CN113549047A - 氟代烷基磺酸内酯的制备方法 - Google Patents
氟代烷基磺酸内酯的制备方法 Download PDFInfo
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- CN113549047A CN113549047A CN202011289698.5A CN202011289698A CN113549047A CN 113549047 A CN113549047 A CN 113549047A CN 202011289698 A CN202011289698 A CN 202011289698A CN 113549047 A CN113549047 A CN 113549047A
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- compound
- sultone
- fluoroalkyl
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- -1 fluoro alkyl sultone Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000005935 Sulfuryl fluoride Substances 0.000 claims abstract description 17
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000004321 preservation Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 35
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims description 9
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 9
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 9
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 8
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 claims description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 4
- TTYVECQWCUJXCS-UHFFFAOYSA-N 4-fluoropyridine Chemical compound FC1=CC=NC=C1 TTYVECQWCUJXCS-UHFFFAOYSA-N 0.000 claims description 4
- FCSKOFQQCWLGMV-UHFFFAOYSA-N 5-{5-[2-chloro-4-(4,5-dihydro-1,3-oxazol-2-yl)phenoxy]pentyl}-3-methylisoxazole Chemical compound O1N=C(C)C=C1CCCCCOC1=CC=C(C=2OCCN=2)C=C1Cl FCSKOFQQCWLGMV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 claims description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- CELKOWQJPVJKIL-UHFFFAOYSA-N 3-fluoropyridine Chemical compound FC1=CC=CN=C1 CELKOWQJPVJKIL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000011267 electrode slurry Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 4
- 239000002000 Electrolyte additive Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- HFUSECPXGUISGB-UHFFFAOYSA-N benzoyl benzenecarboperoxoate;2-tert-butylperoxy-2-methylpropane Chemical compound CC(C)(C)OOC(C)(C)C.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 HFUSECPXGUISGB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000008053 sultones Chemical class 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ASGMFNBUXDJWJJ-JLCFBVMHSA-N (1R,3R)-3-[[3-bromo-1-[4-(5-methyl-1,3,4-thiadiazol-2-yl)phenyl]pyrazolo[3,4-d]pyrimidin-6-yl]amino]-N,1-dimethylcyclopentane-1-carboxamide Chemical compound BrC1=NN(C2=NC(=NC=C21)N[C@H]1C[C@@](CC1)(C(=O)NC)C)C1=CC=C(C=C1)C=1SC(=NN=1)C ASGMFNBUXDJWJJ-JLCFBVMHSA-N 0.000 description 1
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 1
- ABJSOROVZZKJGI-OCYUSGCXSA-N (1r,2r,4r)-2-(4-bromophenyl)-n-[(4-chlorophenyl)-(2-fluoropyridin-4-yl)methyl]-4-morpholin-4-ylcyclohexane-1-carboxamide Chemical compound C1=NC(F)=CC(C(NC(=O)[C@H]2[C@@H](C[C@@H](CC2)N2CCOCC2)C=2C=CC(Br)=CC=2)C=2C=CC(Cl)=CC=2)=C1 ABJSOROVZZKJGI-OCYUSGCXSA-N 0.000 description 1
- IUSARDYWEPUTPN-OZBXUNDUSA-N (2r)-n-[(2s,3r)-4-[[(4s)-6-(2,2-dimethylpropyl)spiro[3,4-dihydropyrano[2,3-b]pyridine-2,1'-cyclobutane]-4-yl]amino]-3-hydroxy-1-[3-(1,3-thiazol-2-yl)phenyl]butan-2-yl]-2-methoxypropanamide Chemical compound C([C@H](NC(=O)[C@@H](C)OC)[C@H](O)CN[C@@H]1C2=CC(CC(C)(C)C)=CN=C2OC2(CCC2)C1)C(C=1)=CC=CC=1C1=NC=CS1 IUSARDYWEPUTPN-OZBXUNDUSA-N 0.000 description 1
- YJLIKUSWRSEPSM-WGQQHEPDSA-N (2r,3r,4s,5r)-2-[6-amino-8-[(4-phenylphenyl)methylamino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1CNC1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O YJLIKUSWRSEPSM-WGQQHEPDSA-N 0.000 description 1
- VIJSPAIQWVPKQZ-BLECARSGSA-N (2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-acetamido-5-(diaminomethylideneamino)pentanoyl]amino]-4-methylpentanoyl]amino]-4,4-dimethylpentanoyl]amino]-4-methylpentanoyl]amino]propanoyl]amino]-5-(diaminomethylideneamino)pentanoic acid Chemical compound NC(=N)NCCC[C@@H](C(O)=O)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)(C)C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CCCNC(N)=N)NC(C)=O VIJSPAIQWVPKQZ-BLECARSGSA-N 0.000 description 1
- STBLNCCBQMHSRC-BATDWUPUSA-N (2s)-n-[(3s,4s)-5-acetyl-7-cyano-4-methyl-1-[(2-methylnaphthalen-1-yl)methyl]-2-oxo-3,4-dihydro-1,5-benzodiazepin-3-yl]-2-(methylamino)propanamide Chemical compound O=C1[C@@H](NC(=O)[C@H](C)NC)[C@H](C)N(C(C)=O)C2=CC(C#N)=CC=C2N1CC1=C(C)C=CC2=CC=CC=C12 STBLNCCBQMHSRC-BATDWUPUSA-N 0.000 description 1
- UDQTXCHQKHIQMH-KYGLGHNPSA-N (3ar,5s,6s,7r,7ar)-5-(difluoromethyl)-2-(ethylamino)-5,6,7,7a-tetrahydro-3ah-pyrano[3,2-d][1,3]thiazole-6,7-diol Chemical compound S1C(NCC)=N[C@H]2[C@@H]1O[C@H](C(F)F)[C@@H](O)[C@@H]2O UDQTXCHQKHIQMH-KYGLGHNPSA-N 0.000 description 1
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 1
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- OMBVEVHRIQULKW-DNQXCXABSA-M (3r,5r)-7-[3-(4-fluorophenyl)-8-oxo-7-phenyl-1-propan-2-yl-5,6-dihydro-4h-pyrrolo[2,3-c]azepin-2-yl]-3,5-dihydroxyheptanoate Chemical compound O=C1C=2N(C(C)C)C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C(C=3C=CC(F)=CC=3)C=2CCCN1C1=CC=CC=C1 OMBVEVHRIQULKW-DNQXCXABSA-M 0.000 description 1
- YQOLEILXOBUDMU-KRWDZBQOSA-N (4R)-5-[(6-bromo-3-methyl-2-pyrrolidin-1-ylquinoline-4-carbonyl)amino]-4-(2-chlorophenyl)pentanoic acid Chemical compound CC1=C(C2=C(C=CC(=C2)Br)N=C1N3CCCC3)C(=O)NC[C@H](CCC(=O)O)C4=CC=CC=C4Cl YQOLEILXOBUDMU-KRWDZBQOSA-N 0.000 description 1
- KQZLRWGGWXJPOS-NLFPWZOASA-N 1-[(1R)-1-(2,4-dichlorophenyl)ethyl]-6-[(4S,5R)-4-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]-5-methylcyclohexen-1-yl]pyrazolo[3,4-b]pyrazine-3-carbonitrile Chemical compound ClC1=C(C=CC(=C1)Cl)[C@@H](C)N1N=C(C=2C1=NC(=CN=2)C1=CC[C@@H]([C@@H](C1)C)N1[C@@H](CCC1)CO)C#N KQZLRWGGWXJPOS-NLFPWZOASA-N 0.000 description 1
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种氟代烷基磺酸内酯的制备方法,包括以下步骤:将烷基磺酸内酯和引发剂、缚酸剂、溶剂投入高压反应釜中,氮气氛置换保护;低温下,通入定量硫酰氟和氮气的混合气,密闭后先保温反应再升温反应;反应结束后,将釜液水洗、萃取、脱挥得到浓缩液,浓缩液经过减压精馏得到氟代烷基磺酸内酯。本发明制备方法简单,易于操作,原辅料简单易得,成本低,制备的氟代烷基磺酸内酯纯度高,能满足锂电池电解液应用。
Description
技术领域
本发明涉及电解液添加剂的合成方法,特别涉及氟代丙烷磺酸内酯的制备方法。
背景技术
含S类电解液添加剂可在锂离子电池正负极表面成膜,提高高电压及高镍体系下的高温循环及存储性能(ACS Appl.Energy Mater.2018,1,2582-2591);含F类物质如FEC等可在负极表面成有机无机复合的SEI膜,提升Si负极的循环稳定性(Energy StorageMaterials 2017,6,26-35)。
专利文献KR10-0908570报道了一种氟代磺酸内酯的合成路线,使用氯代试剂对磺酸内酯进行取代,再进行卤素置换反应。该反应第一步进行氯代,产物为氯代磺酸内酯,反应选择性较好,第二步进行卤素置换反应,该反应是个平衡反应,原料难以反应完全,导致该工艺路线总收率偏低,产品精制困难,残留的氯元素难以除去。
专利文献US20120172619A1报道了一种氟代磺酸内酯的合成方法,该方法使用含氟和溴的醇,使用亚硫酸钠对溴进行磺酸化反应,得到含端羟基的氟代磺酸,再进行关环反应得到产物。该路线的含有氟、溴的醇底物,原料不易获得成本较高,反应需要大量水或碱除去副产亚硫酸、溴化物。三废较多,后处理繁琐。
发明内容
本发明的目的在于提供一种经济、环保的氟代磺酸内酯的制备方法。
本发明的目的可以这样实现,设计一种氟代烷基磺酸内酯的制备方法,包括以下步骤:
将底物烷基磺酸内酯和引发剂、缚酸剂、溶剂投入高压反应釜中,氮气氛置换保护;低温下,通入定量硫酰氟和氮气的混合气,密闭后先保温反应再升温反应;反应结束后,将釜液水洗、萃取、脱挥得到浓缩液,浓缩液经过减压精馏得到氟代烷基磺酸内酯。
进一步地,烷基磺酸内酯、引发剂、缚酸剂、溶剂的投料摩尔比为1:(0.001~0.1):(0.5~5):(3~10)。
进一步地,反应先通入定量的硫酰氟气体,再通入定量氮气进行稀释和增压;通气时,温度为-20℃~30℃;硫酰氟投料量为原料烷基磺酸内酯摩尔量的1~5倍,硫酰氟和氮气投料摩尔比为(0.1~10):1;反应釜压力为0.1~10MPa。
进一步地,所述底物烷基磺酸内酯结构为化合物I、化合物II、化合物III、化合物IV的其中之一;
进一步地,所述的产物氟代烷基磺酸内酯,结构对应为化合物V、化合物VI、化合物VII、化合物VIII,
其中,a、b、c、d均为整数,且1≤a≤12、1≤b≤12、1≤c≤12、1≤d≤12,氟元素可以在同一个碳原子上,也可以在不同的碳原子上。
进一步地,所述的产物氟代烷基磺酸内酯结构,优选为:
化合物1化合物2化合物3化合物4化合物5化合物6化合物7化合物8化合物9化合物10化合物11化合物12化合物13化合物14化合物15化合物16化合物17化合物18化合物19化合物20化合物21化合物22化合物23
进一步地,引发剂为偶氮二异丁腈、偶氮二异庚腈、过氧化苯甲酰、过氧化苯甲酰叔丁酯、异丙苯过氧化氢、叔丁基过氧化氢、过氧化环己酮、过氧化甲乙酮、过硫酸钠、过硫酸铵、过氧化氢中的一种或两种。引发剂使用量为原料烷基磺酸内酯摩尔量的0.001~0.1倍。
进一步地,缚酸剂为三甲胺、三乙胺、四甲基乙二胺、四甲基-1,3-丙二胺、吡啶、2-甲基吡啶、4-甲基吡啶、2-氟代吡啶、4-氟代吡啶、N,N-二异丙基乙基胺、4-二甲氨基吡啶中的一种;缚酸剂使用量为原料烷基磺酸内酯的0.5~5倍。
进一步地,所述的溶剂为二氯甲烷、1,2-二氯乙烷、乙腈、丙腈、丁腈、二甲基亚砜、环丁砜中的一种。溶剂用量为原料烷基磺酸内酯摩尔量的3~10倍。
进一步地,加料温度为-20~30℃,加料后保温时间为1~8h;升温温度为0~180℃,升温后保温时间为1~8h。
本发明的制备方法简单,易于操作,原辅料简单易得,成本低,制备的氟代磺酸内酯收率高,纯度高,可以满足锂电池电解液添加剂的应用。
具体实施方式
以下结合实施例对本发明作进一步的描述。
一种氟代烷基磺酸内酯的制备方法,包括以下步骤:将烷基磺酸内酯和引发剂、缚酸剂、溶剂投入高压反应釜中,氮气氛置换保护;低温下,通入定量硫酰氟和氮气的混合气,密闭后先保温反应再升温反应;反应结束后,将釜液水洗、萃取、脱挥得到浓缩液,浓缩液经过减压精馏得到氟代烷基磺酸内酯。
烷基磺酸内酯、引发剂、缚酸剂的投料的摩尔比为1:(0.001~0.1):(0.5~5);溶剂用量为烷基磺酸内酯摩尔量的3~10倍;反应先通入定量的硫酰氟气体,再通入定量氮气进行稀释和增压;通气时,加料温度为-20℃~30℃;硫酰氟投料量为烷基磺酸内酯摩尔量的1~5倍,硫酰氟和氮气投料摩尔比为(0.1~10):1,反应釜压力为0.1~10MPa;加料后保温时间为1~8h;升温温度为0~180℃,升温后保温时间为1~8h。
所述底物烷基磺酸内酯结构为化合物I、化合物II、化合物III、化合物IV其中之一;结构通式对应为:
对应的产物氟代烷基磺酸内酯,结构对应为化合物V、化合物VI、化合物VII、化合物VIII,结构通式对应为:
其中,a、b、c、d为整数,且1≤a≤6,1≤b≤8,1≤c≤10,1≤d≤12;氟元素可以在同一个碳原子上,也可以在不同的碳原子上。
化合物I对应的产物为化合物V,化合物II对应的产物为化合物VI,化合物III对应的产物为化合物VII,化合物IV的产物对应为化合物VIII。
上述的产物氟代烷基磺酸内酯结构,优选为:
化合物1化合物2化合物3化合物4化合物5化合物6化合物7化合物8化合物9化合物10化合物11化合物12化合物13化合物14化合物15化合物16化合物17化合物18化合物19化合物20化合物21化合物22化合物23
以化合物III为底物可生成:化合物24:化合物25:化合物26:化合物27:化合物28:化合物29:化合物30:化合物31:化合物32:化合物33:化合物34:化合物35:化合物36:化合物37:化合物38:化合物39:
以化合物IV为底物可生成:化合物40:化合物41:化合物42:化合物43:化合物44:化合物45:化合物46:化合物47:化合物48:化合物49:化合物50:化合物51:化合物52:化合物53:化合物54:化合物55:化合物56:化合物57:化合物58:
引发剂为偶氮二异丁腈、偶氮二异庚腈、过氧化苯甲酰、过氧化苯甲酰叔丁酯、异丙苯过氧化氢、叔丁基过氧化氢、过氧化环己酮、过氧化甲乙酮、过硫酸钠、过硫酸铵、过氧化氢中的一种或两种。引发剂使用量为原料烷基磺酸内酯摩尔量的0.001~0.1倍。
缚酸剂为三甲胺、三乙胺、四甲基乙二胺、四甲基-1,3-丙二胺、吡啶、2-甲基吡啶、4-甲基吡啶、2-氟代吡啶、4-氟代吡啶、N,N-二异丙基乙基胺、4-二甲氨基吡啶中的一种;缚酸剂使用量为原料烷基磺酸内酯的0.5~5倍。
所述的溶剂为二氯甲烷、1,2-二氯乙烷、乙腈、丙腈、丁腈、二甲基亚砜、环丁砜中的一种;溶剂用量为原料烷基磺酸内酯摩尔量的3~10倍。
本发明克服上述现有技术存在的原辅料不易获得、反应和提纯精制操作繁琐、反应选择性差、总收率低、三废多等不足。本发明合成的氟代磺酸內酯可降低锂离子电池阻抗的同时,提升高镍、高电压及Si体系的高低温循环寿命及满充存储性能。
实施例1:
向1L高压反应釜(物料内压力在0.1-10MPa范围)中加入1,3-丙烷磺酸内酯(12.2g,0.1mol)、偶氮二异丁腈(16mg,0.0001mol)、三乙胺(5.06g,0.05mol)、乙腈(12.2g,0.3mol),氮气氛置换保护,将釜温降至-20℃,密闭后通入高纯硫酰氟(10.2g,0.1mol),流速为5ml/min,再通入高纯氮气(28g,1mol),将反应釜密封,高压反应釜压力为2.4Mpa,开启搅拌,保温时间为1小时,升温至0℃并保温反应8小时,反应结束后,泄压,将釜液过滤,减压回收溶剂,经水洗、萃取、脱挥得到浓缩液,将浓缩液进行减压精馏,得到3-氟-1,3-丙烷磺酸内酯(10.85g,0.0774mol),选择性83.6%,收率77.4%,纯度99.82%(GC),水分含量12ppm,酸度18ppm。
实施例2:
在30℃的环境下,向1L高压反应釜中加入1,3-丙烷磺酸内酯(12.2g,0.1mol)、偶氮二异丁腈(1.64g,0.01mol)、吡啶(39.6g,0.5mol)、环丁砜(36.05g,0.3mol),氮气氛置换保护,密闭后通入高纯硫酰氟(51.03g,0.5mol),流速为5ml/min,再通入高纯氮气(1.4g,0.05mol),将反应釜密封,高压反应釜压力为1.5Mpa,开启搅拌,保温时间为8小时,升温至180℃并保温反应8小时,反应结束后,泄压,将釜液过滤,减压回收溶剂,经水洗、萃取、脱挥得到浓缩液,将浓缩液进行减压精馏,得到全氟代1,3-丙烷磺酸内酯(19.833g,0.0862mol),选择性92.7%,收率86.2%,纯度99.93%(GC),水分含量10ppm,酸度15ppm。
实施例3:
向1L高压反应釜中加入1,4-丁烷磺酸内酯(13.6g,0.1mol)、过氧化苯甲酰(1.21g,0.005mol)、三乙胺(20.2g,0.2mol)、乙腈(41.06g,1mol),氮气氛置换保护,将釜温降至0℃,密闭后通入高纯硫酰氟(15.3g,0.15mol),流速为5ml/min,再通入高纯氮气(8.4g,0.35mol),将反应釜密封,高压反应釜压力为1.2Mpa,开启搅拌,保温时间为4小时,升温至80℃并保温反应1小时,反应结束后,泄压,将釜液过滤,减压回收溶剂,经水洗、萃取、脱挥得到浓缩液,将浓缩液进行减压精馏,得到3-氟-1,4-丁烷磺酸内酯(11.114g,0.0721mol),选择性78.3%,收率72.1%,纯度99.68%(GC),水分含量17ppm,酸度11ppm。
实施例4:
向1L高压反应釜中加入1,4-丁烷磺酸内酯(13.6g,0.1mol)、过硫酸铵(0.685g,0.003mol)、4-二甲氨基吡啶(48.868g,0.4mol)、环丁砜(120.17g,1mol),氮气氛置换保护,将釜温降至-20℃,密闭后通入高纯硫酰氟(40.8g,0.4mol),流速为5ml/min,再通入高纯氮气(11.2g,0.4mol),将反应釜密封,高压反应釜压力为2.0Mpa,开启搅拌,保温时间为1小时,升温至30℃并保温反应4小时,反应结束后,泄压,将釜液过滤,减压回收溶剂,经水洗、萃取、脱挥得到浓缩液,将浓缩液进行减压精馏,得到全氟代1,4-丁烷磺酸内酯(24.9g,0.0889mol),选择性93.5%,收率88.9%,纯度99.86%(GC),水分含量15ppm,酸度17ppm。
电池的制备
正极极片制备:
将正极活性材料钴酸锂(LiCoO2)或Li(NixCoyMn1-x-y)O2、导电剂Super P、聚偏二氟乙烯按照重量比96:2:2进行混合,加入N-甲基吡咯烷酮(NMP),在真空搅拌机作用下搅拌均匀,获得正极浆料,其中正极浆料的固含量为72wt%。将正极浆料均匀涂覆于正极集流体铝箔上,将涂有正极材料的铝箔在90℃下烘干,然后经过冷压、裁片、分切后,得到正极片。正极片为常规正极片。
负极极片制备:
将负极活性材料石墨或SiO、导电助剂Super P、羧甲基纤维素钠(CMC)、粘结剂丁苯橡胶(SBR)按照重量比95:2:1:2进行混合,加入去离子水,在真空搅拌机作用下获得负极浆料,其中负极浆料的固含量为54wt%;将负极浆料均匀涂覆在负极集流体铜箔上;将铜箔在80℃下烘干,然后经过冷压、裁片、分切后,在110℃的真空条件下干燥12h,得到负极片。负极片为常规负极片。
电解液的制备:
在干燥的氩气气氛手套箱中,将碳酸乙烯酯(EC)、碳酸丙烯酯(PC)、碳酸二乙酯(DEC)、丙酸丙酯(PP)、按照重量比为EC:PC:DEC:PP=20:20:40:20进行混合,接着加入添加剂,溶解并充分搅拌后加入锂盐LiPF6,混合均匀后获得电解液。其中,LiPF6的浓度为1.1mol/L。电解液中所用到的添加剂的具体种类以及含量下面的表1所示。在下面的表1中,添加剂的含量为基于电解液的总重量计算得到的重量百分数。
选用16μm厚的聚乙烯(PE)隔离膜。隔离膜为常规隔离膜。
电池组装:
将正极片、隔离膜、负极片按顺序叠好,使隔离膜处于正、负极片之间起到隔离的作用,然后卷绕、焊接极耳后,置于外包装箔铝塑膜中、干燥,注入上述制备好的电解液,经过真空封装、静置、化成、整形、容量测试等工序,获得锂离子电池。
性能测试
循环性能测试
将锂离子电池置于25℃,45℃恒温箱中,静置30分钟,使锂离子电池达到恒温。将达到恒温的锂离子电池以0.5C恒流充电至电压为4.45V(LCO)或4.2V(NCM811),然后恒压充电至电流为0.05C,接着以0.5C恒流放电至电压为3.0V,此为一个充放电循环。如此充电/放电,分别计算电池循环100次后的容量保持率。
存储性能的测试
将锂离子电池以0.5C恒流充电至4.45V(LCO)或4.2V(NCM811),恒压充电至电流为0.05C,至满充状态。测试满充状态下锂离子电池的厚度THK0。将满充状态电芯置于60℃高温炉中存储7天,测试电芯厚度THK1。根据下式计算锂离子电池的膨胀率:膨胀率=(THK1-THK0)/THK0
表1:不同体系条件下的性能测试
实施例1与对比例1对比可得知,FPS的加入可有效提升高电压LCO体系循环寿命及满充存储性能。
实施例2与对比例2对比可得知,FPS的加入可有效提升高Ni体系循环寿命及满充存储性能。
在上述实施例实例中,烷基磺酸内酯仅用了1,3-丙磺酸内酯(1,3-PS)、1,4-丁烷磺酸内酯,由于化合物I、化合物II、化合物III、化合物IV中其他的烷基磺酸内酯在本发明制备方法的反应中均能作为底物,具有相同功效,所以适用于本发明。
在上述实施例实例中,引发剂仅采用了偶氮二异丁腈、过氧化苯甲酰、过硫酸铵,由于偶氮二异庚腈、过氧化苯甲酰、过氧化苯甲酰叔丁酯、异丙苯过氧化氢、叔丁基过氧化氢、过氧化环己酮、过氧化甲乙酮、过硫酸钠、过氧化氢等化合物在本发明制备方法的反应中均能作为引发剂,具有相同功效,所以适用于本发明。
在上述实施例实例中,缚酸剂仅用了三乙胺、吡啶、4-二甲氨基吡啶,由于三甲胺、四甲基乙二胺、四甲基-1,3-丙二胺、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、2-氟代吡啶、3-氟代吡啶、4-氟代吡啶、N,N-二异丙基乙基胺等化合物在本发明制备方法的反应中均能作为缚酸剂,具有相同功效,所以适用于本发明。
在上述实施例实例中,溶剂仅用了乙腈、环丁砜,由于二氯甲烷、1,2-二氯乙烷、丙腈、丁腈、二甲基亚砜等化合物在本发明制备方法的反应中均能作为溶剂,具有相同功效,所以适用于本发明。
本发明的制备方法简单,易于操作,原辅料简单易得,成本低,制备的氟代磺酸内酯收率高,纯度高,可以满足锂电池电解液添加剂的应用。
Claims (10)
1.一种氟代烷基磺酸内酯的制备方法,其特征在于,包括以下步骤:
将烷基磺酸内酯和引发剂、缚酸剂、溶剂投入高压反应釜中,氮气氛置换保护;低温下,通入定量硫酰氟和氮气的混合气,密闭后先保温反应再升温反应;反应结束后,将釜液水洗、萃取、脱挥得到浓缩液,浓缩液经过减压精馏得到氟代烷基磺酸内酯。
2.根据权利要求1所述的氟代烷基磺酸内酯的制备方法,其特征在于:烷基磺酸内酯、引发剂、缚酸剂、溶剂的投料摩尔比为1:(0.001~0.1):(0.5~5):(3~10)。
3.根据权利要求1或2所述的氟代烷基磺酸内酯的制备方法,其特征在于:反应先通入定量的硫酰氟气体,再通入定量氮气进行稀释和增压;通气时,温度为-20℃~30℃;硫酰氟投料量为原料烷基磺酸内酯摩尔量的1~5倍,硫酰氟和氮气投料摩尔比为(0.1~10):1;反应釜压力为0.1~10MPa。
7.根据权利要求1所述的氟代磺酸内酯的制备方法,其特征在于:引发剂为偶氮二异丁腈、偶氮二异庚腈、过氧化苯甲酰、过氧化苯甲酰叔丁酯、异丙苯过氧化氢、叔丁基过氧化氢、过氧化环己酮、过氧化甲乙酮、过硫酸钠、过硫酸铵、过氧化氢中的一种或两种。
8.根据权利要求1所述的氟代烷基磺酸内酯的制备方法,其特征在于:缚酸剂为三甲胺、三乙胺、四甲基乙二胺、四甲基-1,3-丙二胺、吡啶、2-甲基吡啶、3-甲基吡啶、4-甲基吡啶、2-氟代吡啶、3-氟代吡啶、4-氟代吡啶、N,N- 二异丙基乙基胺、4-二甲氨基吡啶中的一种。
9.根据权利要求1所述的氟代烷基磺酸内酯的制备方法,其特征在于:所述的溶剂为二氯甲烷、1,2-二氯乙烷、乙腈、丙腈、丁腈、二甲基亚砜、环丁砜中的一种。
10.根据权利要求3所述的氟代烷基磺酸内酯的制备方法,其特征在于:加料温度为-20~30℃,加料后保温时间为1~8h;升温温度为0~180℃,升温后保温时间为1~8h。
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WO2024113667A1 (zh) * | 2022-11-29 | 2024-06-06 | 湖北亿纬动力有限公司 | 一种电解液和锂离子电池 |
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