• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    A process for preparing bis-fluorosulfonylimide acid comprising reacting the sulfamic acid or a salt thereof with a halosulfuric acid and at least one fluorinating agent selected from SOF2, F-SO2-F and SF4 then the recovery of bis-fluorosulfonylimide acid. Also disclosed is a process for the preparation of bis-fluorosulfonylimide salts from the bis-fluorosulfonylimide acid thus prepared.
    公开号:FR3014439A1
    申请号:FR1362137
    申请日:2013-12-05
    公开日:2015-06-12
    发明作者:Olivier Buisine
    申请人:Rhodia Operations SAS；
    IPC主号:
    专利说明:

    [0001] PROCESS FOR THE PREPARATION OF BIS-FLUOROSULFONYLIM IDE ACID AND ITS SALTS The subject of the present invention is a process for the preparation of bis-5-fluorosulphonylimide acid (FSIH) and its salts, in particular of lithium bisfluorosulfonylimide LiFSI. The production of FISH and LiFSI is widely described in the literature. Among the various technologies described, the majority implements a fluorination reaction either by HF or by metal fluorides. The use of metal fluorides is problematic because it is often not very effective and uses expensive reagents such as fluorosulphuric acid. For example, the fluorination of potassium fluoride in nitromethane or other polar organic solvents is inefficient in terms of yield (WO 2002/053494). Other technologies have been developed, for example by using chlorosulfonyl isocyanate in the presence of oleum and ammonium fluoride (JP 2012-162470) or by using urea and fluorosulfonic acid, but these technologies suffer from the strong corrosion of the medium as well as from the exothermic reaction. These disadvantages make these technologies unsuitable for industrial production of bis-fluorosulfonylimide acid (FSIH) and its salts. Also the need to produce bis-fluorosulfonylimide acid (FSIH) and its salts by an alternative method overcoming the disadvantages mentioned above is great. Surprisingly, the Applicant has developed a new process for producing bis-fluorosulfonylimide acid (FSIH) and its salts operating under mild conditions and without exotherm. The process according to the present invention has the advantage of being easy to implement on an industrial scale. The present invention relates to a process for preparing bisfluorosulfonylimide acid of the formula F-502-NH-502-F (FSIH) comprising reacting the sulfamic acid or a salt thereof with at least one acid halosulfuric acid and at least one fluorinating agent selected from sulfonyl fluoride (SOF2), sulfuryl fluoride (F-502-F) and sulfur tetrafluoride (SF4) and then recovering bis-fluorosulfonylimide acid.
    [0002] According to the process of the invention, the halosulfuric acid has the formula X-SO 2 -OH where X is a halogen selected from fluorine, chlorine, bromine and iodine. Preferably, said halogen is fluorine (fluorosulfuric acid) or chlorine (chlorosulfuric acid). The sulfamic acid or a salt thereof has the general formula M10-SO2-NH2, where M1 = H, an alkali metal or an alkaline earth metal. Advantageously, said fluorinating agent is sulfuryl fluoride (F-SO 2 -F). The reaction carried out in the process of the invention is advantageously carried out in the presence of a solvent, preferably an organic solvent. Said solvent is for example a linear or branched aliphatic hydrocarbon or an aromatic hydrocarbon, for example toluene, xylene, chlorobenzene, dichlorobenzene or nitrobenzene. Preferably, dichlorobenzene is used.
    [0003] In accordance with the process of the invention, said fluorinating agent advantageously represents from 1 to 10, preferably from 2 to 5, molar equivalent (s) expressed relative to the sulphamic acid or its salts. When the reaction according to the process of the invention is carried out in the presence of a solvent, it advantageously represents from 10 to 90% by weight of the mass of the reaction mixture, which comprises all of the reactants and the solvent. According to one embodiment of the process of the invention consisting in using sulfuryl fluoride (SO2F2) as fluorinating agent, the halosulphuric acid advantageously represents from 1 mol% to 5 molar equivalents expressed relative to the acid. sulphamic acid or its salts, preferably from 5 mol% to 1 molar equivalent expressed (s) relative to the sulphamic acid or its salts. This embodiment is preferred because it limits the amount of halosulfuric acid to be introduced for carrying out the process of the invention.
    [0004] According to another embodiment of the process of the invention consisting in using sulfonyl fluoride (SOF2) or sulfur tetrafluoride (SF4) as fluorinating agent, the halosulfuric acid represents from 1 to 5, preferably from 1 to 2 molar equivalent (s) expressed relative to the sulphamic acid or its salts. The reaction carried out according to the process of the invention is carried out at a temperature preferably between 0 ° C. and 180 ° C., very preferably between 80 and 150 ° C. It is advantageously conducted at a pressure ranging between 1 and 100 bar, preferably it is conducted under autogenous pressure.
    [0005] The process for preparing FSIH according to the invention is simple to implement. The reagents can be introduced in any order according to different variants but some are preferred. A preferred embodiment comprises mixing the sulfamic acid or its salts, optionally present in said solvent, and the halosulfuric acid and then introducing said fluorinating agent. The said fluorinating agent is introduced either in gaseous form, generally at atmospheric pressure and / or at room temperature, or in liquid form, generally under pressure and / or at a low temperature. The reaction mixture is stirred at the temperature of the reaction selected in the range as previously defined. The heating of the reaction mixture is maintained for a variable duration, for example for a period ranging from 1 hour to 48 hours and preferably ranging from 3 to 12 hours. It is further advantageous to introduce said fluorinating agent once the medium has been brought to the reaction temperature. After stirring the reaction medium at the selected temperature, the bis-fluorosulfonylimide acid is obtained at the end of the reaction. The reaction medium obtained at the end of the reaction is brought back to atmospheric pressure if necessary. The volatile products present in said medium, generally HF, SO3 and optionally the fluorination reagent in excess, are evaporated. Said bis-fluorosulfonylimide acid is then recovered by various techniques known per se to those skilled in the art. A first embodiment consists in recovering the bis-fluorosulfonylimide acid by distillation. The reaction medium resulting from the reaction and devoid of volatile products is subjected to distillation, preferably under reduced pressure, at a temperature preferably between 100 and 250 ° C, and at a pressure preferably between 0.5 and 10 bar. The FSIH is recovered in liquid form.
    [0006] A second embodiment consists of recovering bis-fluorosulfonylimide acid by sublimation. The reaction medium resulting from the reaction and devoid of volatile products is subjected to a sublimation treatment at a temperature preferably between 50 and 250 ° C, very preferably between 80 and 140 ° C and at a pressure preferably between 1 mbar and 1 bar, very preferably between 10 mbar and 500 mbar. The FSIH is recovered in solid form.
    [0007] A third embodiment consists simply in maintaining the bis-fluorosulfonylimide acid in the reaction mixture resulting from the reaction and free of volatiles by bringing said medium back to atmospheric pressure and at a temperature below 160 ° C., preferably between 20 and 80 ° C. The bis-fluorosulfonylimide acid can thus be used directly, in the subsequent salification step, in solution or suspension in the solvent in which said reaction has been carried out.
    [0008] The process of the invention is advantageously carried out in equipment capable of withstanding the corrosion of the reaction medium. For this purpose, materials are chosen for the part in contact with the corrosion-resistant reaction medium such as alloys based on molybdenum, chromium, cobalt, iron, copper manganese, titanium, zirconium, aluminum, carbon and tungsten sold under the HASTELLOY® brands or alloys of nickel, chromium, iron, manganese with added copper and / or molybdenum sold under the name INCONEL®, MONELTM and more particularly alloys HASTELLOY C 276 or INCONEL 600, 625 or 718. It is also possible to choose stainless steels, such as austenitic steels [Robert H. Perry et al, Perry 's Chemical Engineers' Handbook, Sixth Edition (1984), pp. 23-44]. and more particularly 304, 304 L, 316 or 316 L stainless steels. A steel having a nickel content of at most 22% by weight, preferably between 6 and 20%, and more preferably between 8 and 20%, is used. and 14%. The 304 and 304 L steels have a nickel content ranging between 8 and 12% and the 316 and 316 L steels have a nickel content ranging between 10 and 14%. 316 L steels are more particularly chosen. It is also possible to use an apparatus consisting of or coated with a polymeric compound that is resistant to corrosion of the reaction medium. Mention may in particular be made of materials such as PTFE (polytetrafluoroethylene or Teflon) or PFA (perfluoroalkyl resins). It will not be departing from the scope of the invention to use an equivalent material.
    [0009] As other materials that may be suitable for being in contact with the reaction medium, mention may also be made of graphite derivatives. The process for preparing the FSIH according to the invention can be carried out continuously, discontinuously or semi-continuously. It is generally preferred to have FSIH salts because they find an application more easily than the FSIH itself. Also, another object of the invention is a process for preparing at least one bis-fluorosulfonylimide salt from the process for preparing the bis-fluorosulfonylimide acid as described above. Said salt of bisfluorosulfonylimide has the general formula F-SO2-NM-SO2-F, where M represents an alkali metal (Li, Na, K, Rb, Cs), an alkaline earth metal, a transition metal or a selected metal among the lanthanides. Preferably, M is an alkali metal, in particular lithium: the salt thus obtained is lithium bis-fluorosulfonylimide (LiFSI). The process for the preparation of at least one salt of the bis-fluorosulfonylimide according to the invention consists in bringing the bis-fluorosulfonylimide acid prepared according to the process described above into contact with at least one salification agent. The salifying agent is, for example, a metal hydroxide, a metal halide, a metal hydride, a metal trifluoroacetate or a metal trifluoromethanesulfonate. The metal present in said metal hydroxide, said metal halide, said metal hydride, said metal trifluoroacetate or said metal trifluoromethanesulfonate is preferably selected from alkali metals, alkaline earth metals, transition metals or metals selected from lanthanides. The stoichiometry of this salification step is such that 1 to 5, preferably 1 to 2, molar equivalents of salification agent are used relative to the bis-fluorosulfonylimide acid.
    [0010] Said process for preparing at least one salt of bis-fluorosulfonylimide according to the invention is carried out in the presence or absence of a solvent, preferably in the presence of a solvent. The solvent is, for example, water or an organic solvent chosen from linear or branched aliphatic hydrocarbons, aromatic hydrocarbons (toluene, xylene, chlorobenzene, dichlorobenzene), nitrile compounds (acetonitrile, butyronitrile, valeronitrile, adiponitrile) and carbonates. alkyl (carbonate ethylene, carbonate propylene, dimethyl carbonate, diethyl carbonate). Said solvent can represent up to 90% by weight, preferably from 10 to 80% by weight of the mass of the reaction mixture, which comprises all of the reactants and the solvent. The process for preparing a salt of bis-fluorosulfonylimide according to the invention is carried out at a temperature preferably below 100 ° C, very preferably between 20 and 50 ° C. Said process is preferably carried out at atmospheric pressure. The process for preparing a salt of bis-fluorosulfonylimide according to the invention is simple to implement. The FSIH is added to the salification agent or vice versa. One or the other may be in the pure state while at least one of these two reagents is preferably present in a solvent.
    [0011] The salt of the bis-fluorosulfonylimide is isolated by filtration or evaporation of the solvent. The process for preparing salts of the bis-fluorosulfonylimide according to the invention can be carried out continuously, discontinuously or semi-continuously. Another object of the present invention is the use of the bisfluorosulfonylimide salts prepared according to the method described above as electrolyte salts, as antistatic agent precursors or as surfactant precursors. In particular, said salts are advantageously used as electrolytes for the manufacture of batteries, in the field of electrochromism and electronics. They are advantageously used as antistatic agents for the manufacture of pressure sensitive adhesives (PSA). As an anti-static agent, they can still be used as lubricant components. They are used in optical materials such as electroluminescent devices and are used in the composition of photovoltaic panels. An exemplary embodiment of the invention is given below. This example is given for illustrative and non-limiting purposes.
    [0012] Example 1: A 500 mL Hastelloy C276 reactor is charged with a solution of sulfamic acid (22.4 g, 230 mmol) in 30 grams of orthodichlorobenzene. Fluosulphonic acid (1.2 g, 12 mmol) is added and the autoclave is closed. The medium is heated to a temperature of 92 ° C. Sulfuryl fluoride (47 grams, 0.46 moles) is added to keep the pressure below P = 37 bar. The addition is carried out in 9 hours. The temperature is then brought back to ambient temperature and the reactor is decompressed.
    [0013] An analysis of the reaction medium by NMR of the fluorine 19 shows that the expected bis-fluorosulphonic acid is formed in a yield of 52%.
    权利要求:
    Claims (12)
    [0001]
    REVENDICATIONS1. A process for preparing the bis-fluorosulfonylimide acid of the formula F-SO2-NH-502-F (FSIH) comprising reacting the sulfamic acid or a salt thereof with at least one halosulfuric acid and at least one agent fluorination chosen from SOF2, F-502-F and SF4 and recovery of the bis-fluorosulfonylimide acid.
    [0002]
    2. A process for the preparation of the bis-fluorosulfonylimide acid according to claim 1 wherein the halosulfuric acid has the formula X-502-OH wherein X is a halogen selected from fluorine, chlorine, bromine and iodine.
    [0003]
    A process for preparing bis-fluorosulfonylimide acid according to claim 1 or claim 2 wherein said reaction is conducted in the presence of an organic solvent.
    [0004]
    4. Process for the preparation of bis-fluorosulfonylimide acid according to one of claims 1 to 3 wherein the halosulfuric acid is 1 mol% to 5 molar equivalents expressed (s) relative to the sulfamic acid or its salts when the fluorinating agent is F-502-F.
    [0005]
    5. A process for the preparation of bis-fluorosulfonylimide acid according to one of claims 1 to 3 wherein the halosulfuric acid represents from 1 to 5 molar equivalent (s) expressed (s) relative to the acid sulfamic acid or its salts when the fluorinating agent is SOF2 or SF4.
    [0006]
    6. Process for the preparation of bis-fluorosulfonylimide acid according to one of claims 1 to 5 wherein said fluorinating agent represents from 1 to 10 molar equivalent (s) expressed (s) relative to the acid sulfamic acid or its salts.
    [0007]
    7. A process for preparing bis-fluorosulfonylimide acid according to one of claims 1 to 6 wherein said reaction is carried out at a temperature between 0 and 180 ° C.
    [0008]
    8. A process for preparing bis-fluorosulfonylimide acid according to one of claims 1 to 7 wherein said bis-fluorosulfonylimide acid is recovered by distillation or sublimation.
    [0009]
    9. Process for the preparation of at least one salt of bis-fluorosulfonylimide comprising the preparation of bis-fluorosulfonylimide acid according to the process as defined in claims 1 to 8 followed by bringing said acid into contact with at least one agent of salification.
    [0010]
    A process for preparing at least one salt of bis-fluorosulfonylimide according to claim 9 wherein said salifying agent is a metal hydroxide, a metal halide, a metal hydride, a metal trifluoroacetate or a metal trifluoromethanesulfonate.
    [0011]
    A process for preparing at least one salt of bis-fluorosulfonylimide according to claim 9 or claim 10 wherein said salt has the general formula F-SO 2 -NN-SO 2 -F, where M represents an alkali metal, a metal alkaline earth metal, a transition metal or a metal selected from lanthanides.
    [0012]
    12. Use of the bis-fluorosulfonylimide salts prepared according to the process as defined in one of claims 9 to 11 as electrolyte salts, as antistatic agent precursors or as surfactant precursors.
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    法律状态:
    2015-11-10| PLFP| Fee payment|Year of fee payment: 3 |
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    2017-11-13| PLFP| Fee payment|Year of fee payment: 5 |
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    优先权:
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    FR1362137A|FR3014439B1|2013-12-05|2013-12-05|PROCESS FOR THE PREPARATION OF BIS-FLUOROSULFONYLIMIDE ACID AND ITS SALTS|
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