阅读说明：本技术 用于制备双(氟磺酰)亚胺酸及其盐的方法 (Process for the preparation of bis (fluorosulfonyl) imide acid and salts thereof ) 是由 O·比西纳 于 2014-12-03 设计创作，主要内容包括：本发明涉及用于制备双(氟磺酰基)亚胺酸的方法,该方法包括：氨基磺酸或其盐之一与卤代硫酸和至少一种选自SOF-(2)、F-SO-(2)-F和SF-(4)的氟化剂的反应,以及双(氟磺酰)亚胺酸的后续回收。本发明还涉及用于从因此生产的双(氟磺酰)亚胺酸生产双(氟磺酰)亚胺的盐的方法。(The present invention relates to a process for the preparation of bis (fluorosulfonyl) imide acid, said process comprising: sulfamic acid or one of its salts with halogenated sulfuric acid and at least one selected from SOF 2 、F‑SO 2 -F and SF 4 And subsequent recovery of the bis (fluorosulfonyl) imide acid. The invention also relates to a process for the production of bisA process for producing a salt of bis (fluorosulfonyl) imide from (fluorosulfonyl) imide acid.)

1. Used for preparing a compound having a formula of F-SO₂-NH-SO₂A process for the preparation of bis (fluorosulfonyl) imide acid of (i) -F, which comprises reacting sulfamic acid or its salt with at least one halosulfuric acid and at least one SOF₂、F-SO₂-F and SF₄And then recovering the bis (fluorosulfonyl) imide acid.

2. The process as claimed in claim 1 for preparing bis (fluorosulfonic acid)Imide acid process wherein the halosulfuric acid has the formula X-SO₂-OH, wherein X is a halogen selected from fluorine, chlorine, bromine and iodine.

3. The process for producing a bis (fluorosulfonyl) imide acid as claimed in claim 1 or claim 2, wherein said reaction is carried out in the presence of an organic solvent.

4. The process for preparing bis (fluorosulfonyl) imide acid as claimed in one of claims 1 to 3, wherein when said fluorinating agent is F-SO₂-F, the halogenated sulfuric acid represents from 1% mol to 5 molar equivalents expressed with respect to the sulfamic acid or salt thereof.

5. The method for preparing bis (fluorosulfonyl) imide acid as claimed in claim 4, wherein when said fluorinating agent is F-SO₂-F, the halogenated sulfuric acid represents from 5% mol to 1 molar equivalent expressed with respect to the sulfamic acid or salt thereof.

6. The process for preparing bis (fluorosulfonyl) imide acid as claimed in one of claims 1 to 3, wherein when said fluorinating agent is SOF₂Or SF₄When used, the halosulfuric acid represents from 1 to 5 molar equivalents expressed relative to the sulfamic acid or salt thereof.

7. The process for the preparation of bis (fluorosulfonyl) imide acid as claimed in one of claims 1 to 6, wherein said fluorinating agent represents from 1 to 10 molar equivalents expressed with respect to the sulfamic acid or salt thereof.

8. The process for the preparation of bis (fluorosulfonyl) imide acid as claimed in one of claims 1 to 7, wherein said reaction is carried out at a temperature between 0 and 180 ℃.

9. The process for producing a bis (fluorosulfonyl) imide acid as claimed in one of claims 1 to 8, wherein said bis (fluorosulfonyl) imide acid is recovered by distillation, sublimation or extraction.

10. A process for preparing at least one bis (fluorosulfonyl) imide salt, said process comprising preparing the bis (fluorosulfonyl) imide acid according to the process as defined in claims 1 to 9, followed by contacting said acid with at least one salt forming agent.

11. The process for preparing at least one bis (fluorosulfonyl) imide salt of claim 10 wherein the salt forming agent is a metal hydroxide, metal halide, metal hydride, metal trifluoroacetate or metal trifluoromethanesulfonate.

12. The process for the preparation of at least one bis (fluorosulfonyl) imide salt according to claim 10 or claim 11 wherein said salt has the general formula F-SO₂-N-M-SO₂-F, wherein M represents an alkali metal, an alkaline earth metal, a transition metal or a metal selected from the lanthanides.

13. The process for the preparation of at least one bis (fluorosulfonyl) imide salt according to one of claims 10 to 12, wherein said salt is lithium bis (fluorosulfonyl) imide.

14. The process for the preparation of at least one bis (fluorosulfonyl) imide salt according to any one of claims 10 to 13 further comprising the step of purifying said salt.

15. The process for preparing at least one bis (fluorosulfonyl) imide salt of claim 14 wherein the purification step consists of recrystallization.

16. Use of a bis (fluorosulfonyl) imide salt prepared according to the process as defined in one of claims 10 to 15 as electrolyte salt, as antistatic agent precursor or as surfactant precursor.

A technical field

The subject of the present invention is a process for the preparation of bis (fluorosulfonyl) imide acid (HFSI) and its salts, in particular lithium bis (fluorosulfonyl) imide LiFSI.

Second, background Art

The production of HFSI and LiFSI is widely described in the literature. Among the different techniques described, most utilize fluorination reactions either with HF or with metal fluorides. The use of metal fluorides is problematic because it is often not very effective and uses expensive reagents such as fluorosulfonic acid. For example, fluorination using potassium fluoride in nitromethane or other polar organic solvents is not very efficient in terms of yield (WO 2002/053494). Other techniques have been developed, for example the use of chlorosulfonyl isocyanate or else urea and fluorosulfonic acid in the presence of oleum and ammonium fluoride (JP 2012-162470), but these techniques are limited by the strong corrosion of the medium and also the exothermicity of the reaction. These disadvantages make these techniques less suitable for the industrial production of bis (fluorosulfonyl) imide acid (HFSI) and its salts. Methods for preparing bis-fluorosulfonylimide acid and salts thereof are also described by Beran and Prihoda scientific publications (journal of inorganic chemistry, z. However, the proposed synthetic route involves the use of thionyl chloride, followed by conversion of the obtained chlorinated compound into a fluorinated compound.

There is therefore a great need for the production of bis (fluorosulfonyl) imide acid (HFSI) and its salts according to an alternative process, which remedies the above-mentioned disadvantages. Surprisingly, the applicant has developed a novel process for the production of bis (fluorosulfonyl) imide acid (HFSI) and salts thereof, which operates under mild conditions and without exothermicity. The process according to the invention has the advantage that it can be carried out easily on an industrial scale.

Third, the invention

Subject of the invention is the preparation of a compound of formula F-SO₂-NH-SO₂Process for the preparation of bis (fluorosulfonyl) imide acid (HFSI) of (F) comprising reacting sulfamic acid or a salt thereof with at least one halosulfuric acid and at least one compound selected from the group consisting of sulfonyl fluorides (SOF)₂) Sulfuryl fluoride (F-SO)₂-F) and sulfur tetrafluoride (SF)₄) And then recovering the bis (fluorosulfonyl) imide acid.

Fourth, detailed description of the invention

According to the process of the invention, the halogenated sulfuric acid has the formula X-SO₂-OH, wherein X is a halogen selected from fluorine, chlorine, bromine and iodine. Preferably, theThe halogen is fluorine (fluorosulfonic acid) or chlorine (chlorosulfonic acid). The sulfamic acid or salt thereof has the general formula M₁O-SO₂-NH₂Wherein M is₁H, alkali metal or alkaline earth metal. Advantageously, the 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. The solvent is, for example, a linear or branched aliphatic or aromatic hydrocarbon, such as toluene, xylene, chlorobenzene, dichlorobenzene or nitrobenzene. Preferably, dichlorobenzene is used.

According to the process of the invention, said fluorinating agent advantageously represents from 1 to 10, preferably from 2 to 5, molar equivalents expressed with respect to the sulfamic acid or salt thereof. When the reaction according to the process of the invention is carried out in the presence of a solvent, said solvent advantageously represents from 10% to 90% by weight of the reaction mixture comprising all the reagents and the solvent.

The process according to the invention consists in using sulfuryl fluoride (SO)₂F₂) As an example of a fluorinating agent, the halogenated sulfuric acid advantageously represents from 1% mol to 5mol equivalents expressed with respect to the sulfamic acid or salt thereof, preferably from 5% mol to 1mol equivalents expressed with respect to the sulfamic acid or salt thereof. Advantageously, when the fluorinating agent used is sulfuryl fluoride, the halogenated sulfuric acid can be used in catalytic amounts, preferably less than 1 molar equivalent. This example is preferred because it makes it possible to limit the amount of halogenated sulfuric acid introduced for carrying out the process of the invention.

The process according to the invention consists in using sulfuryl fluoride (SOF)₂) Or sulfur tetrafluoride (SF)₄) As another example of the fluorinating agent, the halogenated sulfuric acid means from 1 to 5, preferably from 1 to 2, molar equivalents relative to the sulfamic acid or salt thereof.

The reaction carried out according to the process of the invention is preferably carried out at a temperature between 0 ℃ and 180 ℃ and very preferably between 80 ℃ and 150 ℃. The reaction is advantageously carried out at a pressure in the range between 1 and 100 bar, the reaction preferably being carried out at autogenous pressure.

The process for the preparation of HFSI according to the present invention is easy to carry out.

The reagents may be introduced in any order according to different variants, but some order is preferred.

A preferred embodiment consists in mixing the sulfamic acid or salt thereof, optionally in the solvent, with the halogenated sulfuric acid and then in introducing the fluorinating agent. The fluorinating agent is introduced either in gaseous form, generally at atmospheric pressure and/or at ambient temperature, or in liquid form, generally under pressure and/or at low temperature. The reaction mixture is brought to the selected reaction temperature with stirring at time intervals as defined previously. The heating of the reaction mixture is maintained for a variable period of time, for example for a period of time ranging from 1 hour to 48 hours and preferentially ranging from 3 to 12 hours. It is further advantageous to introduce the fluorinating agent immediately once the medium has been brought to the reaction temperature.

After the reaction medium has been kept at the chosen temperature with stirring, the bis (fluorosulfonyl) imide acid is obtained at the end of the reaction. The reaction medium obtained at the end of the reaction is brought, where appropriate, back to atmospheric pressure. Volatile products, typically HF, SO, present in the medium₃And possibly the excess fluorinating agent is evaporated off.

The bis (fluorosulfonyl) imide acid is then recovered using a variety of techniques, which are themselves known to those skilled in the art.

The first embodiment consists in recovering the bis (fluorosulfonyl) imide acid by distillation. The reaction medium obtained from the reaction and free of volatile products is subjected to distillation, preferably under reduced pressure, preferentially at a temperature between 100 ℃ and 250 ℃, and preferentially at a pressure between 0.5 and 10 bar. The HFSI is recovered as a liquid.

A second embodiment consists in recovering the bis (fluorosulfonyl) imide acid by sublimation. The reaction medium obtained from the reaction and free of volatile products is subjected to a treatment by sublimation preferentially at a temperature between 50 ℃ and 250 ℃, very preferentially between 80 ℃ and 140 ℃, and preferentially at a pressure between 1 mbar and 1 bar, very preferentially between 10 mbar and 500 mbar. The HFSI is recovered as a solid.

A third example consists in simply maintaining the bis (fluorosulfonyl) imide acid in the reaction mixture resulting from the reaction and free of volatile products while returning the medium to atmospheric pressure and to a temperature lower than 160 ℃, preferably between 20 ℃ and 80 ℃. Thus, in the subsequent salification step, the bis (fluorosulfonyl) imide acid can be used directly in solution or suspension in the solvent in which the reaction is carried out.

A fourth example is the recovery of the bis (fluorosulfonyl) imide acid by extraction using a solvent. The solvent may be selected from organic solvents. The solvent may be, for example, a linear or branched aliphatic hydrocarbon or a halogenated aliphatic hydrocarbon, such as dichloromethane or dichloroethane. Preferably, dichloroethane can be used.

The process of the invention is advantageously carried out in a plant capable of withstanding the corrosion of the reaction medium.

For this purpose, the material chosen for the part in contact with the reaction medium is corrosion-resistant, for example based on molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminium, carbon and tungsten, andalloys sold under the brand name, or nickel, chromium, iron and manganese with copper and/or molybdenum added thereto, by nameOr Monel^TMAlloys sold, and more specifically Hastelloy C276 or Inconel 600, 625 or 718 alloys. Stainless steels may also be chosen, such as austenitic steels [ Robert H.Perry et al, Handbook of the Peltier Chemical Engineers' Handbook, sixth edition (1984), pages 23-44]And more particularly type 304, 304L, 316 or 316L stainless steel. Steels with a nickel content of at most 22%, preferably between 6% and 20% and more preferentially between 8% and 14% by weight are used. These 304 and 304L steels have nickel contents varying between 8% and 12%, and 316L steels have nickel varying between 10% and 14%And (4) content. More particularly, 316L steel is chosen.

It is also possible to use equipment consisting of or coated with a polymeric compound resistant to corrosion by the reaction medium. Materials such as PTFE (polytetrafluoroethylene or teflon) or PFA (perfluoroalkyl resin) may be mentioned in particular. Equivalent materials may be used without departing from the scope of the invention.

As other materials that can be suitably brought into contact with the reaction medium, mention may also be made of graphite derivatives.

The process for the preparation of HFSI according to the present invention may be carried out continuously, batchwise or semi-continuously.

It is generally preferred to have HFSI salts because they find use more readily than HFSI itself. Therefore, another subject of the present invention is a process for preparing at least one bis (fluorosulfonyl) imide salt using a process for preparing bis (fluorosulfonyl) imide acid as described above. The bis (fluorosulfonyl) imide salt has the general formula F-SO₂-N-M-SO₂-F, wherein M represents an alkali metal (Li, Na, K, Rb, Cs), an alkaline earth metal, a transition metal or a metal selected from the lanthanides. Preferably, M is an alkali metal, in particular lithium: the salt produced is lithium bis (fluorosulfonyl) imide (LiFSI). The process according to the invention for preparing at least one bis (fluorosulfonyl) imide salt consists in contacting the bis (fluorosulfonyl) imide acid prepared according to the process described above with at least one salt-forming agent. The salt former is, for example, a metal hydroxide, a metal halide, a metal hydride, a metal trifluoroacetate or a metal trifluoromethanesulfonate. The metal present in the metal hydroxide, the metal halide, the metal hydride, the metal trifluoroacetate or the metal trifluoromethanesulfonate is preferably selected from the group consisting of alkali metals, alkaline earth metals, transition metals or metals from the group of lanthanides. The stoichiometry of this salt formation step is such that from 1 to 5, preferably from 1 to 2, molar equivalents of salt-forming agent are used relative to the bis (fluorosulfonyl) imide acid.

The process according to the invention for preparing at least one bis (fluorosulfonyl) imide salt 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 selected from the group consisting of linear or branched aliphatic hydrocarbons, aromatic hydrocarbons (toluene, xylene, chlorobenzene, dichlorobenzene), nitrile compounds (acetonitrile, butyronitrile, valeronitrile, adiponitrile) and alkyl carbonates (ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate). The solvent may represent up to 90% by weight, preferably from 10 to 80% by weight of the reaction mixture comprising all reagents and the solvent.

The process according to the invention for the preparation of bis (fluorosulfonyl) imide salts is carried out at temperatures preferably below 100 ℃ and very preferably between 20 ℃ and 50 ℃. The process is preferably carried out at atmospheric pressure.

The process for preparing bis (fluorosulfonyl) imide salts according to the present invention is easy to carry out. The HFSI is added to the salt former or vice versa. Either may be in pure form, however at least one of the two reagents is preferably present in the solvent.

The bis (fluorosulfonyl) imide salt is isolated by filtration or evaporation of the solvent.

The process according to the invention for preparing the bis (fluorosulfonyl) imide salt can be carried out continuously, batchwise or semi-continuously.

The process according to the invention for the preparation of a bis (fluorosulfonyl) imide salt further comprises a step of purifying said salt. This purification step may in particular consist of recrystallization. The recrystallization solvent may be selected from oxygen-containing solvents, such as ethers or esters. Examples of ether solvents are tetrahydrofuran, dioxane and glyme.

Purification of the bis (fluorosulfonyl) imide salt by recrystallization can also be the subject of the present invention independently of the process used to obtain said salt.

After its isolation and optional purification, the bis (fluorosulfonyl) imide salt can be dried by conventional methods known to those skilled in the art, for example, by conventional drying, by drying under reduced pressure, or by spray drying.

Another subject of the invention is the use of the bis (fluorosulfonyl) imide salt prepared according to the process described above as electrolyte salt, as antistatic agent precursor or as surfactant precursor. In particular, the salts are advantageously used as electrolytes for the manufacture of batteries and in the fields of chromium electroplating and electronics. They are advantageously used as antistatic agents for the manufacture of pressure-sensitive adhesives (PSA). As antistatic agents, they can also be used as components of lubricants. They are used in optical materials such as electroluminescent devices and incorporated into the composition of photovoltaic panels.

Exemplary embodiments of the present invention are given below. This example is given by way of non-limiting illustration.

Example 1:

a solution of sulfamic acid (22.4 g; 230mmol) in 30 grams of o-dichlorobenzene was charged to a 500ml C276 hastelloy reactor. Fluorosulfonic acid (1.2 g; 12mmol) was added and the autoclave was closed. The medium is heated to a temperature of 92 ℃. Sulfuryl fluoride (47 g; 0.46mol) was added in such a way as to maintain the pressure below P37 bar. The addition was carried out within 9 hours.

The temperature was then returned to room temperature and the reactor was depressurized. Analysis of the reaction medium by fluorine 19NMR showed the formation of the expected bis (fluorosulfonyl) imide acid with a yield of 52%.

Example 2:

a solution of sulfamic acid (22.4 g; 230mmol) in 300 grams of dichloroethane was charged to a 500ml C276 hastelloy reactor. Fluorosulfonic acid (1.2 g; 12mmol) was added and the autoclave was closed. The medium is heated to a temperature of 92 ℃. Sulfuryl fluoride (47 g; 0.46mol) was added in such a way as to maintain the pressure below P37 bar. The addition was carried out within 10 hours.

The temperature was then returned to room temperature and the reactor was depressurized. Analysis of the reaction medium by fluorine 19NMR showed the formation of the expected bis (fluorosulfonyl) imide acid with a yield of 53%.

Example 3:

200g of dichloroethane were charged to a 500ml C276 hastelloy reactor, which was then closed and kept stirring at room temperature and purged with nitrogen. Thionyl fluoride (60 g; 0.34mol) was then added to the reactor under pressure. A solution of sulfamic acid (22.3 g; 0.23mol) in dichloroethane (100g) and then chlorosulfonic acid (26.8 g; 0.23mol) was added to the autoclave. Then, the temperature was maintained at 80 ℃ for 17 hours. The pressure observed reached 22 bar at this temperature at the end of the reaction. After returning to room temperature, the reactor was depressurized.

The medium passes through¹⁹Analysis by F NMR showed that bis (fluorosulfonyl) imide acid was obtained with a yield of 77%.

Example 4:

the solution containing the bis (fluorosulfonyl) imide acid obtained in example 3 was concentrated at ambient temperature under reduced pressure while maintaining the temperature of the medium below 80 ℃.

The residue obtained is distilled under reduced pressure (P ═ 5 mbar) while maintaining the boiler temperature below 80 ℃.

The bis (fluorosulfonyl) imide acid thus distilled off was slowly added to a suspension of lithium hydride (1.15 g; 0.145mol) in anhydrous butyl acetate (55g) under an inert atmosphere. The solution was then cooled to-20 ℃ and the solid obtained was recovered by filtration.

The solid was purified a second time from butyl acetate by recrystallization.

The solid obtained was then washed with dichloromethane and dried under vacuum.

The lithium bis (fluorosulfonyl) imide obtained has a purity of greater than 90% by weight.