CN106800280A - It is a kind of double（Fluorosulfonyl）The preparation method of inferior amine salt - Google Patents
It is a kind of double（Fluorosulfonyl）The preparation method of inferior amine salt Download PDFInfo
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- CN106800280A CN106800280A CN201611245365.6A CN201611245365A CN106800280A CN 106800280 A CN106800280 A CN 106800280A CN 201611245365 A CN201611245365 A CN 201611245365A CN 106800280 A CN106800280 A CN 106800280A
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- Prior art keywords
- double
- fluorosulfonyl
- solvent
- inferior amine
- preparation
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- -1 amine salt Chemical class 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims abstract description 25
- 150000002466 imines Chemical class 0.000 claims abstract description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000004807 desolvation Methods 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002576 ketones Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 claims description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 3
- 229940011051 isopropyl acetate Drugs 0.000 claims description 3
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000005049 silicon tetrachloride Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940117958 vinyl acetate Drugs 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 17
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 17
- 238000001556 precipitation Methods 0.000 description 14
- 230000006837 decompression Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 0.000 description 7
- 239000011698 potassium fluoride Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 241000255964 Pieridae Species 0.000 description 4
- 229910003910 SiCl4 Inorganic materials 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 4
- 229910010941 LiFSI Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910003676 SiBr4 Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- SHOBVAQMOOFCMB-UHFFFAOYSA-N [K].[SH2]=N.[F] Chemical compound [K].[SH2]=N.[F] SHOBVAQMOOFCMB-UHFFFAOYSA-N 0.000 description 2
- DEWWEJYRYIORMG-UHFFFAOYSA-N [Na].[SH2]=N.[F] Chemical compound [Na].[SH2]=N.[F] DEWWEJYRYIORMG-UHFFFAOYSA-N 0.000 description 2
- PWORGPNOUCYYCW-UHFFFAOYSA-N [SH2]=N.[Cl] Chemical compound [SH2]=N.[Cl] PWORGPNOUCYYCW-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004816 dichlorobenzenes Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- IDGCBXSROJHVOG-UHFFFAOYSA-N [Li].[SH2]=N.[F] Chemical compound [Li].[SH2]=N.[F] IDGCBXSROJHVOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- JWZCKIBZGMIRSW-UHFFFAOYSA-N lead lithium Chemical compound [Li].[Pb] JWZCKIBZGMIRSW-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
It is more particularly to a kind of double the present invention relates to the field of chemical synthesis of fluorine material（Fluorosulfonyl）The preparation method of inferior amine salt.The present invention provides a kind of double（Fluorosulfonyl）The preparation method of inferior amine salt, comprises the following steps：It is double（Fluorosulfonyl）Imines enters line replacement reaction in the presence of a solvent with alkali metal fluoride MF, silicon tetrahalogen, prepares double（Fluorosulfonyl）Inferior amine salt.It is provided by the present invention double（Fluorosulfonyl）The preparation method of inferior amine salt avoids using substantial amounts of water in process of production, alleviates environmental protection pressure, while Disassembling Products Quality Down caused by avoiding introducing moisture, is more suitable for industrialized production.
Description
Technical field
The present invention relates to the field of chemical synthesis of fluorine material, more particularly to a kind of system of double (fluorosulfonyl) inferior amine salts
Preparation Method.
Background technology
Double (fluorosulfonyl) inferior amine salts, the crucial additive material of matter are electrolysed as secondary cell, with industry very high
Change application value.Double (fluorosulfonyl) inferior amine salts meet water or wet environment is heated and can cause to go bad, and decompose and produce hydrogen fluoride；Electrolysis
Solvent in liquid can be polymerized under hydrogen fluoride catalyzed effect, so as to cause electrolyte viscosity to increase, electrical conductivity reduction.Separately
Outward, influence of the hydrogen fluoride to battery performance is essentially consisted in：The hydrogen fluoride contained in electrolyte is in lithium battery first charge-discharge process
In, following electrochemical reducting reaction can occur on Carbon anode：
HF+e-+Li+→LiF+1/2H2
It is a kind of thermodynamically stable component to react the LiF for producing, and it is poor to lead lithium ability in the battery, Carbon anode surface
LiF contents increase in SEI membrane components, can cause the increase of electrode and electrolyte interface impedance, so as to increase the internal resistance of cell.In addition
Hydrogen fluoride in electrolyte can and electrode surface on SEI films react, generate water, and the water for producing further with it is double
(fluorosulfonyl) imines reactant salt generates hydrogen fluoride, and the process is constantly circulated, and causes battery specific capacity, cycle efficieny etc. constantly to subtract
It is small, until whole battery is destroyed.
Patent CN103391896A discloses a kind of preparation method of two (fluorosulfonyl) imines sodium salts, i.e., by two (fluorine sulphurs
Acyl group) imines ammonium salt butyl acetate solution and sodium hydrate aqueous solution reduced-pressure backflow under the conditions of react, reaction solution is after dividing liquid
Repeatedly distilled afterwards with n-butyl acetate extraction, be recrystallized to give product.The method is cumbersome, will to appointed condition in industrial production
Ask very high；In addition, reaction is carried out under Aquo System, a large amount of industrial wastewaters are on the one hand produced to pollute, (fluorine sulphonyl double in addition
Base) inferior amine salt to water sensitive, need to pass through complicated program by moisture removal, and otherwise product is easily decomposed, and causes purity to decline.
Patent US2004097757 discloses a kind of pair of preparation method of fluorine sulfimide sylvite, that is, use KF and double chlorine sulphurs
Acid imide reacts in nitromethane solvent and is made.Yet with used 5 times amount KF, not only increased industrial production into
This, and react remaining KF and be blended in KFSI products, there is no effective ways to remove it totally, the KF of residual is to cell performance
It is unfavorable to influence.
Patent CN103935970A discloses a kind of pair of preparation method of fluorine sulfimide lithium (LiFSI), first by 80mol
Hydrogen fluoride carries out fluorination reaction with double chlorine sulfimide (HClSI) of 6mol, and the hydrogen fluoride for obtaining double fluorine sulfimide (HFSI) is molten
Liquid.Ion-exchange reactions is carried out to addition 6mol lithium fluoride in the solution again, double fluorine sulphurs are obtained through filtering and vacuum and heating drying
Imide li.Reaction is as follows：
HCISI+HF→HFSI+HCI
Substantial amounts of hydrogen fluoride being used in the method, LiF is consumed because there is following reaction, reduce feed stock conversion.
HF+LiF→LiHF2
In addition, hydrogen fluoride can form the complex compound of stabilization under Hyarogen-bonding with LiFSI, it is difficult to take off through filtering or distillation
Except pure LiFSI products are obtained, the final performance to electrolyte quality even battery has a negative impact.
Therefore, the method for this area double (fluorosulfonyl) inferior amine salts in the urgent need to prepared by one kind, to solve production mistake
Disassembling Products Quality Down caused by wastewater flow rate causes greatly environmental protection pressure and moisture to introduce in journey, and reaction carries out not thorough, product
Thing purification process is complicated and be unfavorable for industrial production, and hydrogen fluoride remains exceeded problem in product；Make double (fluorosulfonyls)
Inferior amine salt quality meets the use requirement of battery electrolyte.
The content of the invention
The shortcoming of prior art in view of the above, it is an object of the invention to provide a kind of double (fluorosulfonyl) inferior amine salts
Preparation method, for solving the problems of the prior art.
In order to achieve the above objects and other related objects, the present invention provides a kind of preparation side of double (fluorosulfonyl) inferior amine salts
Method, comprises the following steps：
It is anti-that double (fluorosulfonyl) imines enter line replacement in the presence of a solvent with alkali metal fluoride MF, silicon tetrahalogen
Should, double (fluorosulfonyl) inferior amine salts are prepared, the structural formula of described double (fluorosulfonyl) inferior amine salts is shown in formula I：
Wherein, M is selected from Li, Na or K.
In some implementation methods of the invention, double (fluorosulfonyl) imines are with the mol ratio of alkali metal fluoride MF
1~1.1：1.
In some implementation methods of the invention, the silicon tetrahalogen is 0.25~2 with the mol ratio of alkali metal fluoride MF：
1。
In some implementation methods of the invention, the mol ratio of the silicon tetrahalogen and alkali metal fluoride MF for 0.3~
0.8：1.
In some implementation methods of the invention, the silicon tetrahalogen is selected from the one kind or many in silicon tetrachloride, silicon bromide
The combination planted.
In some implementation methods of the invention, the reaction temperature of the reaction is 0~50 DEG C.
In some implementation methods of the invention, the reaction temperature is 15~40 DEG C.
In some implementation methods of the invention, the reaction is carried out under conditions of gas shield.
In some implementation methods of the invention, the gas that the gas shield is used is selected from nitrogen, inert gas
One or more of combination.
In some implementation methods of the invention, the solvent is organic solvent.
In some implementation methods of the invention, the organic solvent is selected from ketones solvent, esters solvent or ether solvent
One or more of combination.
In some implementation methods of the invention, the ketones solvent is selected from 1-METHYLPYRROLIDONE, acetone, Methylethyl
One or more in ketone, butanone, methyl tertbutyl ketone, 4-methyl-2 pentanone of combination.
In some implementation methods of the invention, the esters solvent is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate
Ester, ethylene carbonate, propene carbonate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, acetic acid
One or more in isobutyl ester, vinylacetate of combination.
In some implementation methods of the invention, the ether solvent be selected from ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether,
One or more in tetrahydrofuran, methyltetrahydrofuran, cyclopentyl methyl ether, dioxane, dioxolane, glycol dimethyl ether
Combination.
In some implementation methods of the invention, double (fluorosulfonyl) imines are carried out with alkali metal fluoride MF, silicon tetrahalogen
Replacing the specific method for reacting is：To double (fluorosulfonyl) imines are added in the solvent containing alkali metal fluoride MF, add
Silicon tetrahalogen.
In some implementation methods of the invention, after displacement reaction terminates, desolvation, separation of solid and liquid, solid phase are double (fluorine
Sulfonyl) inferior amine salt.
In some implementation methods of the invention, the specific method of desolvation is distillation.
In some implementation methods of the invention, the vapo(u)rizing temperature is 25-100 DEG C.
In some implementation methods of the invention, the vapo(u)rizing temperature is 30-60 DEG C.
It is also bad molten to being added in reaction system during the desolvation in some implementation methods of the invention
Agent.
In some implementation methods of the invention, the poor solvent is 2~10 with the mass ratio of double (fluorosulfonyl) imines：
1；
In some implementation methods of the invention, the poor solvent is selected from saturated hydrocarbons solvent, the halogenated hydrocarbon of low polarity
One or more in solvent, aromatic hydrocarbon solvent and Polyhalogenated aromatic hydrocarbons solvent of combination；
In some implementation methods of the invention, the poor solvent is selected from n-hexane, hexamethylene, dichloromethane, two chloroethenes
Alkane, toluene, dimethylbenzene, chlorobenzene, one or more in dichloro-benzenes of combination.
The preparation method of double (fluorosulfonyl) inferior amine salts provided by the present invention is more environmentally-friendly, and the double (fluorine for preparing
Sulfonyl) inferior amine salt product quality stabilization, meet the use requirement of battery electrolyte, therefore the method is more suitable for industrial metaplasia
Produce.
Specific embodiment
Inventor is fluorinated with double (fluorosulfonyl) imines as raw material by double (fluorosulfonyl) imines and alkali metal
The displacement reaction of thing MF, silicon tetrahalogen, has prepared double (fluorosulfonyl) inferior amine salts, so as to provide a kind of environmental protection, product
The preparation method of quality double (fluorosulfonyl) inferior amine salts high, completes the present invention on this basis.
One aspect of the present invention provides a kind of preparation method of double (fluorosulfonyl) inferior amine salts, comprises the following steps：
It is anti-that double (fluorosulfonyl) imines enter line replacement in the presence of a solvent with alkali metal fluoride MF, silicon tetrahalogen
Should, double (fluorosulfonyl) inferior amine salts are prepared, the structural formula of described double (fluorosulfonyl) inferior amine salts is shown in formula I：
The specific reaction equation of the preparation method of double (fluorosulfonyl) inferior amine salts provided by the present invention is as follows：
In the preparation method of double (fluorosulfonyl) inferior amine salts provided by the present invention, the alkali metal fluoride MF is often referred to
The compound that alkali metal (for example, Li, Na, K etc.) is formed with F, in above-mentioned chemical structural formula, M can be selected from Li, Na or K, institute
State the combination that alkali metal fluoride MF can be one or more including but not limited in LiF, NaF or KF etc.；Double (fluorine
Sulfonyl) inferior amine salt generally can be described double (fluorosulfonyl) imines alkali metal salt, described double (fluorosulfonyl) inferior amine salts
Can be including but not limited to double (fluorosulfonyl) imines lithium salts, double (fluorosulfonyl) imines sodium salts or double (fluorosulfonyl) imines
One or more in sylvite etc. of combination.The consumption of described double (fluorosulfonyl) imines is commonly angled relative to alkali metal fluoride MF
It is equivalent (in molar ratio) or slight excess of, those skilled in the art can suitably adjust double (fluorosulfonyl) imines and alkali metal
The mol ratio of fluoride MF, for example, double (fluorosulfonyl) imines can be 1~1.1 with the mol ratio of alkali metal fluoride MF：1.
In the preparation method of double (fluorosulfonyl) inferior amine salts provided by the present invention, the silicon tetrahalogen can be removed
Silicon tetrahalogen beyond ocratation, for example, the silicon tetrahalogen can be including but not limited to silicon tetrachloride, silicon bromide etc.
In one or more of combination.The silicon tetrahalogen is usually not less than 0.25 with the mol ratio of alkali metal fluoride MF：1, this
Art personnel can suitably adjust the mol ratio of double (fluorosulfonyl) imines and alkali metal fluoride MF, for example, four halogen
SiClx can be 0.25~2 with the mol ratio of alkali metal fluoride MF：1, can also be 0.3~0.8：1.
In the preparation method of double (fluorosulfonyl) inferior amine salts provided by the present invention, those skilled in the art can be according to reaction
The response situation adjustment reaction temperature of system, to ensure the smooth of reaction and/or smoothly carry out.For example, the reaction is anti-
It can be 0~50 DEG C to answer temperature, or 15~40 DEG C.Those skilled in the art can control to react according to real reaction situation
Process, for example, reaction process can be judged by monitoring the response situation of raw material, then for example, the reaction time can be 10~30
Hour.
In the preparation method of double (fluorosulfonyl) inferior amine salts provided by the present invention, the reaction can be in gas shield
Under the conditions of carry out, the gas that the gas shield is used generally can be difficult with reaction system main component (for example,
Double (fluorosulfonyl) imines and alkali metal fluoride MF, silicon tetrahalogen etc.) gas that chemically reacts, for example, the gas
The used gas of protection can be the combination of one or more including but not limited in nitrogen, inert gas etc., described lazy
Property gas can be the combination of one or more including but not limited in helium, neon, argon gas, Krypton, xenon etc..
In the preparation method of double (fluorosulfonyl) inferior amine salts provided by the present invention, the solvent can be organic solvent,
The organic solvent is usually for reaction raw materials (for example, double (fluorosulfonyl) imines and alkali metal fluoride MF, silicon tetrahalogen
Deng) there is preferable deliquescent solvent, the organic solvent can be including but not limited to ketones solvent, esters solvent or ethers
One or more in solvent etc. of combination.The ketones solvent can be including but not limited to 1-METHYLPYRROLIDONE, acetone,
One or more in methyl ethyl ketone, butanone, methyl tertbutyl ketone, 4-methyl-2 pentanone etc. of combination；The esters solvent
Can be including but not limited to dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propene carbonate, acetic acid
One kind in methyl esters, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, vinylacetate etc. or
Various combinations；The ether solvent can be including but not limited to ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, tetrahydrochysene furan
Mutter, one or more in methyltetrahydrofuran, cyclopentyl methyl ether, dioxane, dioxolane, glycol dimethyl ether etc. of group
Close.Those skilled in the art can (for example, the solubility etc. of solvent for reaction raw materials) adjustment solvent as needed usage amount,
For example, the usage amount of solvent can be 1-10 times of double fluorine sulfimide quality.
In the preparation method of double (fluorosulfonyl) inferior amine salt provided by the present invention, double (fluorosulfonyl) imines and alkali metal
Fluoride MF, silicon tetrahalogen enter line replacement reaction specific method be：It is double to being added in the solvent containing alkali metal fluoride MF
(fluorosulfonyl) imines, adds silicon tetrahalogen.
In the preparation method of double (fluorosulfonyl) inferior amine salts provided by the present invention, after displacement reaction terminates, desolvation
Separated out wholly or in part to solid, separation of solid and liquid, solid phase is double (fluorosulfonyl) inferior amine salts.The method of the desolvation does not have
Have specifically limited, as long as not producing limitation to goal of the invention of the invention, for example, the specific method of desolvation can be right
Reaction system is heated, and more specifically can be the modes such as distillation, and the heating-up temperature can be 25-100 DEG C, or
30-60℃；Again for example, during desolvation, can be by the way of decompression；Again for example, in the process of desolvation
In, can also be to adding poor solvent, the poor solvent to be often referred to for target product (for example, double (fluorine sulphurs in reaction system
Acyl group) inferior amine salt) the relatively low solvent of solubility, the poor solvent can be including but not limited to saturated hydrocarbons solvent, halo
One or more in varsol, aromatic hydrocarbon solvent and Polyhalogenated aromatic hydrocarbons solvent etc. of combination, the poor solvent leads to
It is often the solvent of low polarity.In some specific embodiments of the invention, the poor solvent can be including but not limited to just
One or more in hexane, hexamethylene, dichloromethane, dichloroethanes, toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes etc. of combination.
Those skilled in the art can as the case may be (such as amount of precipitation of solid etc. during species, the desolvation of poor solvent)
The consumption of poor solvent is adjusted, for example, the poor solvent can be 2~10 with the mass ratio of double (fluorosulfonyl) imines：1.
In the preparation method of double (fluorosulfonyl) inferior amine salts provided by the present invention, for the reaction that reaction system is generated
Tail gas (for example, SiF4, HCl, HBr etc.) can be absorbed with conventional tail gas absorption method, and those skilled in the art can be according to anti-
The species of tail gas is answered to select suitable exhaust gas treating method, it is, for example possible to use alkali absorbs to tail gas.
Another aspect of the present invention provides double (the fluorine sulphonyl obtained by the preparation method preparation of described double (fluorosulfonyl) inferior amine salts
Base) inferior amine salt.
The preparation method of double (fluorosulfonyl) inferior amine salts provided by the present invention is avoided in process of production using substantial amounts of
Water, alleviates environmental protection pressure, while Disassembling Products Quality Down caused by avoiding introducing moisture；Additionally, silicon tetrahalogen makes
Carried out thoroughly with being not only able to make reaction to balance forward direction, additionally it is possible in time except the hydrogen fluoride that dereaction is produced, prevent hydrogen fluoride and
The complexing of double fluorine sulfimide salts, so that product is easy to extract, and effectively reduces hydrogen fluoride residual quantity in product.Present invention system
Standby double (fluorosulfonyl) inferior amine salt product quality stabilizations, meet the use requirement of battery electrolyte, therefore the method is more fitted
Close industrialized production.
Embodiments of the present invention are illustrated below by way of specific instantiation, those skilled in the art can be by this specification
Disclosed content understands other advantages of the invention and effect easily.The present invention can also be by specific realities different in addition
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints with application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
It should be clear that process equipment not specific dated in the following example or device using conventional equipment in the art or
Device.
In addition, it is to be understood that one or more method and steps mentioned in the present invention do not repel before and after the combination step
Can also there is other method step or other method step can also be inserted between the step of these are specifically mentioned, unless separately
It is described；It should also be understood that the combination annexation between one or more the equipment/devices mentioned in the present invention is not repelled
Can also exist before and after the unit equipment/device other equipment/device or two equipment/devices specifically mentioning at these it
Between can also insert other equipment/device, unless otherwise indicated.And, unless otherwise indicated, the numbering of various method steps is only
Differentiate the convenient tool of various method steps, rather than to limit the ordering of various method steps or limiting enforceable model of the invention
Enclose, being altered or modified for its relativeness is of the invention enforceable when being also considered as in the case of without essence change technology contents
Category.
Embodiment 1
The preparation of double fluorine sulfimide lithiums：
In 500mL reaction bulbs, it is added dropwise under the lower addition ether 200g, lithium fluoride 13g, 30 of nitrogen protection~35 DEG C of stirrings
95.3g HFSI and 21.3g SiCl4.Tail gas Alkali absorption.Stirring obtains shallow in 18 hours after decompression precipitation 2 hours at 30 DEG C
Yellow liquid.To 200g dichloromethane is added in concentrate, continue precipitation 1 hour.Product is separated out through filtering, and less than 60 DEG C depressurize
Drying, obtains 86.3g, yield 92%.Testing result：F-(50ppm), moisture 65ppm.Product is white powdery solids, fusing point
124-128℃。
Embodiment 2
The preparation of double fluorine sulfimide lithiums：
In 500mL reaction bulbs, nitrogen protection is lower to add dimethyl carbonate 300g, lithium fluoride 13g, 20~30 DEG C of lower drops of stirring
Plus 91.7g HFSI and 164g SiBr4.Tail gas Alkali absorption.Stirring obtains shallow in 15 hours after the precipitation that depressurized at 40-45 DEG C
Yellow liquid.To 200g dichloromethane is added in concentrate, continue precipitation 1 hour.White solid is separated out through filtering, less than 60 DEG C
Decompression drying obtains 78.8g, yield 84%.Testing result：F-(39ppm), 121-124 DEG C of fusing point.
Embodiment 3
The preparation of double fluorine sulfimide sodium：
In 500mL reaction bulbs, it is added dropwise under the lower addition isopropyl ether 200g, sodium fluoride 21g, 30 of nitrogen protection~40 DEG C of stirrings
94.6g HFSI and 42.5g SiCl4.Tail gas Alkali absorption.15 hours are stirred after decompression precipitation 2 hours at 40-45 DEG C.To
350g dichloroethanes is added in concentrate, continues precipitation 2 hours.White solid filtering is separated out, less than 60 DEG C decompression dryings must be produced
Product 94.4g, yield 93%.Testing result：F-(60ppm), moisture 84ppm, 124-127 DEG C of fusing point.
Embodiment 4：
The preparation of double fluorine sulfimide sodium：
In 500mL reaction bulbs, nitrogen protection is lower to add dimethyl carbonate 250g, sodium fluoride 21g, the 20-30 DEG C of lower drop of stirring
Plus 91.5g HFSI and 23.8g SiCl4.Tail gas Alkali absorption.After the precipitation that depressurized at 50-60 DEG C, about 4 is small within 18 hours for stirring
When.To 200g toluene is added in concentrate, continue precipitation 2 hours.Product is separated out through filtering, and less than 60 DEG C decompression dryings are obtained
93.5g, yield 92%.Testing result：F-(59ppm), 124-127 DEG C of fusing point.
Embodiment 5
The preparation of double fluorine sulfimide potassium：
In 500mL reaction bulbs, it is added dropwise under the lower addition ether 250g, potassium fluoride 29g, 30 of nitrogen protection~40 DEG C of stirrings
92.2g HFSI and 60.7g SiBr4.Tail gas Alkali absorption.16 hours are stirred after decompression precipitation 1 hour at 30 DEG C.To concentration
200g n-hexanes are added in thing, continues precipitation 2 hours.White solid is separated out through filtering, less than 60 DEG C decompression dryings obtain 98.5g,
Yield 90%.Testing result：F-(50ppm), 122-125 DEG C of fusing point.
Embodiment 6
The preparation of double fluorine sulfimide potassium：
In 1000mL reaction bulbs, 95g is added dropwise under the lower addition acetone 380g, potassium fluoride 29g, 30 of nitrogen protection~40 DEG C of stirrings
HFSI and 21.3g SiCl4.Tail gas Alkali absorption.18 hours are stirred after decompression precipitation 1 hour at 35-40 DEG C.To concentrate
Middle addition 350g dichloroethanes, continues precipitation 2 hours.Product is separated out through filtering, and less than 60 DEG C decompression dryings obtain 102.9g, yield
94%.Testing result：F-(40ppm), moisture 59ppm, 124-127 DEG C of fusing point.
Comparative example 1
The preparation of double fluorine sulfimide lithiums：
Under 5 DEG C of constant temperature stirrings, 160g hydrogen fluoride (8mol) is added in 500mL dry reaction containers, be slowly added to
Double chlorine sulfimide (0.6mol) of 128.4g are chemically reacted, and tail gas is by alkali liquor absorption.Drip 0-5 DEG C of isothermal reaction of holding
3 hours, obtain the hydrogen fluoride solution of HFSI.To addition 15.6g lithium fluoride (6mol) in the solution, 5 DEG C of constant temperature are stirred 2 hours,
Precipitation reclaims hydrogen fluoride, yellow oil is obtained, through vacuum and heating drying, testing result：F-(0.12%).
In sum, the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
The personage for knowing this technology all can carry out modifications and changes under without prejudice to spirit and scope of the invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete with institute under technological thought without departing from disclosed spirit such as
Into all equivalent modifications or change, should be covered by claim of the invention.
Claims (8)
1. a kind of preparation method of double (fluorosulfonyl) inferior amine salts, comprises the following steps：
Double (fluorosulfonyl) imines enter line replacement reaction in the presence of a solvent with alkali metal fluoride MF, silicon tetrahalogen,
Double (fluorosulfonyl) inferior amine salts are prepared, the structural formula of described double (fluorosulfonyl) inferior amine salts is shown in formula I：
Wherein, M is selected from Li, Na or K.
2. the as claimed in claim 1 a kind of double preparation method of (fluorosulfonyl) inferior amine salts, it is characterised in that double (fluorine
Sulfonyl) mol ratio of imines and alkali metal fluoride MF is 1~1.1：1；
And/or, the silicon tetrahalogen is 0.25~2 with the mol ratio of alkali metal fluoride MF：1；
And/or, the silicon tetrahalogen is selected from the combination of one or more in silicon tetrachloride, silicon bromide；
And/or, the reaction temperature of the reaction is 0~50 DEG C；
And/or, the solvent is organic solvent；
And/or, the reaction is carried out under conditions of gas shield.
3. the as claimed in claim 2 a kind of double preparation method of (fluorosulfonyl) inferior amine salts, it is characterised in that four halogenation
Silicon is 0.3~0.8 with the mol ratio of alkali metal fluoride MF：1；
And/or, the reaction temperature is 15~40 DEG C；
And/or, the organic solvent is selected from the combination of one or more in ketones solvent, esters solvent or ether solvent；
And/or, the gas that the gas shield is used is selected from the combination of one or more in nitrogen, inert gas.
4. the preparation method of (fluorosulfonyl) inferior amine salts as claimed in claim 3 a kind of double, it is characterised in that the ketone is molten
Agent is selected from the one kind in 1-METHYLPYRROLIDONE, acetone, methyl ethyl ketone, butanone, methyl tertbutyl ketone, 4-methyl-2 pentanone
Or various combinations；
And/or, the esters solvent is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, carbonic acid third
In alkene ester, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, vinylacetate
One or more of combination；
And/or, the ether solvent be selected from ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, tetrahydrofuran, methyltetrahydrofuran,
One or more in cyclopentyl methyl ether, dioxane, dioxolane, glycol dimethyl ether of combination.
5. the as claimed in claim 1 a kind of double preparation method of (fluorosulfonyl) inferior amine salts, it is characterised in that double (fluorine sulphonyl
Base) imines and alkali metal fluoride MF, the silicon tetrahalogen specific method that enters line replacement reaction is：To containing alkali metal fluoride MF
Solvent in add double (fluorosulfonyl) imines, add silicon tetrahalogen.
6. the as claimed in claim 5 a kind of double preparation method of (fluorosulfonyl) inferior amine salts, it is characterised in that displacement reaction knot
Shu Hou, desolvation, separation of solid and liquid, solid phase is double (fluorosulfonyl) inferior amine salts.
7. the preparation method of (fluorosulfonyl) inferior amine salts as claimed in claim 6 a kind of double, it is characterised in that desolvation
Specific method is distillation；
And/or, during the desolvation, also to adding poor solvent in reaction system.
8. the as claimed in claim 7 a kind of double preparation method of (fluorosulfonyl) inferior amine salts, it is characterised in that the distillation temperature
Spend is 25-100 DEG C；
And/or, the vapo(u)rizing temperature is 30-60 DEG C；
And/or, the poor solvent is 2~10 with the mass ratio of double (fluorosulfonyl) imines：1；
And/or, the poor solvent is selected from saturated hydrocarbons solvent, halogenated hydrocarbon solvent, aromatic hydrocarbon solvent and the halogen of low polarity
One or more in for aromatic hydrocarbon solvent of combination；
And/or, the poor solvent is selected from n-hexane, hexamethylene, dichloromethane, dichloroethanes, toluene, dimethylbenzene, chlorobenzene, two
One or more in chlorobenzene of combination.
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