CN117185934A - 一种双氟磺酰亚胺有机铵盐的制备方法 - Google Patents
一种双氟磺酰亚胺有机铵盐的制备方法 Download PDFInfo
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- CN117185934A CN117185934A CN202311136301.2A CN202311136301A CN117185934A CN 117185934 A CN117185934 A CN 117185934A CN 202311136301 A CN202311136301 A CN 202311136301A CN 117185934 A CN117185934 A CN 117185934A
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- Prior art keywords
- ammonium salt
- difluoro
- organic
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- 150000003863 ammonium salts Chemical class 0.000 title claims abstract description 40
- -1 difluoro sulfonimide Chemical compound 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000005935 Sulfuryl fluoride Substances 0.000 claims abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 11
- XPVRBHCXMWRJEY-UHFFFAOYSA-N difluoro(imino)-$l^{4}-sulfane Chemical compound FS(F)=N XPVRBHCXMWRJEY-UHFFFAOYSA-N 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-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
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000003682 fluorination reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000002341 toxic gas Substances 0.000 abstract description 3
- 229910052744 lithium Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 239000007795 chemical reaction product Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- KTQDYGVEEFGIIL-UHFFFAOYSA-N n-fluorosulfonylsulfamoyl fluoride Chemical class FS(=O)(=O)NS(F)(=O)=O KTQDYGVEEFGIIL-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000005270 trialkylamine group Chemical group 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- XXYVTWLMBUGXOK-UHFFFAOYSA-N [Na].FS(=N)F Chemical compound [Na].FS(=N)F XXYVTWLMBUGXOK-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005571 anion exchange chromatography Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical group 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/087—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms
- C01B21/093—Compounds containing nitrogen and non-metals and optionally metals containing one or more hydrogen atoms containing also one or more sulfur atoms
- C01B21/096—Amidosulfonic acid; Salts thereof
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Abstract
本发明公开了一种双氟磺酰亚胺有机铵盐的制备方法,属于化学合成技术领域,其特征在于,包括如下步骤:以硫酰氟和铵盐为反应原料,在非质子极性溶剂和有机碱性缚酸剂作用下,获得双氟磺酰亚胺有机铵盐;本发明提供了一种双氟磺酰亚胺有机盐的制备方法,反应步骤少、收率高,且规避了高温高压条件下的氟化反应步骤,不使用氟化氢、氟气等高危险性有毒气体物料,反应安全性高,易操作及设备要求不苛刻,适合工业化生产,所制备的双氟磺酰亚胺有机铵盐,可用于进一步通过金属交换反应制备双氟磺酰亚胺金属盐。
Description
技术领域
本发明涉及一种双氟磺酰亚胺有机铵盐的制备方法,属于化学合成技术领域。
背景技术
近年来,随着国家对新能源汽车产业的大力支持,促进新能源电动汽车(ElectricVehicle,EV),储能等产业的快速发展,随之对新能源关键核心技术的锂离子电池能量密度、循环寿命、安全性和环保等要求不断提高。为了确保新能源市场健康地发展,迫切地需要开发高性能、高安全性和环保,并又能以较合理成本生产锂离子电池产业技术。考虑到锂离子电池生产成本、电化学、安全和环保等综合性能,六氟磷酸锂(Lithiumhexafluorophosphate,LiPF6)是目前已经产业化的锂离子电池最被广泛采用的电解质,起到输送电荷作用,是决定电池性能优劣的关键要素之一,但LiPF6具有无法克服对热和化学稳定性、安全性和低温循环效率差等天然缺陷,比如60℃左右LiPF6就开始分解,这一过程如再遇微量水将进一步加快电解质的降解。伴随着LiPF6降解过程还会产生高腐蚀性的氟化氢(HF)气体,不仅会破坏电解质的化学结构而降低电解质浓度,同时还可能会引发电解液和电极化学结构的变化,破坏电池可逆循环工作条件,导致电池容量快速衰减,给实际生产和应用带来了巨大挑战和安全隐患。因此开发更安全、更高效、并能适用于低温和高温等苛刻条件下的优质电解质,将是改善各类离子电池的综合性能以及拓展它们应用范围最经济和最有效的途径。双氟磺酰亚胺锂(Lithium bisfluorosulfonylimide,LiFSI)及其它金属双氟磺酰亚胺盐的电导率、耐热稳定性、耐水稳定性、以及低温循环效率等综合电化学性能均比相应的六氟磷酸盐(MPF6)更优异。双氟磺酰亚胺碱金属盐已被国内外业内专家公认为是替代相应六氟磷酸盐电解质的下一代新型离子电池电解质,是当前最具有产业化前景的理想电解质,将成为新能源锂电企业的核心竞争力。
双氟磺酰亚胺锂及其它金属盐的制备首先是通过合成双氟磺酰亚胺;最初在实验室中,双氟磺酰亚胺的制备是通过氨基磺酸和五氯化磷为原料经多步反应合成得到(J.K.Ruff,et.al.,Inorg.Synth.1968,11,138;J.M.Shreeve,et al.,Inorg.Chem.1998,37,6295.),但该反应工艺路线复杂、中间产物种类多、产物提纯困难、致使生产难度大且生产成本高,制约其商业化使用。近年来,随着双氟磺酰亚胺生产技术的突破以及生产成本不断下降,双氟磺酰亚胺已具备产业化生产及大规模商业化应用的条件。目前已经产业化的双氟磺酰亚胺合成路线主要有两条:
(1).基于传统合成反应工艺的优化,通过改变原材料的选择,以氯磺酸和氨基磺酸或者氯磺酰异氰酸酯为原料先通过反应合成双氯磺酰亚胺(HClSI)中间产物,随后通过氟化反应并蒸馏得到双氟磺酰亚胺(HFSI)中间产物,最后通过锂化等三步反应得到LiFSI(例如:CN105731399B和CN106044728B等)。相比传统反应工艺,上述优化后的生产工艺减少了反应步骤和反应中间产物种类,生产难度和生产成本均比传统工艺有显著的降低,目前大多数化工企业如多氟多等公司都采用该反应工艺生产双氟磺酰亚胺锂。但该工艺所采用的氟化过程通常采用氟化氢或氟气等腐蚀性极强的原料在高温高压下反应,反应工艺过程风险大,并且对生产设备要求很高。由于需要经过三步反应合成才能得到双氟磺酰亚胺锂,反应步骤多、反应复杂、提纯困难、收率低、污染大、生产成本较高,导致其综合性价比很难满足锂离子电池市场井喷式发展对高质量和高产能生产双氟磺酰亚胺锂等盐的需求和期待。
(2).以硫酰氟和氨气为原料直接反应合成双氟磺酰亚胺(HFSI)中间产物,随后经过锂化两步反应合成生产双氟磺酰亚胺锂(例如:CN 111620315A)。尽管该合成反应工艺收率高、步骤少、但由于反应涉及到两种有毒气体同时参与反应,反应控制难度大,目前仅少部分企业正在开发采用该生产工艺,如操作不当极易引起安全事故等隐患。。
发明内容
本发明目的在于解决当前双氟磺酰亚胺盐生产过程中的部分缺陷,提供一种反应产物纯度好、收率高、安全、环保、及高效的双氟磺酰亚胺有机铵盐的全新制备方法。为实现上述目的,本发明采用的技术方案是:
一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于,包括如下步骤:以硫酰氟和铵盐为反应原料,在非质子极性溶剂和有机碱性缚酸剂作用下反应,获得双氟磺酰亚胺有机铵盐。
本发明的合成路线如下所示:
进一步的设置在于:
所述非质子性溶剂为:乙腈、丙酮、酯类如碳酸二甲酯、碳酸二乙酯、乙酸乙酯等、醚类如四氢呋喃、甲基叔丁基醚、乙二醇二甲醚等的任意一种,优选为乙腈。
所述硫酰氟、有机碱性缚酸剂与铵盐的摩尔比为1:1~10:0.2~1,优选为1:1.5:0.5。
所述有机碱性缚酸剂为:三甲胺、三乙胺、N,N-二异丙基乙胺、三正丙胺、三正丁胺、吡啶等的任意一种,优选为三乙胺。
所述铵盐选自以下任意一种铵盐:氟化铵,氯化铵,溴化铵,硫酸氢铵,碳酸氢铵,草酸氢铵。
所述反应温度为0~60℃,优选为10~30℃。
本发明制备的双氟磺酰亚胺有机铵盐,可不经提纯,直接用于进一步通过金属交换反应制备双氟磺酰亚胺金属盐,如用于制备双氟磺酰亚胺钠、双氟磺酰亚胺锂。
一种双氟磺酰亚胺钠的制备方法,其特征在于:以双氟磺酰亚胺有机铵盐为原料,在极性溶剂中,与碱性钠试剂反应,获得双氟磺酰亚胺钠。
所述的碱性钠试剂选自氢氧化钠、醋酸钠、醇钠如甲醇钠或乙醇钠等、碳酸钠、碳酸氢钠、氧化钠、硫酸钠等一种。
所述极性溶剂为:水、醇类如甲醇或乙醇等、腈类如乙腈或丙腈等、酮类如丙酮或2-丁酮等、酯类如碳酸二甲酯、碳酸二乙酯、乙酸乙酯等、醚类如四氢呋喃、甲基叔丁基醚、乙二醇二甲醚等的任意一种或按不同比例配成的混合溶剂,优选为乙醇或乙腈;所述有机碱性缚酸剂为:三甲胺、三乙胺、N,N-二异丙基乙胺、三丙胺、三丁胺、吡啶等的任意一种,优选为三乙胺或三正丁胺。
所述反应温度为-40~120℃;优选反应温度为0~60℃。
进一步地,反应获得的双氟磺酰亚胺钠反应液,除去不溶的无机物,减压蒸馏回收反应溶剂和三烷基胺缚酸剂,所得固体物经纯化为双氟磺酰亚胺钠白色固体。
一种双氟磺酰亚胺锂盐的制备方法,其特征在于:以双氟磺酰亚胺有机铵盐为原料,直接与碱性锂试剂反应,获得双氟磺酰亚胺锂。
所述双氟磺酰亚胺三烷基铵盐与碱性锂试剂反应的摩尔比为1:0.5~10,优选为1:1.0~1.2。
所述碱性锂试剂选自:醇锂(如甲醇锂、乙醇锂或叔丁醇基锂等)、有机羧酸锂(如甲酸锂、醋酸锂等)、氧化锂、氢氧化锂、碳酸锂等碱性锂试剂中的任意一种。
所述反应优选在溶剂存在下进行,所述溶剂为极性有机溶剂或水溶液,优选为:水、腈类如乙腈或丙腈等、醇类如甲醇或乙醇等,酮类如丙酮或2-丁酮等、酯类如碳酸二甲酯、碳酸二乙酯、乙酸乙酯等、醚类如四氢呋喃、甲基叔丁基醚、乙二醇二甲醚等的任意一种或混合溶剂,特别优选为乙醇或乙腈。
所述反应温度为-50~50℃,优选为-20~5℃。申请人通过实验发现:当反应温度较高时,会得到分解产物;而当反应在较低温度下进行,则可明显地减小水解产物,得到理想的产物收率,因此,当反应温度控制在-20~5℃时,反应的产率和纯度均较高。
反应完成后,过滤除去反应生成的不溶无机物,所得反应液经减压蒸馏回收反应溶剂和三烷基胺缚酸剂,得到白色固体双氟磺酰亚胺锂反产应物。
与现有技术相比,本发明的有益效果主要体现在:
1、本发明提供了一种双氟磺酰亚胺有机盐的制备方法,反应步骤少、安全、环保、易操作、产品纯度好、收率高等优点。
2、本发明规避了高温高压条件下的氟化反应步骤,不使用氟化氢、氟气等高危险性有毒气体物料,反应安全性高,易操作及设备要求不苛刻,适合工业化生产等优点。
3、本发明原料便宜和易得,且主反应原料铵盐可通过简单的粉末固体或配成准确浓度的溶液方式加到反应体系中,避免多种有毒气体原料的同时使用,有效的降低反应控制难度以及反应风险。
4、本发明制备的双氟磺酰亚胺三乙铵盐,可进一步用于制备双氟磺酰亚胺锂盐、双氟磺酰亚胺钠盐、双氟磺酰亚胺钾盐等,上述产物是制备锂离子电池、钠离子电池、钾离子电池的重要原料,因此,具有极高的工业应用前景。
下面结合具体实施例对本发明进行进一步描述,但本发明的保护范围并不仅限于此。
附图说明
图1为本发明实施例1制备的双氟磺酰亚胺三乙铵盐的1HNMR谱图。
图2为本发明实施例1制备的双氟磺酰亚胺三乙铵盐的19FNMR谱图。
图3为本发明实施例7制备的双氟磺酰亚胺锂盐的19FNMR谱图。
图4为本发明实施例8制备的双氟磺酰亚胺钠盐的19FNMR谱图。
具体实施方式
实施例1:制备双氟磺酰亚胺三乙铵盐
氮气气氛下,250mL高压反应釜中,加入氟化铵9.3克,控温至10℃,依次泵入三乙胺75.5克,乙腈60.0克,搅拌0.5小时,控温10℃缓慢通入硫酰氟气体51.0克,连续保温10℃,4小时,结束反应。反应液减压蒸馏回收反应溶剂,浓缩液水洗并干燥后得到65.0克双氟磺酰亚胺三乙铵盐,收率95%(1HNMR谱图如图1所示和19FNMR谱图如图2所示)。
产物确认:
反应产物经LC/MS检测表明,负离子分子量(m/e)为180,与双氟磺酰亚胺负离子的化学结构(IV)一致,
反应产物的1HNMR谱图如图1所示,与双氟磺酰亚胺三乙铵盐(II)(R=CH2CH3)的化学结构一致。
实施例2
制备方法的实验条件同实施例1,区别在于:调整铵盐的选择与用量,并检测其对产物收率的影响,如表1所示。
表1、不同铵盐的选择与用量对反应收率的影响
序号 | 铵盐 | 用量 | 收率 |
实施例2-1 | 氯化铵 | 13.4克(0.25摩尔) | 92% |
实施例2-2 | 溴化铵 | 24.5克(0.25摩尔) | 95% |
实施例2-3 | 硫酸氢铵 | 28.8克(0.25摩尔) | 95% |
实施例2-4 | 碳酸氢铵 | 19.8克(0.25摩尔) | 93% |
实施例2-5 | 草酸氢铵 | 26.8克(0.25摩尔) | 90% |
实施例3
制备方法的实验条件同实施例1,区别在于:调整非质子极性溶剂,并检测其对产物收率的影响,如表2所示。
表2、不同非质子极性溶剂对反应收率的影响
序号 | 非质子极性溶剂 | 收率 |
实施例3-1 | 乙腈 | 95% |
实施例3-2 | 丙酮 | 70% |
实施例3-3 | 碳酸二乙酯 | 80% |
实施例3-4 | 乙酸乙酯 | 55% |
如表2所示:由于反应物和产物都是强极性离子型化合物,故极性溶剂有利于反应进行完全,并获得相应较高的反应产率,很明显乙腈是优选的反应溶剂。
实施例4
制备方法的实验条件同实施例1,区别在于:调整有机碱性缚酸剂的化学结构,并检测其对产物收率的影响,如表3所示。
表3、不同有机碱性缚酸剂对反应收率的影响
序号 | 有机碱性缚酸剂 | 收率 |
实施例4-1 | 三甲胺 | 90% |
实施例4-2 | 三乙胺 | 95% |
实施例4-3 | N,N-二异丙基乙胺 | 92% |
实施例4-4 | 三丙胺 | 85% |
实施例4-5 | 三正丁胺 | 65% |
。
如表3所示:选择不同化学结构的有机碱性缚酸剂,产物收率随着缚酸剂中烷基变大而逐渐降低,可能与缚酸剂吸附反应所生成的氢氟酸副产物的能力有关。很明显,三乙胺是优选的有机碱性缚酸剂。
实施例5
制备方法的实验条件同实施例1,区别在于:调整硫酰氟、有机碱性缚酸剂与铵盐的摩尔比,并检测其对反应纯度的影响,如表4所示。
表4、不同反应物料比对反应收率的影响
序号 | 硫酰氟、有机碱性缚酸剂与铵盐(摩尔比) | 收率 |
实施例5-1 | 1:1:0.5 | 81% |
实施例5-2 | 1:1:1 | 80% |
实施例5-3 | 1:1.5:0.5 | 95% |
实施例5-4 | 1:1.5:0.3 | 60% |
实施例5-5 | 1:1.5:1 | 94% |
实施例5-6 | 1:2:0.5 | 94.5% |
。
如表4所示:有机碱性缚酸剂不仅参与吸附反应所生成的氢氟酸副产物,同时也参与反应产物的成盐过程,因此选择不同的反应物料比,对反应产物的收率有较大影响,一般而言,硫酰氟、有机碱性缚酸剂与铵盐的摩尔比控制在1:1~10:0.2~1,最佳实施例为:硫酰氟、有机碱性缚酸剂与铵盐的摩尔比为1:1.5:0.5。
实施例6:
制备方法的实验条件同实施例1,区别在于:调整反应温度,并检测其对反应收率的影响,如表5所示。
表5、不同反应温度对反应收率的影响
序号 | 反应温度 | 保温时间 | 收率 |
实施例6-1 | 0℃ | 4h | 90% |
实施例6-2 | 10℃ | 4h | 95% |
实施例6-3 | 30℃ | 4h | 90% |
实施例6-4 | 60℃ | 4h | 75% |
。
如表5所示:反应温度为0℃时,反应收率为90%。当反应温度升高到10℃时,反应收率达到95%,继续升高反应温度,反应产率不但没有明显地提高,反而逐渐降低,推测在较高反应温度下,生成副产物的速度也许增加得更快。
实施例7:制备双氟磺酰亚胺锂
在氮气气氛下和250mL三口反应瓶中,加入70.5克双氟磺酰亚胺三乙铵盐和141克乙腈,待反应体系降温到-30℃,然后加入甲醇锂9.49克,搅拌反应约3个小时,然后升温到室温,用真空泵使体系真空度达到约0.06Pa继续反应,等到反应完成后,过滤除去不溶的无机副产物,反应液在50℃下减压蒸馏除去反应过程中所生成的三烷基胺以及水,回收反应溶剂,得双氟磺酰亚胺锂白色固体42.1克,收率90.0%。
产物确认:
反应产物经LC/MS测试表明其负离子分子量(m/e)为180,与双氟磺酰亚胺负离子的化学结构(II)一致,
反应产物进一步经负离子色谱测试,所得双氟磺酰亚胺锂的离子峰保留时间和峰型均与标准的双氟磺酰亚胺锂标准样品一致。所得双氟磺酰亚胺锂反应产物的19FNMR谱图如图3所示,只含一个51.90ppm氟共振吸收峰,与双氟磺酰亚胺锂盐的化学结构一致。
反应产物经原子吸收光谱测试得到如下结果,证明反应产物为锂盐
序号 | 检测项目(Test Items) | 测试方法(Methods) | 结果(Results) |
1 | 锂(Li,ppm) | WI-24-19 | 148725 |
2 | 钠(Na,ppm) | WI-24-16 | 11.59 |
3 | 钙(Ca,ppm) | WI-24-16 | 1.33 |
4 | 钾(K,ppm) | WI-24-16 | 1.97 |
5 | 铅(Pb,ppm) | WI-24-16 | 0.15 |
6 | 铁(Fe,ppm) | WI-24-16 | 0.66 |
7 | 铜(Cu,ppm) | WI-24-16 | 0.21 |
8 | 锌(Zn,ppm) | WI-24-16 | 1.98 |
9 | 镁(Mg,ppm) | WI-24-16 | 0.12 |
10 | 铬(Cr,ppm) | WI-24-16 | 0.01 |
11 | 镍(Ni,ppm) | WI-24-16 | ND |
12 | 锰(Mn,ppm) | WI-24-16 | 0.02 |
13 | 钡(Ba,ppm) | WI-24-16 | ND |
14 | 镉(Cd,ppm) | WI-24-16 | 0.01 |
15 | 铝(Al,ppm) | WI-24-16 | 0.19 |
。
实施例8:制备双氟磺酰亚胺钠
氮气气氛下,250mL三口反应瓶中,加入56.4克双氟磺酰亚胺三乙铵盐和56.4克乙腈,然后加入碳酸钠10.6克,搅拌并加热至50℃,直到无二氧化碳气体生成为止。过滤除去不溶的无机物,反应液在50℃下减压蒸馏回收反应溶剂,得白色固体39.8克,收率98.0%
产物确认:
反应产物经LC/MS测试表明负离子分子量(m/e)为180,与双氟磺酰亚胺负离子的化学结构(II)一致,
反应产物进一步经负离子色谱测试,所得产物的离子峰的保留时间和峰型均与标准的双氟磺酰亚胺盐一致。反应产物的19FNMR谱图如图4所示,只含一个51.90ppm氟共振吸收峰,与双氟磺酰亚胺钠的化学结构一致。
反应物经原子吸收光谱测试得到如下结果,证明反应产物为钠盐
。
Claims (10)
1.一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于,包括如下步骤:以硫酰氟和铵盐为反应原料,在非质子极性溶剂和有机碱性缚酸剂作用下反应,获得双氟磺酰亚胺有机铵盐。
2.根据权利要求1所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述非质子极性溶剂选自以下任意一种:乙腈,丙酮,碳酸二甲酯,碳酸二乙酯,乙酸乙酯,四氢呋喃、甲基叔丁基醚或乙二醇二甲醚。
3.根据权利要求2所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述非质子极性溶剂为乙腈。
4.根据权利要求1所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述铵盐选自以下任意一种铵盐:氟化铵,氯化铵,溴化铵,硫酸氢铵,碳酸氢铵,草酸氢铵。
5.根据权利要求1所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述有机碱性缚酸剂选自:三甲胺、三乙胺、N,N-二异丙基乙胺、三正丙胺、三正丁胺、吡啶的任意一种。
6.根据权利要求5所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述有机碱性缚酸剂为三乙胺或三正丁胺。
7.根据权利要求1所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述硫酰氟、有机碱性缚酸剂与铵盐的摩尔比为1:1~10:0.2~1。
8.根据权利要求7所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述硫酰氟、有机碱性缚酸剂与铵盐优选的摩尔比为1:1.5:0.5。
9.根据权利要求1所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述反应温度为0~60℃。
10.根据权利要求9所述的一种双氟磺酰亚胺有机铵盐的制备方法,其特征在于:所述反应温度为10~30℃。
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