239000003446 ligand Substances 0.000 claims description 116
- -1 (2,4,6-triisopropyl)phenyl Chemical group 0.000 claims description 90
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 65
- 239000005977 Ethylene Substances 0.000 claims description 65
- 229910052757 nitrogen Inorganic materials 0.000 claims description 51
- 229920000642 polymer Polymers 0.000 claims description 50
- 238000006116 polymerization reaction Methods 0.000 claims description 47
- 125000003118 aryl group Chemical group 0.000 claims description 34
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 28
- 239000004215 Carbon black (E152) Substances 0.000 claims description 22
- 229930195733 hydrocarbon Natural products 0.000 claims description 22
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 claims description 19
- 125000001072 heteroaryl group Chemical group 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- 229910052735 hafnium Inorganic materials 0.000 claims description 15
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 15
- 239000012986 chain transfer agent Substances 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000012190 activator Substances 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 3
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 287
- 238000006243 chemical reaction Methods 0.000 description 160
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 150
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 143
- 239000000243 solution Substances 0.000 description 128
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 126
- 238000005481 NMR spectroscopy Methods 0.000 description 122
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 106
- 235000019439 ethyl acetate Nutrition 0.000 description 98
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 85
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 80
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 69
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 64
- 239000011541 reaction mixture Substances 0.000 description 62
- 239000000047 product Substances 0.000 description 61
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 58
- 239000002904 solvent Substances 0.000 description 55
- 239000000741 silica gel Substances 0.000 description 49
- 229910002027 silica gel Inorganic materials 0.000 description 49
- 229920006395 saturated elastomer Polymers 0.000 description 45
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 44
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 40
- 235000019341 magnesium sulphate Nutrition 0.000 description 40
- 125000004432 carbon atom Chemical group C* 0.000 description 39
- 238000003818 flash chromatography Methods 0.000 description 39
- 239000012044 organic layer Substances 0.000 description 39
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000000203 mixture Substances 0.000 description 35
- 238000003756 stirring Methods 0.000 description 30
- 238000007792 addition Methods 0.000 description 29
- 239000011780 sodium chloride Substances 0.000 description 29
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- 239000007787 solid Substances 0.000 description 27
- 125000005842 heteroatom Chemical group 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 22
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 19
- 238000012546 transfer Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 18
- 235000019198 oils Nutrition 0.000 description 18
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 18
- 239000004711 α-olefin Substances 0.000 description 18
- 229910000024 caesium carbonate Inorganic materials 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 17
- 150000003254 radicals Chemical class 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000000543 intermediate Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 238000000746 purification Methods 0.000 description 15
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [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 14
- 230000003213 activating effect Effects 0.000 description 14
- 125000002947 alkylene group Chemical group 0.000 description 14
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 14
- 125000003636 chemical group Chemical group 0.000 description 13
- 239000000460 chlorine Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 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 11
- 230000007935 neutral effect Effects 0.000 description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 description 11
- 235000011152 sodium sulphate Nutrition 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 10
- 125000001424 substituent group Chemical group 0.000 description 10
- ZMTJPCINWIHHJX-UHFFFAOYSA-N BrC=1C(=C(C=CC=1)N1C2=CC=CC=C2C=2C=CC=CC1=2)N=C=S Chemical compound BrC=1C(=C(C=CC=1)N1C2=CC=CC=C2C=2C=CC=CC1=2)N=C=S ZMTJPCINWIHHJX-UHFFFAOYSA-N 0.000 description 9
- 239000012267 brine Substances 0.000 description 9
- 150000001721 carbon Chemical group 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000007363 ring formation reaction Methods 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 8
- CTFSRKPOYLJDIC-UHFFFAOYSA-N BrC1=NC2=C(N1C(C)C)C=CC=C2C1=C(C=C(C=C1C)C)C Chemical compound BrC1=NC2=C(N1C(C)C)C=CC=C2C1=C(C=C(C=C1C)C)C CTFSRKPOYLJDIC-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- URYRCFZCOBHJBO-UHFFFAOYSA-N BrC=1C(=C(C=CC=1)C1=C(C=C(C=C1C)C)C)N=C=S Chemical group BrC=1C(=C(C=CC=1)C1=C(C=C(C=C1C)C)C)N=C=S URYRCFZCOBHJBO-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- QSLMQGXOMLSFAW-UHFFFAOYSA-N methanidylbenzene;zirconium(4+) Chemical compound [Zr+4].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 QSLMQGXOMLSFAW-UHFFFAOYSA-N 0.000 description 7
- 125000006657 (C1-C10) hydrocarbyl group Chemical group 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 6
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 125000004474 heteroalkylene group Chemical group 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 229910020008 S(O) Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- DKNWSYNQZKUICI-UHFFFAOYSA-N amantadine Chemical compound C1C(C2)CC3CC2CC1(N)C3 DKNWSYNQZKUICI-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 125000002619 bicyclic group Chemical group 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 125000002950 monocyclic group Chemical group 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
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- 239000012071 phase Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- DWOZNANUEDYIOF-UHFFFAOYSA-L 4-ditert-butylphosphanyl-n,n-dimethylaniline;dichloropalladium Chemical compound Cl[Pd]Cl.CN(C)C1=CC=C(P(C(C)(C)C)C(C)(C)C)C=C1.CN(C)C1=CC=C(P(C(C)(C)C)C(C)(C)C)C=C1 DWOZNANUEDYIOF-UHFFFAOYSA-L 0.000 description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007832 Na2SO4 Substances 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 229910021482 group 13 metal Inorganic materials 0.000 description 4
- 125000004404 heteroalkyl group Chemical group 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- SOEVKJXMZBAALG-UHFFFAOYSA-N octylalumane Chemical compound CCCCCCCC[AlH2] SOEVKJXMZBAALG-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- 235000011181 potassium carbonates Nutrition 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- BZXQRXJJJUZZAJ-UHFFFAOYSA-N (2,4,6-trimethylphenyl)boronic acid Chemical compound CC1=CC(C)=C(B(O)O)C(C)=C1 BZXQRXJJJUZZAJ-UHFFFAOYSA-N 0.000 description 3
- XWCIICLTKWRWCI-UHFFFAOYSA-N 1-(2,4,6-trimethylphenyl)ethanone Chemical group CC(=O)C1=C(C)C=C(C)C=C1C XWCIICLTKWRWCI-UHFFFAOYSA-N 0.000 description 3
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012041 precatalyst Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 1
- 125000004353 pyrazol-1-yl group Chemical group [H]C1=NN(*)C([H])=C1[H] 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000004159 quinolin-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C([H])C(*)=NC2=C1[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 125000005374 siloxide group Chemical group 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004808 supercritical fluid chromatography Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000004523 tetrazol-1-yl group Chemical group N1(N=NN=C1)* 0.000 description 1
- 125000004299 tetrazol-5-yl group Chemical group [H]N1N=NC(*)=N1 0.000 description 1
- 125000000437 thiazol-2-yl group Chemical group [H]C1=C([H])N=C(*)S1 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
- 229940062627 tribasic potassium phosphate Drugs 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- YVWPNDBYAAEZBF-UHFFFAOYSA-N trimethylsilylmethanamine Chemical compound C[Si](C)(C)CN YVWPNDBYAAEZBF-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000001946 ultra-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
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Abstract
Description
本出願は、2019年6月26日に出願された米国仮特許出願第62/867,039号に対する優先権を主張し、その開示全体が参照により本明細書に組み込まれる。
1つ以上の実施形態では、本開示の重合プロセスは、触媒系および連鎖移動剤または連鎖シャトリング剤の存在下で、反応器内でエチレンおよび/または1つ以上の(C3-C12)α-オレフィンを接触させることを含む。そのような実施形態では、重合プロセスは、3つの成分:(A)式(I)の構造を有する金属-配位子錯体を含むプロ触媒および、任意選択で共触媒、(B)プロ触媒(A)とは異なるコモノマー選択性を有するオレフィン重合触媒、ならびに(C)連鎖移動剤または連鎖シャトリング剤を含む。
式(I)の金属-配位子錯体を含む触媒系は、オレフィン重合反応の金属系触媒を活性化するための当該技術分野で既知の任意の技術によって触媒的に活性にされ得る。例えば、式(I)の金属-配位子錯体によるプロ触媒は、錯体を活性化共触媒と接触させるか、または錯体を活性化共触媒と組み合わせることによって、触媒的に活性にされ得る。さらに、式(I)による金属-配位子錯体は、中性であるプロ触媒形態、およびベンジルまたはフェニルなどのモノアニオン配位子の損失によって正に帯電され得る触媒形態の両方を含む。本発明に使用するのに好適な活性化共触媒としては、アルキルアルミニウム、ポリマーまたはオリゴマーアルモキサン(アルミノキサンとしても知られる)、中性ルイス酸、および非ポリマー、非配位、イオン形成化合物(酸化条件下でのそのような化合物の使用を含む)が挙げられる。好適な活性化技術は、バルク電気分解である。前述の活性化共触媒および技法のうちの1つ以上の組み合わせもまた企図される。「アルキルアルミニウム」という用語は、モノアルキルアルミニウムジヒドリドもしくはモノアルキルアルミニウムジハライド、ジアルキルアルミニウムヒドリドもしくはジアルキルアルミニウムハライド、またはトリアルキルアルミニウムを意味する。ポリマーアルモキサンまたはオリゴマーアルモキサンの例としては、メチルアルモキサン、トリイソブチルアルミニウム修飾メチルアルモキサン、およびイソブチルアルモキサンを挙げることができる。
前の段落に記載される触媒系は、オレフィン、主にエチレンおよびプロピレンの重合に利用される。いくつかの実施形態では、重合スキーム中に単一種類のオレフィンまたはα-オレフィンのみが存在し、ホモポリマーを生成する。しかしながら、追加のα-オレフィンを重合手順に組み込んでもよい。追加のα-オレフィンコモノマーは、典型的には、20個以下の炭素原子を有する。例えば、α-オレフィンコモノマーは、3~10個の炭素原子、または3~8個の炭素原子を有し得る。例示的なα-オレフィンコモノマーとしては、プロピレン、1-ブテン、1-ペンテン、1-ヘキセン、1-ヘプテン、1-オクテン、1-ノネン、1-デセン、および4-メチル-1-ペンテンが挙げられるが、これらに限定されない。例えば、1つ以上のα-オレフィンコモノマーは、プロピレン、1-ブテン、1-ヘキセン、および1-オクテンからなる群から、または代替的に1-ヘキセンおよび1-オクテンからなる群から選択され得る。
ポリオレフィン触媒スクリーニングは、ハイスループット並列重合反応器(PPR)システムで行う。PPRシステムは、不活性雰囲気グローブボックス内の48個の単一セル(6×8マトリックス)反応器のアレイで構成されている。各セルは、約5mLの内部作動液体積を有するガラスインサートを備える。各セルは独立した圧力制御を有し、セル内の液体を800rpmで連続的に撹拌する。特に断りのない限り、触媒溶液は、適切な量の配位子をトルエンに溶解し、それをトルエン中のハフニウムテトラベンジルまたはジルコニウムテトラベンジルの溶液と混合して、インサイツでプロ触媒を形成することによって調製される。すべての液体(例えば、溶媒、1-オクテン、実験に適切な連鎖シャトリング剤溶液、および触媒溶液)を、ロボットシリンジを介して単一セル反応器に添加する。ガス状試薬(すなわち、エチレン、H2)は、ガス注入ポートを介して単一セル反応器に添加される。各実行前に、反応器を80℃に加熱し、エチレンでパージし、通気する。
分子量データは、ハイブリッドのSymyx/Dow構築ロボット支援希釈高温度ゲル浸透クロマトグラフィー装置(Sym-RAD-GPC)における分析によって決定する。ポリマー試料を、300百万分率(ppm)のブチル化ヒドロキシルトルエン(BHT)によって安定化された10mg/mLの濃度の1,2,4-トリクロロベンゼン(TCB)中で120分間160℃で加熱することによって溶解する。250μLアリコートの試料を注入する直前に、各試料を1mg/mLに希釈した。GPCは、160℃で2.0mL/分の流速で2つのPolymer Labs PLgelの10μmの混合-Bカラム(300×10mm)を備える。試料検出を、濃度モードでPolyChar IR4検出器を使用して行う。狭ポリスチレン(PS)標準の従来の較正は、この温度でのTCBにおけるPSおよびPEの既知のMark-Houwink係数を使用してホモポリエチレン(PE)に調整された見かけの単位で利用される。
HT-GPC分析用の試料の実行がIR分析に先行する。IR分析の場合、試料の堆積および1-オクテン組み込みの分析には、48ウェルのHTシリコンウエハを利用する。分析では、試料を160℃まで210分間以下加熱し、試料を再加熱して磁気GPC撹拌棒を取り外し、J-KEM Scientific加熱式ロボット振とう機においてガラス棒の撹拌棒を用いて振とうする。試料をTecan MiniPrepの75堆積ステーションを使用して加熱しながら堆積させ、1,2,4-トリクロロベンゼンを窒素パージ下、160℃でウエハの堆積ウェルから蒸発させる。1-オクテンの分析は、NEXUS 670 E.S.P.FT-IRを使用して、HTシリコンウエハ上で行う。
バッチ反応器の重合反応は、2LのParr(商標)バッチ反応器内で行われる。反応器は、電気加熱マントルによって加熱し、冷却水を含有する内部蛇管冷却コイルによって冷却した。反応器および加熱/冷却システムの両方は、Camile(商標)TGプロセスコンピュータによって制御および監視される。反応器の底部には、反応器の内容物をステンレス鋼のダンプポットに移すダンプ弁が取り付けられている。ダンプポットには、触媒失活溶液(典型的には、5mLのIrgafos/Irganox/トルエン混合液)が事前に充填されている。ポットおよびタンクの両方を窒素でパージして、ダンプポットを30ガロンのブローダウンタンクに通気する。重合または触媒補給のために使用したすべての溶媒を溶媒精製カラムに通過させて、重合に影響を及ぼし得る一切の不純物を除去する。1-オクテンおよびIsoparEを、A2アルミナを含有する第1のカラム、Q5を含有する第2のカラムの2つのカラムに通す。エチレンを2つのカラムに通し、第1のカラムはA204アルミナおよび
1H NMR(400MHz,CDCl3)δ7.41(ddd,J=8.0,1.5,0.6Hz,1H),6.97(s,2H),6.86(ddd,J=7.4,1.5,0.5Hz,1H),6.67(ddd,J=7.9,7.3,0.6Hz,1H),3.84(s,2H),2.33(s,3H),2.00(s,6H)。13C NMR(101MHz,CDCl3)δ141.67,137.62,137.07,134.50,131.45,129.25,128.72,127.30,119.02,109.36,21.22,20.17。
1H NMR(400MHz,CDCl3)δ7.57(dd,J=8.0,1.5Hz,1H),7.18(t,J=7.8Hz,1H),7.12(dd,J=7.6,1.6Hz,1H),6.96(s,2H),2.35(s,3H),1.98(s,6H)。13C NMR(101MHz,CDCl3)δ140.98,138.33,136.28,134.29,132.01,129.79,128.43(2C),128.04,119.90,21.28,20.32。
1H NMR(400MHz,CDCl3)δ7.62(d,J=7.8Hz,1H),7.13(t,J=7.6Hz,1H),7.05(d,J=7.4Hz,1H),6.97(s,2H),5.36(t,J=5.4Hz,1H),3.27(q,J=6.9Hz,2H),2.35(s,3H),2.01(s,6H),1.70-1.56(m,2H),1.42(dq,J=14.5,7.3Hz,2H),0.96(t,J=7.3Hz,3H)。13C NMR(101MHz,CDCl3)δ167.27,151.08,136.81,136.57,136.29,131.44,130.82,128.05,127.24,120.99,119.50,45.71,31.62,21.19,20.64,19.96,13.69。
1H NMR(400MHz,CDCl3)δ7.71(d,J=8.0Hz,1H),7.30(t,J=7.8Hz,1H),7.19(d,J=7.6Hz,1H),6.92(s,2H),6.82(s,1H),5.46(s,1H),3.04(s,2H),2.30(s,3H),1.91(s,6H),0.02(s,9H)。13C NMR(101MHz,CDCl3)δ181.49,141.87,137.85,135.10,133.64,132.96,130.84,129.68,128.76(2C),123.61,21.10,20.41,-2.55。
1H NMR(500MHz,CDCl3)δ7.62(dd,J=7.8,1.4Hz,1H),7.10(t,J=7.6Hz,1H),7.03(dd,J=7.4,1.4Hz,1H),6.95(s,2H),5.24(s,1H),2.66(d,J=4.8Hz,2H),2.32(s,3H),1.99(s,6H),0.11(s,9H)。13C NMR(101MHz,CDCl3)δ170.56,151.51,136.97,136.76,136.45,131.38,130.95,128.18,127.30,120.91,119.68,36.53,21.33,20.75,-2.57。
1H NMR(400MHz,CDCl3)δ7.70(dd,J=8.0,1.5Hz,1H),7.30(t,J=7.8Hz,1H),7.19(dd,J=7.6,1.5Hz,1H),6.93(s,2H),5.29(s,2H),4.49(dq,J=13.0,6.3Hz,1H),2.30(s,3H),1.93(s,6H),1.14(d,J=6.6Hz,6H)。13C NMR(101MHz,CDCl3)δ178.89,141.81,138.07,135.20,133.61,133.26,131.01,129.80,128.94(2C),123.52,47.69,22.30,21.17,20.59。
1H NMR(500MHz,CDCl3)δ7.60(dt,J=7.8,1.1Hz,1H),7.12(td,J=7.6,0.9Hz,1H),7.04(dt,J=7.5,1.1Hz,1H),6.96(s,2H),5.23(d,J=7.9Hz,1H),3.66(h,J=6.5Hz,1H),2.34(s,3H),2.01(s,6H),1.27(d,J=6.4Hz,6H)。13C NMR(126MHz,CDCl3)δ166.14,151.05,136.94,136.64,136.40,131.58,130.99,128.16,127.33,121.16,119.59,48.14,23.19,21.32,20.79。
1H NMR(400MHz,CDCl3)δ7.62(dd,J=7.7,1.4Hz,1H),7.13(t,J=7.6Hz,1H),7.07(dd,J=7.4,1.4Hz,1H),6.99(s,2H),5.42(d,J=8.3Hz,1H),3.31(dddd,J=13.5,9.7,8.1,3.8Hz,1H),2.36(s,3H),2.16-2.06(m,2H),2.04(s,6H),1.84-1.73(m,2H),1.70-1.59(m,1H),1.50-1.34(m,2H),1.34-1.22(m,3H)。13C NMR(101MHz,CDCl3)δ166.22,151.05,136.92,136.61,136.35,131.43,130.88,128.15,127.27,121.04,119.55,55.09,33.29,25.50,24.68,21.29,20.77。
1H NMR(400MHz,CDCl3)7.62(dd,J=7.7,1.4Hz,1H),7.15(t,J=7.6Hz,1H),7.08(dd,J=7.4,1.4Hz,1H),6.99(s,2H),5.40(s,1H),2.38(s,3H),2.05(s,6H),1.42(s,9H)。13C NMR(101MHz,CDCl3)δ163.99,150.50,137.04,136.43,136.40,131.68,131.38,127.99,127.15,121.30,119.25,52.77,29.15,21.29,20.76。
1H NMR(400MHz,CDCl3)δ7.60(dd,J=7.7,1.3Hz,1H),7.13(t,J=7.6Hz,1H),7.06(dd,J=7.4,1.4Hz,1H),6.98(s,2H),5.46(s,1H),2.36(s,3H),2.18-2.11(m,3H),2.03(s,6H),2.01(d,J=2.9Hz,6H),1.70(qd,J=12.2,5.9Hz,6H)。13C NMR(101MHz,CDCl3)δ163.45,150.04,136.99,136.53,136.41,131.56,131.48,128.04,127.09,121.19,119.20,52.86,42.00,36.29,29.60,21.27,20.77。
1H NMR(400MHz,CDCl3)δ7.61(d,J=7.8Hz,1H),7.39-7.30(m,5H),7.15(t,J=7.6Hz,1H),7.07(d,J=6.1Hz,1H),6.97(s,2H),5.67(s,1H),4.49(d,J=5.8Hz,2H),2.35(s,3H),2.01(s,6H)。13C NMR(101MHz,CDCl3)δ136.83,136.32,129.56,128.09,127.42,124.02,122.38,119.61,119.46,41.00,21.20,20.65。
1H NMR(400MHz,CDCl3)δ7.69(ddd,J=8.0,1.5,0.5Hz,1H),7.50(s,1H),7.35-7.26(m,4H),7.17(ddd,J=7.6,1.5,0.6Hz,1H),6.96(s,2H),6.89(s,1H),6.85(d,J=7.4Hz,2H),2.36(s,3H),1.95(s,6H)。13C NMR(101MHz,CDCl3)δ180.26,141.87,137.72,136.54,135.03,134.57,132.67,130.17,129.87,129.65,128.77,127.58,125.70(2C),125.12,21.26,20.75。
1H NMR(400MHz,CDCl3)δ7.63(dd,J=7.8,1.3Hz,1H),7.42(s,1H),7.39-7.32(m,2H),7.30(dt,J=8.3,0.9Hz,2H),7.21(t,J=7.6Hz,1H),7.15-7.09(m,2H),6.98(s,2H),2.35(s,3H),2.02(s,6H)。13C NMR(101MHz,CDCl3)δ162.99,149.66,140.05,136.86,136.46,136.38,132.23,130.48,129.51,128.20,127.58,123.94,122.46,119.70,119.47,21.29,20.80。
1H NMR(400MHz,CDCl3)δ7.66(dd,J=7.9,1.3Hz,1H),7.29-7.26(d,2H),7.23(t,J=7.6Hz,1H),7.17(t,J=1.7Hz,1H),7.14(dd,J=7.4,1.3Hz,1H),6.99(s,2H),2.38(s,3H),2.05(s,6H),1.31(s,18H)。13C NMR(101MHz,CDCl3)δ152.18,136.59,136.27,129.06,128.25,128.09,127.26,125.32,122.28,119.45,117.80,113.76,34.98,31.35,21.21,20.69。
1H NMR(400MHz,CDCl3)δ7.52(dd,J=7.7,1.4Hz,1H),7.27-7.20(m,1H),7.19(d,J=7.9Hz,2H),7.15(t,J=7.6Hz,1H),7.09(dd,J=7.5,1.4Hz,1H),7.07(s,1H),7.00(s,2H),2.39(s,3H),2.30(s,6H),2.07(s,6H)。13C NMR(101MHz,CDCl3)δ167.79,150.92,137.52,137.18,136.80,136.62,136.40,131.61,131.10,128.98,128.38,128.29,127.37,121.54,119.66,21.33,20.77,18.23。
1H NMR(400MHz,CDCl3)δ7.53(dd,J=7.6,1.5Hz,1H),7.41(t,J=7.7Hz,1H),7.28(d,J=7.7Hz,2H),7.15(t,J=7.5Hz,1H),7.10(dd,J=7.5,1.5Hz,1H),7.03(s,2H),6.73(s,1H),3.29(hept,J=6.8Hz,2H),2.38(s,3H),2.10(s,6H),1.21(d,J=6.9Hz,12H)。13C NMR(101MHz,CDCl3)δ168.90,151.30,148.16,136.96,136.78,136.46,133.96,131.84,131.40,129.44,128.34,127.31,124.42,121.53,119.76,28.51,25.41,21.35,20.84。
1H NMR(400MHz,クロロホルム-d)δ7.15(ddt,J=7.9,7.3,1.6Hz,1H),6.96(s,2H),6.90(dt,J=7.5,1.5Hz,1H),6.84-6.74(m,2H),3.38(s,2H),2.32(d,J=0.7Hz,3H),2.01(d,J=0.8Hz,6H)。13C NMR(101MHz,クロロホルム-d)δ143.53,137.02,136.95,134.85,129.95,128.37,128.01,126.16,118.46,114.93,21.03,20.07。C15H17N[M+H]+についての計算値HRMS(ESI):212.1434、測定値:212.1431。
H NMR(400MHz,クロロホルム-d)δ7.45(dd,J=8.0,1.5Hz,1H),7.40(ddd,J=8.2,7.4,1.6Hz,1H),7.30(td,J=7.4,1.5Hz,1H),7.19-7.15(m,1H),7.13(s,1H),6.43(s,2H),2.29(s,3H),1.90(s,6H)。13C NMR(101MHz,クロロホルム-d)δ181.24,138.05,136.18,135.55,134.91,133.03,131.93,128.90,128.74,127.23,123.93,21.22,20.40。
1H NMR(400MHz,クロロホルム-d)δ7.54(dd,J=7.8,1.3Hz,1H),7.15-7.10(m,1H),7.05-7.00(m,3H),6.11(s,2H),2.46(s,3H),1.99(s,6H)。13C NMR(101MHz、クロロホルム-d)δ167.28,150.70,137.58,137.36,136.45,130.90,130.49,127.72,126.67,121.60,119.64,21.07,20.55。
1H NMR(400MHz,クロロホルム-d)δ8.95(s,1H),7.81(dd,J=7.9,1.2Hz,1H),7.34(dd,J=7.9,7.4Hz,1H),7.17(dd,J=7.4,1.2Hz,1H),7.00(s,2H),2.36(s,3H),1.96(s,6H),1.31(s,9H)13C NMR(101MHz、クロロホルム-d)δ176.59、157.16、147.00、137.17、136.45、136.15、133.61、132.57、128.09、127.21、123.82、120.14、39.32、27.22、21.26、20.56。C21H24N2OS[M+H]+についての計算値HRMS(ESI):353.1682、測定値:353.1694。
1H NMR(400MHz,クロロホルム-d)δ7.58(dd,J=7.8,1.4Hz,1H),7.09(t,J=7.6Hz,1H),7.02(dd,J=7.4,1.4Hz,1H),6.94(t,J=0.6Hz,2H),5.74(s,1H),2.93(d,J=5.7Hz,2H),2.32(s,3H),1.99(s,6H),0.93(s,9H)。13C NMR(101MHz,cdcl3)δ168.23,151.00,136.79,136.58,136.33,131.16,130.50,128.05,127.26,120.89,119.41,58.40,32.42,27.20,21.16,20.63。C21H26N2S[M+H]+についての計算値HRMS(ESI):339.1889、測定値:339.1890。
1H NMR(400MHz,CDCl3)δ8.10(ddd,J=7.7,1.3,0.7Hz,2H),7.88(dd,J=8.1,1.3Hz,1H),7.56(t,J=8.1Hz,1H),7.45(td,J=8.2,8.1,1.3Hz,2H),7.40(dd,J=7.1,1.2Hz,1H),7.32(td,J=7.7,1.0Hz,2H),7.14(dt,J=8.1,0.9Hz,2H)。13C NMR(101MHz,CDCl3)δ141.56,134.34,132.30,132.02,130.61,126.52,123.96,121.09,120.56,114.62,109.88(2C)。
1H NMR(400MHz,CDCl3)δ8.18(dt,J=7.7,1.0Hz,2H),7.62(dd,J=8.1,1.4Hz,1H),7.44(ddd,J=8.3,7.2,1.2Hz,2H),7.33(ddd,J=8.1,7.3,1.0Hz,2H),7.26(dd,J=7.8,1.4Hz,1H),7.19(dt,J=8.1,0.8Hz,2H),6.80(t,J=7.9Hz,1H),4.04(s,2H)。13C NMR(101MHz,CDCl3)δ142.50,140.47,132.97,129.04,126.30,123.60,123.01,120.53,120.34,118.77,110.24,110.16。
1H NMR(400MHz,CDCl3)δ8.18(d,J=7.8Hz,2H),7.78(dd,J=8.1,1.3Hz,1H),7.53(d,J=9.2Hz,1H),7.46(t,J=7.7Hz,2H),7.36(td,J=7.9,2.4Hz,3H),7.16(d,J=8.1Hz,2H)。13C NMR(101MHz,CDCl3)δ140.62,135.41,133.01,128.95,128.09,126.32,123.73,121.20,120.66,120.62,109.65。
1H NMR(400MHz,CDCl3)δ8.18(dt,J=7.7,1.0Hz,2H),7.69(dd,J=7.9,1.2Hz,1H),7.51(dd,J=7.8,1.2Hz,1H),7.40(ddd,J=8.2,6.9,1.3Hz,2H),7.33-7.27(m,4H),7.27-7.23(m,1H),5.13(s,1H),2.01-1.91(m,3H),1.84(d,J=2.9Hz,6H),1.57(dt,J=12.2,3.0Hz,3H),1.43(dq,J=12.5,2.0Hz,3H)。13C NMR(101MHz,CDCl3)δ163.44,149.26,141.47,133.21,127.58,125.45,125.02,123.54,121.59,120.05,119.98,119.50,111.27,53.96,41.43,36.12,29.47。
1H NMR(400MHz,CDCl3)δ8.17(d,J=7.5Hz,2H),7.73(dd,J=7.9,1.2Hz,1H),7.47(dd,J=7.8,1.1Hz,1H),7.38(ddd,J=8.3,7.2,1.2Hz,2H),7.28-7.32(m,5H),7.27-7.22(m,5H),5.67(t,J=5.6Hz,1H),4.39(d,J=5.8Hz,2H)。13C NMR(101MHz,CDCl3)δ167.71,149.24,141.26,137.21,132.79,128.58,127.60,127.47,125.54,125.37,123.45,121.68,120.46,120.05,119.63,110.98,49.09。
1H NMR(400MHz,CDCl3)δ8.17(d,J=7.6Hz,2H),7.74(dd,J=7.8,1.1Hz,1H),7.48-7.44(m,1H),7.41-7.36(m,2H),7.32-7.26(m,4H),5.79(t,J=5.4Hz,1H),3.16-2.89(q,2H),1.42(p,J=7.3Hz,2H),1.23(dq,J=14.4,7.3Hz,2H),0.83(t,J=7.3Hz,3H)。13C NMR(101MHz,CDCl3)δ168.01,149.53,141.26,132.71,127.27,125.49,125.35,123.46,121.34,120.40,120.04,119.56,110.95,45.51,31.30,19.81,13.59。
1H NMR(400MHz,CDCl3)δ8.16(d,J=7.7Hz,2H),7.73(d,J=7.8Hz,1H),7.43(d,J=6.9Hz,1H),7.38(t,J=7.6Hz,2H),7.28(d,J=7.1Hz,2H),7.27-7.21(m,3H),2.90(d,J=6.2Hz,2H),0.88(s,9H)。13C NMR(101MHz,CDCl3)δ169.38,149.20,141.09,132.25,126.82,125.49,125.18,123.49,121.10,120.23,119.99,119.68,111.10,58.01,32.36,26.83。
1H NMR(400MHz,CDCl3)δ8.18(d,J=7.7Hz,2H),7.76(d,J=8.4Hz,1H),7.44(d,J=7.7Hz,1H),7.39(t,J=7.6Hz,2H),7.29(d,J=7.3Hz,2H),7.23(d,J=7.7Hz,2H),5.67(s,1H),2.50(d,J=5.4Hz,2H),0.01(s,9H)。13C NMR(101MHz,CDCl3)δ171.00,150.09,141.34,132.72,127.06,125.55,125.52,123.46,121.09,120.55,120.10,119.56,110.88,36.52,-2.84。
1H NMR(400MHz,CDCl3)δ8.18(d,J=7.7Hz,2H),7.75(d,J=7.8Hz,1H),7.46(d,J=8.7Hz,1H),7.40(t,J=7.6Hz,2H),7.36-7.28(m,2H),7.27-7.23(m,2H),5.18(d,J=7.9Hz,1H),3.68(dq,J=12.9,6.7Hz,1H),1.22(d,J=6.4Hz,6H)。13C NMR(101MHz,CDCl3)δ166.39,149.69,141.37,132.88,127.48,125.51,125.42,123.47,121.54,120.43,120.09,119.51,110.93,47.92,22.79。
1H NMR(400MHz,CDCl3)δ8.22-8.14(m,2H),7.70(dd,J=7.8,1.2Hz,1H),7.47(dd,J=7.8,1.2Hz,1H),7.41-7.35(m,2H),7.31-7.23(m,5H),5.16(s,1H),1.26(s,9H)。13C NMR(101MHz,CDCl3)δ164.27,149.47,141.48,133.20,127.77,125.54,125.19,123.54,121.76,120.09,119.53,111.18,53.59,28.88。
1H NMR(400MHz,CDCl3)δ8.19(d,J=7.7Hz,2H),7.80(dd,J=7.9,1.0Hz,1H),7.51(dd,J=7.7,1.0Hz,1H),7.40(t,J=8.2Hz,2H),7.35(t,J=7.8Hz,1H),7.31-7.23(m,4H),7.16(m,J=2.5Hz,3H),1.23(s,18H)。13C NMR(101MHz,CDCl3)δ163.85,152.32,149.27,141.42,138.66,132.44,129.05,128.06,125.82,125.65,123.48,122.69,120.55,120.19,119.60,118.40,114.11,110.64,34.90,31.26。
1H NMR(400MHz,CDCl3)δ8.14(dd,J=7.7,1.2Hz,2H),7.90(s,1H),7.59(dd,J=7.8,1.2Hz,1H),7.42(ddd,J=8.3,7.1,1.3Hz,2H),7.38(dd,J=7.8,1.2Hz,1H),7.32(td,J=7.5,1.1Hz,2H),7.28(d,J=8.3Hz,2H),7.20(t,J=7.8Hz,1H),7.09(dd,J=8.3,6.8Hz,1H),7.00(d,J=7.5Hz,2H),2.14(s,6H)。13C NMR(101MHz,CDCl3)δ169.43,149.37,141.44,137.01,136.39,132.96,128.78,128.45,127.99,125.68,125.21,123.83,121.83,120.33,120.22,119.76,111.12,18.01。
1H NMR(400MHz,CDCl3)δ8.39-8.30(m,3H),7.90(d,J=8.9Hz,1H),7.83(d,J=1.4Hz,1H),7.57(dd,J=9.2,2.1Hz,1H),7.51(dd,J=8.8,1.5Hz,1H),1.58(s,12H),1.44(d,J=7.3Hz,18H)。13C NMR(101MHz,CDCl3)δ147.35,146.63,135.82,134.74,131.01,129.89,128.65,128.27,127.87,125.29,124.31,122.87,122.74,84.14,35.29,34.76,31.02,30.95,25.27。
1H NMR(400MHz,CDCl3)δ8.42(s,1H),7.97(d,J=8.9Hz,1H),7.90(d,J=1.8Hz,1H),7.63-7.53(m,3H),7.50(s,1H),7.47(dd,J=9.2,2.0Hz,1H),7.10(dd,J=7.4,1.4Hz,1H),6.80(t,J=7.7Hz,1H),3.78(s,2H),1.42(s,9H),1.30(s,9H)。13C NMR(101MHz,CDCl3)δ148.09,147.38,142.83,132.11,131.50,131.47,131.33,130.42,129.76,128.78,128.13,126.68,125.75,125.57,124.80,124.75,122.74,120.10,118.70,109.56,35.06,34.85,30.94,30.87。
1H NMR(400MHz,CDCl3)8.48(s,1H),8.00(d,J=8.9Hz,1H),7.93(s,1H),7.78(dd,J=8.0,1.4Hz,1H),7.57(dd,J=8.9,1.7Hz,1H),7.49(dd,J=9.2,1.9Hz,1H),7.44-7.39(m,2H),7.36-7.30(m,2H),1.44(s,9H),1.32(s,9H)。13C NMR(101MHz,CDCl3)δ148.43,147.22,139.20,138.53,132.78,132.56,131.73,131.05,129.96,128.35,127.51,127.45,125.80,125.01,124.81,124.71,123.16,122.93,122.76,119.32,35.09,34.82,31.36,30.89。
1H NMR(400MHz,CDCl3)δ8.37(s,1H),7.94(m,1H),7.88(d,J=1.9Hz,1H),7.72(dd,J=7.7,1.3Hz,1H),7.53-7.45(m,2H),7.36(dd,J=9.3,2.0Hz,1H),7.31(dd,J=7.4,1.3Hz,1H),7.23(t,J=7.6Hz,1H),5.00(s,1H),2.29(d,J=2.2Hz,1H),1.91(s,3H),1.78(s,6H),1.52(d,J=9.6Hz,5H),1.41(s,9H),1.23(s,9H)。13C NMR(101MHz,CDCl3)δ162.84,151.81,146.49,146.39,134.44,131.41,131.30,130.28,129.90,129.25,129.17,128.94,127.78,127.05,127.00,125.71,124.24,124.12,122.43,121.59,120.92,119.78,53.29,41.61,36.08,34.88,34.71,31.58,31.12,30.97,30.92,30.81,29.74,29.35,22.64,14.11。
1H NMR(400MHz,クロロホルム-d)δ6.89-6.85(m,2H),4.26(d,J=0.5Hz,2H),2.30(s,3H),2.23(s,6H)。
1H NMR(400MHz,DMSO-d6)δ9.15(s,2H),7.00(s,2H),6.79(s,1H),2.28(s,3H),2.13(s,6H)。
1H NMR(400MHz,クロロホルム-d)δ9.19(s,1H),6.91(s,2H),6.71(d,J=0.7Hz,1H),2.30(s,3H),2.08(s,6H),1.32(d,J=0.9Hz,9H)。13C NMR(101MHz,cdcl3)δ176.28,157.58,148.81,137.86,137.36,132.13,128.30,111.30,39.27,27.34,21.22,20.42。
1H NMR(400MHz,クロロホルム-d)δ6.87(s,2H),6.18(d,J=0.9Hz,1H),5.29(s,1H),3.04(d,J=5.2Hz,2H),2.28(s,3H),2.14(s,6H),0.98(d,J=0.9Hz,9H)。13C NMR(101MHz,cdcl3)δ170.20,150.47,137.44,137.36,133.10,128.12,103.18,58.30,32.43,27.45,21.20,20.37。
1H NMR(400MHz,クロロホルム-d)δ11.61(s,1H),6.90(s,2H),6.72(d,J=0.6Hz,1H),2.30(s,3H),2.08(s,6H),1.69(t,J=7.5Hz,2H),1.43(p,J=7.6Hz,2H),1.35-1.09(m,7H),0.88(t,J=7.0Hz,3H)。13C NMR(101MHz、クロロホルム-d)δ171.79,158.90,147.70,137.91,137.24,131.82,128.57,111.07,34.71,31.56,28.64,24.49,22.50,21.04,20.37,14.03。
1H NMR(400MHz,クロロホルム-d)δ6.87(s,2H),6.17(s,1H),6.10(s,1H),3.09(td,J=7.2,5.2Hz,2H),2.28(s,3H),2.14(s,6H),1.50(p,J=7.2Hz,2H),1.34-1.21(m,8H),0.89(t,J=6.8Hz,3H)。13C NMR(101MHz,クロロホルム-d)δ169.73,150.29,137.32,137.18,133.04,127.96,102.82,46.24,31.76,29.27,28.96,26.88,22.59,21.05,20.24,14.07。
エタノールおよびジクロロメタン(4mL、1:1)中のチオ尿素(0.21mmol)の混合物に、ヨードメタン(0.028mL、0.45mmol、2.15当量)を添加した。次に、混合物を室温で一晩撹拌した。次に、無色透明の溶液を、NaHCO3の飽和水性混合物(6mL)で中和し、ジクロロメタン(2mL)で希釈し、2分間激しく(1000rpm)撹拌した。次に、NaOHの水溶液(1mL、1N)を添加し、二相混合物を分液漏斗に注ぎ、分配し、有機層をNaHCO3の飽和水性混合物(3×5mL)で洗浄した。残留有機物を、ジクロロメタン(2×5mL)を使用して水層から逆抽出し、すべての有機層を合わせ、ブライン(1×5mL)で洗浄し、固体Na2SO4で乾燥し、濾過し、濃縮して、黄色の油として生成物(83.2mg、99%)を得た。この生成物をさらに精製することなく次の反応にキャリーオーバーした。
1H NMR(400MHz,CDCl3)δ7.55(dd,J=8.0,1.5Hz,1H),7.04(dd,J=7.5,1.5Hz,1H),6.92(t,J=7.7Hz,1H),6.88-6.82(m,2H),3.93(s,1H),3.84(q,J=6.4Hz,1H),2.29(s,3H),2.17(s,3H),2.09(s,6H),1.04(d,J=6.2Hz,6H)。13C NMR(101MHz,CDCl3)δ146.54,136.58,136.37,136.16,135.56,131.53,129.89,127.86,123.37,117.37,44.76,23.15,21.15,20.72,14.31。
1H NMR(400MHz,CDCl3)δ7.55(dd,J=7.5,2.1Hz,1H),7.03-6.95(m,4H),3.24(hept,J=6.5Hz,1H),2.34(s,3H),2.01(s,6H),1.00(d,J=6.4Hz,6H)。13C NMR(101MHz,CDCl3)δ137.86,137.59,137.45,136.67,135.39,132.01,129.71,128.33,125.32,118.93,49.33,24.08,21.19,20.48。
1H NMR(400MHz,CDCl3)δ7.55(dd,J=7.9,1.5Hz,1H),7.02(dd,J=7.4,1.5Hz,1H),6.90-6.82(m,3H),3.61(q,J=6.7Hz,2H),3.20(d,J=8.2Hz,2H),2.28(s,3H),2.07(s,6H),1.00(d,J=6.4Hz,12H)。13C NMR(101MHz,CDCl3)δ147.57,146.58,137.36,137.14,136.22,135.83,131.71,129.97,127.74,122.44,119.40,43.10,23.35,21.09,20.79。
1H NMR(400MHz,CDCl3)δ7.22(dd,J=7.9,1.1Hz,1H),7.03(t,J=7.7Hz,1H),6.96(s,2H),6.85(dd,J=7.5,1.1Hz,1H),4.39(hept,J=7.0Hz,1H),4.06(hept,J=13.0,6.5Hz,1H),3.70(d,J=8.0Hz,1H),2.35(s,3H),2.05(s,6H),1.62(d,J=6.9Hz,6H),1.21(d,J=6.3Hz,6H)。13C NMR(101MHz,CDCl3)δ152.89,141.22,137.10,136.54,136.21,133.29,129.31,128.02,122.32,118.72,107.91,46.37,45.54,23.38,21.26,21.21,20.92。
1H NMR(500MHz,CDCl3)δ7.55(td,J=8.0,5.3Hz,1H),7.28(ddd,J=9.6,8.4,1.3Hz,1H),7.05(dt,J=7.7,1.1Hz,1H),6.92(s,2H),2.32(s,3H),2.02(s,6H)。13C NMR(126MHz,CDCl3)δ153.85(d,J=257.9Hz),138.53,136.40,133.85(d,J=19.5Hz),131.97(d,J=8.2Hz),128.74(d,J=24.2Hz),128.58,128.36,126.67(d,J=3.7Hz),115.93(d,J=19.0Hz),21.20,20.31。
1H NMR(400MHz,CDCl3)δ7.35(dd,J=8.4,7.4Hz,1H),6.88(s,2H),6.82(dt,J=8.6,0.9Hz,1H),6.38(dd,J=7.3,1.2Hz,1H),6.13(d,J=7.1Hz,1H),3.86-3.68(m,J=6.4Hz,1H),2.30(s,3H),2.01(s,6H),1.30(d,J=6.3Hz,6H)。
1H NMR(400MHz,CDCl3)δ7.92(s,1H),7.41(d,J=7.5Hz,1H),7.33(t,J=7.7Hz,1H),7.06(d,J=6.5Hz,1H),6.97(s,2H),4.66(hept,J=6.8Hz,1H),2.33(s,3H),1.98(s,6H),1.66(d,J=6.7Hz,6H)。
1H NMR(400MHz,CDCl3)δ7.51(dd,J=8.3,1.1Hz,1H),7.26(t,J=7.8Hz,1H),7.00(dd,J=7.4,1.0Hz,1H),6.94(s,2H),4.97(hept,J=6.9Hz,1H),2.32(s,3H),1.97(s,6H),1.70(d,J=7.0Hz,6H)。13C NMR(101MHz,CDCl3)δ142.60,136.96,136.56,134.98,134.14,132.86,129.44,128.31,123.49,122.50,109.83,109.83,50.57,21.27,21.27,20.83。
1H NMR(400MHz,CDCl3)δ7.38-7.27(m,5H),7.23(dd,J=7.9,1.1Hz,1H),7.06(t,J=7.7Hz,1H),6.97(s,2H),6.88(dd,J=7.5,1.0Hz,1H),4.60(s,2H),4.41(hept,J=7.0Hz,1H),4.19(s,1H),2.35(s,3H),2.06(s,6H),1.62(d,J=6.9Hz,6H)。13C NMR(101MHz,CDCl3)δ153.35,141.07,139.53,137.03,136.42,136.22,133.61,129.63,128.67,128.19,128.04,127.51,122.48,118.97,107.93,48.32,46.47,21.28,20.98。
1H NMR(500MHz,DMSO-d6)δ7.80(s,1H),7.42-7.36(m,1H),7.06-6.92(m,4H),6.79(s,2H),6.62(dd,J=7.4,1.2Hz,1H),4.91(hept,J=6.8Hz,1H),2.19(s,3H),2.11(s,6H),1.84(s,6H),1.62(d,J=6.8Hz,6H)。13C NMR(126MHz,DMSO-d6)δ151.60,141.01,137.53,136.59,135.72,135.17,135.01,132.90,128.88,128.18,127.96,127.91,127.57,125.40,121.30,118.48,108.54,45.77,20.59,20.53,20.39,18.08。
1H NMR(400MHz,CDCl3)δ7.22(d,J=8.0Hz,1H),7.04(t,J=7.7Hz,1H),6.97(s,2H),6.86(d,J=7.4Hz,1H),4.53-4.33(m,1H),3.78(m,2H),2.36(s,3H),2.06(s,6H),1.77-1.67(m,4H),1.64(d,J=6.9Hz,6H),1.40(q,J=14.5,13.3Hz,2H),1.24-1.14(m,2H)。13C NMR(101MHz,CDCl3)δ152.73,141.13,136.98,136.41,136.04,133.24,129.11,128.22,127.93,122.28,118.50,107.67,60.40,51.91,46.25,33.66,25.83,24.72,21.13,21.10,20.82,14.21。
1H NMR(400MHz,CDCl3)δ7.22(dd,J=7.9,1.1Hz,1H),7.05(t,J=7.7Hz,1H),6.97(s,2H),6.86(dd,J=7.5,1.1Hz,1H),4.42(p,J=7.0Hz,1H),3.86(t,J=5.7Hz,1H),3.41(q,J=6.6Hz,2H),2.36(s,3H),2.07(d,J=1.4Hz,6H),1.64(m,8H),1.35(q,J=3.7Hz,4H),0.95-0.86(m,3H)。13C NMR(101MHz,CDCl3)δ153.51,141.10,136.96,136.41,136.05,133.39,129.22,127.89,122.22,118.56,107.62,60.40,46.23,44.08,29.66,29.10,22.48,21.14,21.10,21.06,20.82,14.21,14.00。
1H NMR(400MHz,CDCl3)δ7.26(dd,J=7.9,1.1Hz,1H),7.05(t,J=7.7Hz,1H),6.95(s,2H),6.88(dd,J=7.5,1.1Hz,1H),4.55(hept,J=7.0Hz,1H),3.60(s,1H),2.35(s,3H),2.07(s,9H),2.00(d,J=2.9Hz,6H),1.68-1.59(m,12H)。13C NMR(101MHz,CDCl3)δ151.36,141.23,136.98,136.48,135.97,132.79,129.92,127.96,122.49,118.96,108.17,53.46,46.56,42.91,36.59,29.90,21.30,21.25,21.01。
1H NMR(400MHz,CDCl3)δ7.21(dd,J=7.9,1.1Hz,1H),7.02(t,J=7.7Hz,1H),6.96(s,2H),6.85(dd,J=7.4,1.1Hz,1H),4.37(hept,J=7.0Hz,1H),3.80(s,1H),2.37(s,3H),2.08(s,6H),1.89(s,2H),1.63(d,J=6.9Hz,6H),1.48(s,6H),0.98(s,9H)。13C NMR(101MHz,CDCl3)δ151.43,141.65,136.98,136.88,135.73,132.70,129.51,127.74,122.07,118.29,107.58,56.29,51.29,46.23,31.85,31.66,30.06,21.29,21.27,20.97。
1H NMR(400MHz,CDCl3)δ7.18(d,J=7.8Hz,1H),7.07-6.99(m,1H),6.96(s,2H),6.84(d,J=7.5Hz,1H),4.45(p,J=7.0Hz,1H),3.98(s,1H),3.27(s,2H),2.35(s,3H),2.09-1.99(m,6H),1.73-1.59(m,6H),1.00-0.89(m,9H)。13C NMR(101MHz,CDCl3)δ154.17,141.08,137.11,136.57,136.16,133.71,129.21,128.03,122.41,118.63,107.43,55.17,46.28,32.21,27.45,21.27,20.92。
1H NMR(400MHz,CDCl3)δ8.16-8.06(m,2H),7.80-7.68(m,1H),7.48(td,J=8.7,1.2Hz,1H),7.44-7.37(m,3H),7.32(ddd,J=8.2,7.3,1.0Hz,2H),7.17(dt,J=8.2,0.9Hz,2H)。13C NMR(101MHz,CDCl3)δ141.08,133.01,132.92,132.43,126.60,126.55,124.07,121.19,120.70,117.64,117.45,109.52。
1H NMR(400MHz,CDCl3)δ8.11(dt,J=7.7,1.1Hz,2H),7.52(ddd,J=8.4,7.6,0.6Hz,1H),7.38(ddd,J=8.3,7.2,1.3Hz,2H),7.30-7.22(m,4H),7.04-6.95(m,1H),6.81(dd,J=7.6,1.2Hz,1H),6.39(d,J=7.1Hz,1H),3.89-3.78(m,1H),1.35(d,J=6.3Hz,6H)。
1H NMR(400MHz,CDCl3)δ8.15(dd,J=7.9,1.3Hz,2H),7.99(s,1H),7.56(q,J=4.2Hz,1H),7.50-7.45(m,2H),7.36(ddd,J=8.2,6.9,1.3Hz,2H),7.31-7.22(m,4H),4.74(hept,J=6.8Hz,1H),1.71(d,J=6.8Hz,6H)。
1H NMR(400MHz,CDCl3)δ8.15(dd,J=8.1,1.4Hz,2H),7.66(p,J=4.0Hz,1H),7.45-7.33(m,4H),7.32-7.24(m,4H),5.03(hept,J=7.1Hz,1H),1.75(d,J=7.0Hz,6H)。13C NMR(101MHz,CDCl3)δ141.49,140.57,135.96,130.26,128.84,125.75,123.94,123.19,121.38,120.22,119.90,110.85,110.80,50.93,21.24。
1H NMR(400MHz,CDCl3)δ8.17(d,J=7.7Hz,2H),7.51(d,J=8.2Hz,2H),7.36(ddd,J=8.4,7.1,1.5Hz,3H),7.34-7.22(m,3H),7.15(t,J=7.9Hz,1H),4.42(hept,J=7.0Hz,1H),3.80(s,1H),2.04-1.96(m,9H),1.65(d,J=6.9Hz,6H),1.62-1.43(m,6H)。13C NMR(101MHz,CDCl3)δ151.28,141.23,138.79,134.73,126.07,125.06,123.61,119.76,119.28,118.91,118.77,112.20,108.07,53.12,46.52,42.21,36.43,29.77,21.22。
1H NMR(400MHz,CDCl3)δ8.17(dd,J=7.8,1.3Hz,2H),7.46(dd,J=8.3,1.1Hz,2H),7.37(ddd,J=8.3,7.1,1.3Hz,2H),7.31(dd,J=8.0,1.0Hz,1H),7.27(ddd,J=8.3,6.9,1.2Hz,3H),7.13(t,J=7.8Hz,1H),4.36(hept,J=7.0Hz,1H),3.95(s,1H),1.78(s,2H),1.66(d,J=6.9Hz,6H),1.38(s,6H),0.96(s,9H)。13C NMR(101MHz,CDCl3)δ151.60,141.50,139.40,134.74,125.92,125.32,123.53,119.81,119.21,119.08,118.76,111.89,108.14,56.40,51.09,46.45,31.83,31.70,29.83,21.25。
1H NMR(500MHz,C6D6)δ7.15(dd,J=6.1,3.0Hz,1H),7.03(t,J=7.7Hz,6H),6.87-6.81(m,5H),6.77(s,2H),6.46(d,J=7.6Hz,6H),2.92(s,2H),2.08(s,6H),2.05(s,3H),2.04(s,6H),0.77(s,9H)。13C NMR(126MHz,C6D6)δ179.24,148.38,143.15,138.11,137.10,136.74,129.88,129.60,129.51,129.31,128.74,127.67,123.12,122.17,120.44,79.68,65.96,34.70,28.09,21.19,21.09。
1H NMR(500MHz,C6D6)δ7.19-7.17(m,1H),7.13(t,J=7.8Hz,6H),6.90-6.85(m,5H),6.82(s,2H),6.81-6.75(m,6H),2.88(s,2H),2.13(s,3H),2.10(s,6H),1.99(s,6H),0.66(s,9H)。13C NMR(126MHz,C6D6)δ179.00,148.25,143.18,138.24,136.96,136.37,129.60,129.42,129.34,129.26,129.04,128.57,123.05,122.47,120.36,89.87,65.59,34.35,27.87,21.35,21.12。
1H NMR(400MHz,C6D6)δ7.21(ddd,J=5.6,3.6,0.5Hz,1H),7.11-7.06(m,6H),6.91-6.86(m,3H),6.84(dd,J=2.0,0.4Hz,1H),6.83(d,J=0.4Hz,1H),6.79(dt,J=1.2,0.6Hz,2H),6.47-6.40(m,6H),2.82(s,2H),2.07(s,6H),2.07(s,6H),2.07(s,3H),0.04(d,J=0.4Hz,9H)。13C NMR(101MHz,C6D6)δ177.68,148.88,142.87,137.05,136.99,130.97,129.95,129.70,129.29,128.93,128.74,128.54,123.14,121.55,120.50,78.24,45.59,21.43,21.06,-1.5。
1H NMR(400MHz,C6D6)δ7.19(ddd,J=4.8,4.3,0.5Hz,1H),7.16-7.10(m,6H),6.90-6.84(m,5H),6.82(dt,J=1.2,0.6Hz,2H),6.76-6.71(m,6H),2.69(s,2H),2.11(s,3H),2.09(d,J=0.6Hz,6H),1.96(s,6H),-0.10(d,J=0.5Hz,9H)。13C NMR(101MHz,C6D6)δ177.51,148.68,143.13,138.27,136.99,136.55,129.49,129.23,129.10,129.08,128.37,127.91,123.05,121.96,120.46,88.92,44.99,21.44,21.26,-1.89。
1H NMR(500MHz,C6D6)δ7.21(dd,J=7.6,1.5Hz,1H),7.11-7.04(m,6H),6.92-6.85(m,3H),6.86(t,J=7.5Hz,1H),6.82(dd,J=7.5,1.5Hz,1H),6.79(s,2H),6.58-6.52(m,6H),3.46(hept,J=6.8Hz,1H),2.20(s,6H),2.12(s,3H),2.07(s,7H),0.91(d,J=6.7Hz,6H)。13C NMR(126MHz,C6D6)δ177.12,148.21,142.75,138.13,137.12,137.09,129.72,129.53,129.19,129.14,128.60,128.01,123.11,121.88,120.24,79.67,55.17,21.53,21.44,21.23。
1H NMR(500MHz,C6D6)δ7.19(dd,J=7.2,1.9Hz,1H),7.11(dd,J=8.2,7.3Hz,6H),6.90-6.80(m,7H),6.79-6.73(m,6H),3.39(p,J=6.7Hz,1H),2.15(s,3H),2.08(s,6H),2.04(s,6H),0.77(d,J=6.7Hz,6H)。13C NMR(126MHz,C6D6)δ176.67,148.18,142.74,138.23,136.99,136.60,129.46,129.34,129.18,128.97,128.57,128.13,123.00,122.22,120.22,89.49,55.23,21.57,21.31,21.19。
1H NMR(400MHz,C6D6)δ7.23(dd,J=7.6,1.7Hz,1H),7.11-7.06(m,6H),6.88(tdd,J=7.5,3.6,2.3Hz,4H),6.83(dd,J=7.5,1.7Hz,1H),6.81-6.79(m,2H),6.61-6.53(m,6H),3.16-3.00(m,1H),2.23(s,6H),2.13(s,3H),2.07(s,6H),1.67-1.30(m,7H),1.11-0.82(m,3H)。13C NMR(101MHz,C6D6)δ177.28,148.13,142.98,138.15,137.14,137.13,129.71,129.53,129.21,129.14,128.57,128.00,123.10,121.93,120.20,79.99,63.50,31.63,26.08,25.70,21.45,21.24。
1H NMR(400MHz,C6D6)δ7.21(dd,J=7.1,2.0Hz,1H),7.12(t,J=6.8Hz,6H),6.90-6.81(m,7H),6.80-6.75(m,6H),3.03(tt,J=10.6,5.3Hz,1H),2.16(s,3H),2.09(s,6H),2.07(s,6H),1.57-1.46(m,2H),1.42-1.19(m,5H),1.04-0.80(m,3H)。13C NMR(101MHz,C6D6)δ176.87,148.12,143.06,138.24,137.02,136.65,129.48,129.34,129.21,128.97,128.57,128.10,122.97,122.27,120.18,89.81,63.36,31.72,25.91,25.53,21.45,21.31。
1H NMR(400MHz,C6D6)δ7.21(dd,J=7.2,1.9Hz,1H),7.09(dd,J=8.2,7.3Hz,6H),6.94-6.86(m,5H),6.85-6.82(m,2H),6.71-6.67(m,6H),2.33(s,6H),2.21(s,3H),2.10(s,6H),0.99(s,9H)。13C NMR(101MHz,C6D6)δ172.98,147.24,143.33,137.67,137.22,137.09,130.39,129.83,129.80,129.51,129.40,127.97,123.15,122.01,120.02,82.17,56.06,28.73,21.45,21.35。
1H NMR(400MHz,C6D6)δ7.18(ddd,J=6.3,2.9,0.6Hz,1H),7.15-7.09(m,6H),6.92-6.87(m,3H),6.87-6.81(m,10H),2.19(s,3H),2.13(s,6H),2.10(d,J=0.6Hz,6H),0.92(d,J=0.5Hz,9H)。13C NMR(101MHz,C6D6)δ173.50,147.13,143.38,136.89,136.76,130.30,130.13,129.78,129.67,129.37,128.98,128.90,128.16,122.97,122.26,119.79,91.22,55.88,28.83,21.45,21.41。
1H NMR(400MHz,C6D6)δ7.22(dd,J=6.7,2.4Hz,1H),7.13(t,J=7.7Hz,7H),6.95-6.89(m,2H),6.89-6.80(m,10H),2.23(s,3H),2.17(s,6H),2.12(s,6H),1.91-1.83(m,3H),1.55(d,J=2.9Hz,6H),1.45(d,J=3.1Hz,6H)。13C NMR(101MHz,C6D6)δ172.77,146.83,143.98,137.87,136.92,130.51,129.86,129.74,129.43,128.86,128.18,122.92,122.32,119.73,91.75,56.50,40.70,36.25,29.98,21.43,21.38。
1H NMR(400MHz,C6D6)δ7.10(t,J=7.2Hz,8H),7.08-7.05(m,1H),6.87(dt,J=7.5,1.3Hz,4H),6.85-6.79(m,5H),6.69-6.64(m,6H),4.11(s,2H),2.16(s,3H),2.05(s,6H),2.00(s,6H)。13C NMR(101MHz,C6D6)δ179.91,147.99,142.97,138.32,138.04,137.02,136.59,129.46,129.43,129.23,129.08,128.95,128.73,127.76,127.42,123.10,122.35,120.39,89.06,55.31,21.44,21.24。
1H NMR(400MHz,C6D6)δδ7.07-7.01(m,6H),6.99(dd,J=6.9,2.3Hz,1H),6.89(s,3H),6.87(s,2H),6.85-6.78(m,5H),6.57-6.51(m,6H),2.22(s,3H),2.10(s,6H),2.06(s,6H),1.84(s,6H)。13C NMR(101MHz,C6D6)δ179.93,148.46,145.20,143.05,138.42,137.21,136.53,133.98,130.29,129.74,129.46,129.31,128.96,128.86,128.69,127.06,122.94,122.79,120.60,91.64,21.44,21.30,18.15。
1H NMR(500MHz,C6D6)δ7.21(s,2H),7.12(t,J=7.3Hz,3H),7.09-6.99(m,8H),6.95-6.84(m,7H),6.79(s,3H),6.70(s,4H),6.42(s,3H),2.13(s,6H),2.08-1.96(m,16H)。
1H NMR(400MHz,C6D6)δ8.04(dt,J=7.6,1.0Hz,2H),7.20(ddd,J=7.9,6.1,1.3Hz,3H),7.16-7.10(m,5H),7.07-6.99(m,5H),6.97(dd,J=7.8,1.3Hz,1H),6.84-6.74(m,4H),6.64(d,J=7.3Hz,6H),1.90-1.81(m,3H),1.73(s,6H),1.49-1.39(m,12H)。13C NMR(101MHz,C6D6)δ171.86,145.96,143.38,141.59,132.32,128.69,128.15,126.70,125.99,124.28,122.88,122.63,121.03,120.89,120.58,111.01,91.75,56.32,40.29,36.20,29.95。
1H NMR(400MHz,C6D6)δ8.05(d,J=7.6Hz,4H),7.23-7.15(m,4H),7.15-7.10(m,6H),7.13-7.04(m,4H),6.96(t,J=7.7Hz,4H),6.86(dd,J=7.8,1.3Hz,4H),6.86-6.74(m,2H),6.77-6.69(m,6H),6.58-6.47(m,6H),6.41(dd,J=7.8,1.3Hz,2H),3.80(d,J=15.5Hz,2H),3.15(d,J=15.6Hz,2H),1.88(d,J=12.4Hz,2H),1.54(d,J=11.0Hz,2H)。13C NMR(101MHz,C6D6)δ181.57,147.99,147.07,143.68,137.41,130.60,128.93,128.85,128.39,127.47,127.45,126.78,125.54,121.84,121.49,121.32,110.77,84.64,54.18。
1H NMR(400MHz,C6D6)δ6.71(s,4H),5.23(s,2H),2.87(s,4H),2.09(s,12H),2.08(s,6H),0.86(s,18H),0.42(s,6H)。13C NMR(101MHz、ベンゼン-d6)δ182.79,147.35,137.34,137.19,131.06,127.94,98.43,65.70,54.24,33.95,27.70,20.71,20.05。
1H NMR(400MHz,C6D6)δ7.09(t,J=7.7Hz,6H),7.00(d,J=1.5Hz,1H),6.97(t,J=7.6Hz,1H),6.93-6.87(m,4H),6.85(s,2H),6.66-6.60(m,6H),4.44(hept,J=7.0Hz,1H),3.80(hept,J=6.5Hz,1H),2.24(s,6H),2.19(s,3H),2.15(s,6H),1.20(d,J=6.9Hz,6H),1.02(d,J=6.4Hz,6H)。13C NMR(101MHz,C6D6)δ160.41,144.28,139.72,137.60,137.22,136.48,133.05,129.61,129.15,128.01,125.20,122.59,120.34,110.27,77.28,49.64,48.10,25.01,21.44,21.20,20.43。
1H NMR(400MHz,C6D6)δ7.13(dd,J=8.0,7.2Hz,6H),6.99-6.96(m,2H),6.90(dd,J=5.8,3.2Hz,1H),6.89-6.84(m,5H),6.82-6.78(m,6H),4.33(hept,J=7.0Hz,1H),3.87(hept,J=6.5Hz,1H),2.20(s,3H),2.18(s,6H),2.11(s,6H),1.13(d,J=7.0Hz,6H),0.89(d,J=6.5Hz,6H)。13C NMR(101MHz,C6D6)δ159.26,144.48,139.42,137.80,137.07,136.03,132.81,129.11,128.83,128.12,125.11,122.47,120.52,110.27,87.84,48.91,48.11,24.76,21.44,21.27,20.31。
触媒活性(クエンチ時間およびポリマー収率の観点から)ならびに得られたポリマー特性を、プロ触媒1~22について評価した。重合反応は、半バッチ反応器および並列圧力反応器(PPR)で行った。
Claims (18)
- 式(I)による構造を有するプロ触媒を含む触媒系であって、
式中、
Mが、チタン、ジルコニウム、またはハフニウムから選択される金属であり、前記金属が、+2、+3、または+4の形式酸化状態を有し、
各Xが、独立して、不飽和(C2-C50)炭化水素、不飽和(C2-C50)ヘテロ炭化水素、(C1-C50)ヒドロカルビル、(C6-C50)アリール、(C6-C50)ヘテロアリール、シクロペンタジエニル、置換シクロペンタジエニル、(C4-C12)ジエン、ハロゲン、-N(RN)2、および-NCORCから選択される単座または二座の配位子であり、
mが、1または2であり、
nが、2または3であるが、ただし、m+n=4であり、
各Zが、NRNまたはSであり、RNが、(C1-C40)ヒドロカルビルまたは(C1-C40)ヘテロヒドロカルビルであり、
各R1が、(C1-C40)ヒドロカルビルまたは(C1-C40)ヘテロヒドロカルビルであり、
各R2およびR3が、独立して、(C1-C50)ヒドロカルビル、(C1-C50)ヘテロヒドロカルビル、(C6-C50)アリール、(C4-C50)ヘテロアリール、-Si(RC)3、ハロゲン、および-Hからなる群から選択され、RCが、独立して、(C1-C20)ヒドロカルビル、(C1-C20)ヘテロヒドロカルビル、および-Hからなる群から選択され、
任意選択で、R2およびR3が、共有結合して環を形成する、触媒系。 - R3が、(2,4,6-トリイソプロピル)フェニル、2,4,6-トリメチルフェニル、3,5-ジ-tertブチルフェニル、ナフチル、カルボゾリル(carbozolyl)、またはシクロプロピルである、請求項1に記載の触媒系。
- 各R7が、(C6-C40)アリールまたは(C6-C40)ヘテロアリールである、請求項3に記載の触媒系。
- 各R7が、フェニル、(2,4,6-トリイソプロピル)フェニル、2,4,6-トリメチルフェニル、3,5-ジ-tert-ブチルフェニル、ナフチル、カルボゾリル、またはシクロプロピルである、請求項3に記載の触媒系。
- 各Zが、NRNであり、RNが、(C1-C8)アルキルである、請求項1~5のいずれか一項に記載の触媒系。
- 各Zが、Sである、請求項1~5のいずれか一項に記載の触媒系。
- mが、2である、請求項1~7のいずれか一項に記載の触媒系。
- mが、1である、請求項1~7のいずれか一項に記載の触媒系。
- 各R1が、直鎖(C1-C12)アルキル、分岐(C1-C12)アルキル、(C1-C12)シクロアルキル、トリメチルシリルメチル、ベンジル、および1-アダマンチルから選択される、請求項1~11のいずれか一項に記載の触媒系。
- 各Xが、独立して、ベンジル、フェニル、またはクロロである、請求項1~12のいずれか一項に記載の触媒系。
- 請求項1~13のいずれか一項に記載の1つ以上の金属-配位子錯体と溶液中で混合された連鎖移動剤および活性剤をさらに含む、先行請求項のいずれか一項に記載の触媒系。
- 重合プロセスであって、
オレフィン重合条件下、触媒系の存在下でエチレンおよび1つ以上のオレフィンを重合して、エチレン系ポリマーを形成することを含み、前記触媒系が、式(I)による金属-配位子錯体を含み、
式中、
Mが、チタン、ジルコニウム、またはハフニウムから選択される金属であり、前記金属が、+2、+3、または+4の形式酸化状態を有し、
各Xが、独立して、不飽和(C2-C20)炭化水素、不飽和(C2-C50)ヘテロ炭化水素、(C1-C50)ヒドロカルビル、(C6-C50)アリール、(C6-C50)ヘテロアリール、シクロペンタジエニル、置換シクロペンタジエニル、(C4-C12)ジエン、ハロゲン、-N(RN)2、および-NCORCから選択される単座または二座の配位子であり、
mが、1または2であり、
nが、2または3であるが、ただし、m+n=4であり、
各Zが、NRNまたはSであり、RNが、(C1-C20)ヒドロカルビルまたは(C1-C20)ヘテロヒドロカルビルであり、
各R1が、(C1-C40)ヒドロカルビルまたは(C1-C20)ヘテロヒドロカルビルであり、
各R2およびR3が、独立して、(C1-C50)ヒドロカルビル、(C1-C50)ヘテロヒドロカルビル、(C6-C50)アリール、(C4-C50)ヘテロアリール、-Si(RC)3、ハロゲン、および-Hからなる群から選択され、RCが、独立して、(C1-C20)ヒドロカルビル、(C1-C20)ヘテロヒドロカルビル、および-Hからなる群から選択され、
任意選択で、R2およびR3が、共有結合して環を形成する、重合プロセス。 - Zが、NRNであり、RNが、(C1-C8)アルキルである、請求項15に記載の触媒系。
- Zが、Sである、請求項15に記載の触媒系。
- 前記触媒系が、請求項14に記載の触媒系であり、前記プロセスが、前記連鎖移動剤および前記活性剤を、前記1つ以上の金属-配位子錯体と溶液中で混合することをさらに含む、請求項15に記載の重合プロセス。
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