Method for producing bis(halogenosulfonyl)imides

Abstract

The present invention relates to a novel synthetic route for preparing bis(halogenosulfonyl)imides, which are useful intermediates in the synthesis of lithium bis(fluorosulfonyl)imide (LiFSI).

Description

[Technical Field]

[0001] Cross-reference to related patent applications This application claims priority to European application No. 22306396.7 filed on September 22, 2022, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a novel synthetic route for preparing bis(halogenosulfonyl)imides, which are useful intermediates in the synthesis of lithium bis(fluorosulfonyl)imide (LiFSI). [Background technology]

[0003] Bis(fluorosulfonyl)imides and their salts, particularly the lithium salt of bis(fluorosulfonyl)imide (LiFSI), are useful compounds in various technical fields, such as battery electrolytes.

[0004] Several methods for the preparation of LiFSI have been described in the art. Among the various techniques described, most use a fluorination reaction with a fluorinating agent in a solvent.

[0005] Much effort has also been devoted to improving the manufacturing processes for the intermediate compounds leading to LiFSI, particularly with regard to purity, yield and cost reduction.

[0006] US Patent Application Publication No. 2014 / 0075746 (in the name of Arkema France) discloses a compound of the formula: (III)(SO3 - )-N - -(SO3 - )3C + (In the formula, C + represents a monovalent cation) discloses a process for preparing a bis(sulfonato)imide salt of the formula: (I)HO-SO2-NH2 with an amidosulfonic acid of the formula: (II)HO-SO2-X (wherein X represents a halon atom) with a halosulfuric acid and the cation C + This includes reaction with a base, the salt formed by

[0007] According to an embodiment of such a process, the reaction between compounds of formula (I) and (II) is carried out in a manner similar to that of the formula: (IV)HO-SO2-NH-SO2-OH which is then reacted with a cation C to provide a compound of formula (III) above. + The compound of formula (III) thus obtained is further purified in water or other polar solvents such as alcohols.

[0008] European Patent No. 2415757 (Central Glass Co., Ltd.) discloses the production of the B-XSI structure by reacting a sulfuryl halide (e.g., XSO2X, where X is Cl or F) or a phosphoryl halide with ammonia in the presence of an organic base (B). Comparative Examples 1 and 2 disclose the reaction of SO2F2 with SO2Cl2 and NH3, respectively, without the addition of a base. Only sulfamide compounds were isolated, and it was concluded that the desired ammonium salt was hardly obtained without an organic base.

[0009] U.S. Patent No. 8,840,856 B2 (Central Glass Co., Ltd.) claims a method for preparing imide salts, comprising reacting an alkali metal fluoride, a sulfuryl dihalide or phosphoryl halide, and ammonia or an ammonium salt. The presence of an alkali metal fluoride is essential, and in the examples it is used in molar excess relative to ammonia. Comparative Example 1 shows that a reaction carried out without an alkali metal fluoride did not yield the desired product, and sulfamide was obtained as the main component.

[0010] EP 2920147B1 (TRINAPCO Inc.) claims a method for preparing a salt of a bis(fluorosulfonyl)imide anion, which comprises adding sulfuryl fluoride to solid ammonium fluoride in a solvent in the presence of an aprotic base and isolating the resulting salt. In Comparative Example 1, NH4Cl is used in combination with 1,3-bis(dimethylamino)propane (TMPDA) base. However, the product thus obtained is not disclosed, and only the formation of a mixture is described.

[0011] US Patent Application Publication No. 2012 / 0245386 (TRINAPCO Inc.) discloses a comparison of methods of adding NH to a SOF solution in the presence of an organic base, preferably selected from N,N,N',N'-tetramethyl-1,2-ethanediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, and combinations thereof.

[0012] WO 2007 / 104144 (in the name of TRANSFERT PLUS, SEC) describes a compound of formula R1-SO2-R1 and a compound of formula R6-N - -R6Q + wherein each R is independently F or Cl, each R is H, Li, Na, K, Cs, or (R)Si—, and Q + teeth, [ka] (selected from The reaction between

[0013] Applicant is not aware of any disclosure of preparing NH4XSI (X is Cl or F) starting from an ammonium salt without using a stoichiometric amount of base. Summary of the Invention

[0014] The applicant has recognized that, despite all attempts in the art, there remains a need to produce intermediate compounds suitable for the synthesis of lithium bis(fluorosulfonyl)imide (LiFSI) by a process that can be easily carried out on an industrial scale.

[0015] In particular, the applicant faced the problem of producing an intermediate suitable for the synthesis of LiFSI by a process that meets all of the above requirements.

[0016] Applicants have surprisingly found that bis(halogenosulfonyl)imides can be obtained by reacting a sulfuryl halide with at least one ammonium compound.

[0017] Such processes can be advantageously carried out without a base, resulting in less process complexity and less solid waste generation compared to prior art processes.

[0018] The process according to the invention also has the advantage that the reactants and part of the by-products formed during the reaction can be recycled, resulting in a low environmental coefficient (E-factor) of the process, which is defined as the ratio between the "total waste amount" and the "product amount".

[0019] In addition to the above, the reaction according to the present invention can be easily controlled to suppress both exothermic reactions and side reactions. DETAILED DESCRIPTION OF THE INVENTION

[0020] In this application: - any description, even if made in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the invention; - When an element or component is said to be included in and / or selected from a list of enumerated elements or components, it is to be understood that in the relevant embodiments expressly contemplated herein, the element or component may be any one of the individually enumerated elements or components, or may be selected from a group consisting of any two or more of the explicitly enumerated elements or components, and that any element or component enumerated in a list of elements or components may be omitted from such list.

[0021] In a first aspect, the present invention provides a compound of formula (I) or (II): [ka] (In the formula, each X is independently selected from F, Cl and Br; and R is a linear or branched alkyl group containing 1 to 10 carbon atoms. A method for producing a bis(halogenosulfonyl)imide of the formula: a) Formula X a SO2X b (In the formula, X a and X b each of which is the same or different from one another and is selected from F, Cl and Br; b) providing at least one ammonium salt; c) contacting said sulfuryl halide with said at least one ammonium salt to obtain a bis(halogenosulfonyl)imide of formula (I) or (II). The present invention relates to a method comprising:

[0022] Preferably, the compound of formula X a SO2X b In sulfuryl halides, X a and X b are identical to each other.

[0023] Preferably, the sulfuryl halide is selected from Cl—SO 2 —Cl, Cl—SO 2 —F and F—SO 2 —F, more preferably Cl—SO 2 —Cl.

[0024] Preferably, Cl-SO2-Cl is provided in liquid form.

[0025] Preferably, each of Cl—SO 2 —F and F—SO 2 —F is provided in its gaseous form.

[0026] Preferably, the at least one ammonium salt has the formula (III): [ka] (In the formula, R is a linear or branched alkyl group containing 1 to 10 carbon atoms, and The M anion is preferably selected in the group comprising F, Cl, carboxylate, sulfate, hydrogen-sulfate, carbonate, hydrogen-carbonate, tetrafluoroborate and hexafluorophosphate. Follow.

[0027] Preferably, said at least one ammonium salt is provided in its solid form.

[0028] Preferably, the ammonium salt is NH4Cl or NH4F.

[0029] In step c), a sulfuryl halide is reacted with said at least one ammonium salt to obtain a bis(halogenosulfonyl)imide of formula (I) or (II) as defined above.

[0030] Step c) can be carried out in the presence or absence of a solvent.

[0031] If step c) is carried out in the presence of a solvent, said solvent is preferably selected from the group comprising ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, dimethoxymethane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 4-methyl-1,3-dioxolane, methyl formate, methyl acetate, methyl propionate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, 3-methylsulfolane, dimethyl sulfoxide, N,N-dimethylformamide, N-methyloxazolidinone, acetonitrile, valeronitrile, benzonitrile, ethyl acetate, isopropyl acetate, n-butyl acetate, nitromethane and nitrobenzene.

[0032] When step c) is carried out in the absence of a solvent, the sulfuryl halide is advantageously in its liquid form. According to this embodiment, when Cl-SO2-F and F-SO2-F are used, they are liquefied under pressure before carrying out step c).

[0033] Preferably, step c) is carried out at a temperature of about 15°C to 150°C.

[0034] Preferably, step c) is carried out under stirring.

[0035] According to one embodiment, step c) is carried out in the presence of a solvent.

[0036] According to this embodiment, the temperature is appropriately selected based on the solvent used and its boiling point. For example, the temperature may be maintained at 15°C to 100°C, more preferably 15°C to 75°C, and even more preferably 20°C to 50°C.

[0037] According to this embodiment, the molar ratio between the sulfuryl halide and said at least one ammonium salt in step c) is 100-0.1, preferably 10-1, more preferably also 1.5-1.

[0038] According to another embodiment, step c) is carried out in the absence of a solvent (also called "neat conditions").

[0039] According to this embodiment, the temperature is between 50°C and 100°C, more preferably between 60°C and 70°C.

[0040] According to this embodiment, the molar ratio between the sulfuryl halide and the at least one ammonium salt is 100-0.1, more preferably 50-1, and even more preferably 5-1.

[0041] When sulfuryl halide is used in excess as described in any of the above embodiments, it may be advantageous to distill off the unreacted sulfuryl halide. More preferably, such distilled sulfuryl halide is recycled, i.e., provided in step a).

[0042] Preferably, in the process according to the invention, the sulfuryl halide is ClSO2Cl and the at least one ammonium salt is NH4 + Cl - is.

[0043] According to such an embodiment, the method according to the invention comprises: a*) providing a sulfuryl halide of formula ClSO2Cl, b) Formula NH4 + Cl - providing at least one ammonium salt of c*) contacting said sulfuryl halide with said at least one ammonium salt to obtain a bis(halogenosulfonyl)imide [ammonium-CSI] of formula (I) wherein each X is chlorine. Includes:

[0044] The reaction in step c*) is advantageously carried out under the conditions described above for step c).

[0045] The ammonium-CSI can be isolated or purified from the reaction environment. Alternatively, it can be used directly in subsequent reactions.

[0046] Advantageously, ammonium-CSI can be reacted with a fluorine-containing compound to produce ammonium-FSI.

[0047] According to this embodiment, the process according to the invention comprises, after step c*), a step d) of contacting said ammonium-CSI with at least one fluorinating agent to obtain ammonium-FSI.

[0048] Step d) therefore involves the fluorination reaction of said ammonium-CsI to obtain ammonium-FSI.

[0049] Such a fluorinating agent is preferably HF, more preferably anhydrous HF or X c F (where X c is selected from the group consisting of NH4, Cs, Li, K).

[0050] When the fluorinating agent is NH4F, the reaction proceeds to produce NH4Cl as a by-product, which can be advantageously recycled by providing it in step b).

[0051] Preferably, in the process according to the invention, the sulfuryl halide is ClSO2Cl and the at least one ammonium salt is NH4 + F - is.

[0052] According to this embodiment, the method of the present invention comprises: a**) providing a sulfuryl halide of formula ClSO2Cl, b) Formula NH4 + F - providing at least one ammonium salt of c**) contacting said sulfuryl halide with said at least one ammonium salt to obtain a bis(halogenosulfonyl)imide of formula (I) [ammonium-FSI], wherein each X is fluorine. Includes:

[0053] The reaction in step c**) is advantageously carried out under the conditions described above for step c).

[0054] The ammonium-FSI obtained at the end of step d) or step c**) can be isolated or purified. Alternatively, such ammonium-FSI can be used directly in a subsequent reaction.

[0055] The ammonium-FSI obtained at the end of step d) or step c**) can be advantageously used as an intermediate compound in the preparation of LiFSI.

[0056] According to a preferred embodiment, NH4-FSI is reacted with a lithiating agent to produce LiFSI.

[0057] Therefore, in a further embodiment, the present invention relates to a method for producing LiFSI, comprising the steps of: d with a compound of formula (I), thereby obtaining LiFSI.

[0058] Preferably, the compound LiX d are lithium chloride (LiCl), lithium fluoride (LiF), lithium carbonate (Li2CO3), lithium hydroxide (LiOH, LiOH·H2O), which may optionally be in hydrated form, lithium sulfate (Li2SO4), lithium carboxylate (Li n (RCO2) n ), Li2SiO3, Li2B4O7 and mixtures thereof.

[0059] Preferably, step e) is carried out in the presence of at least one solvent so that LiFSI is obtained as a liquid composition.

[0060] Preferably, the at least one solvent is selected from the group comprising ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, dimethoxymethane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 4-methyl-1,3-dioxolane, methyl formate, methyl acetate, methyl propionate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, 3-methylsulfolane, dimethyl sulfoxide, N,N-dimethylformamide, N-methyloxazolidinone, acetonitrile, valeronitrile, benzonitrile, ethyl acetate, isopropyl acetate, n-butyl acetate, nitromethane and nitrobenzene.

[0061] More preferably, the solvent is selected from ethylene carbonate, propylene carbonate, butylene carbonate, tetrahydrofuran, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate, isopropyl acetate, and n-butyl acetate, and even more preferably, the solvent is selected from dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate, isopropyl acetate, and n-butyl acetate.

[0062] More preferably, the liquid composition contains 1 to 70% by weight, even more preferably 5 to 50% by weight, and even more preferably 15 to 40% by weight of the LiFSI based on the total weight of the liquid composition.

[0063] The process of the present invention is carried out in a reactor.

[0064] Preferably, some or more preferably all of the steps of the process according to the invention are carried out in a reactor that can withstand corrosion from the reagents and products and / or by-products obtained as the reaction proceeds, and for this purpose corrosion-resistant materials are selected for the parts of the reactor that come into contact with the reaction medium.

[0065] Preferably, the corrosion-resistant material is an alloy based on molybdenum, chromium, cobalt, iron, copper, manganese, titanium, zirconium, aluminum, carbon and tungsten, commercially available under the trade name Hastelloy®, in particular Hastelloy® C276, or in particular Inconel® or Monel®, commercially available under the trade name Inconel®, in particular Inconel® 600, 625 or 718. TM The alloy is selected from alloys of nickel, chromium, iron and manganese with additions of copper and / or molybdenum, commercially available as CI 4000004.

[0066] The corrosion-resistant material may be chosen from austenitic steels, more particularly stainless steels such as 304, 304L, 316 or 316L stainless steels. Preferably, steels are used having a nickel content of at most 22% by weight, preferably between 6% and 20% by weight, and more preferentially between 8% and 14% by weight. 304 and 304L steels have a nickel content varying between 8% and 12% by weight, while 316 and 316L steels have a nickel content varying between 10% and 14% by weight. More preferably, 316L steel is chosen.

[0067] The corrosion-resistant material can be a polymeric material that provides a coating on the parts of the reactor that come into contact with the reaction medium and is resistant to corrosion by the reaction medium, such as PTFE (polytetrafluoroethylene, or Teflon) or PFA (perfluoroalkyl resin).

[0068] Alternatively and more preferably, said corrosion resistant material is selected from glass, glass lining and enamel equipment.

[0069] Preferably and advantageously, all raw materials used in the process according to the invention, including the reactants, may preferably exhibit very high purity.

[0070] Preferably, the content of metal components such as Na, K, Ca, Mg, Fe, Cu, Cr, Ni, and Zn is less than 10 ppm, more preferably less than 5 ppm or less than 2 ppm.

[0071] In a further object, the present invention relates to the use of said liquid composition as a non-aqueous electrolyte solution in a battery.

[0072] To the extent that the disclosure of any patents, patent applications, and publications incorporated herein by reference conflicts with the statements of this application to the extent that a term may be unclear, the statements of this application shall control.

[0073] The present invention will now be described in more detail with reference to the following examples, the purpose of which is illustrative only and is not intended to limit the scope of the present disclosure. [Example]

[0074] material Sulfuryl chloride, acetonitrile, and ammonium chloride were purchased and used as received. SO2Cl2: Sigma Aldrich (product code #157767, batch #STBK3652) NH4Cl: Alfa Alesar (product code #12361, batch #Y28E029)

[0075] method 15 N-NMR analysis was carried out using insensitive nuclear enhancement by polarization transfer (INEPT) as a signal enhancement method.

[0076] Example 1 (NEAT condition) Ammonium chloride (1.6 g, 30 mmol, 0.3 equiv.) was added portionwise to neat sulfuryl chloride (8.08 mL, 100 mmol, 1 equiv.) in an oven-dried 25 mL round-bottom flask containing a PTFE-coated magnetic stirrer with stirring at 0 °C. The flask was fitted with a reflux condenser, and the reaction mixture was stirred at reflux for 24 h. The reaction mixture was then cooled to room temperature, filtered, and concentrated under reduced pressure to give an orange solid.

[0077] Final trituration in acetonitrile gave the pure product as a white solid.

[0078] The yield was 44% (1.54 g, 6.6 mmol). 1 H-NMR and 15 Characteristic peaks were observed in N-NMR analysis.

[0079] Example 2 (using acetonitrile as solvent) The reaction of excess sulfuryl chloride with ammonium chloride was carried out according to the procedure disclosed in Example 1 above, but in the presence of acetonitrile as the solvent.

[0080] The reaction medium was filtered to remove ammonium chloride, yielding a mixture. 1 The product was analyzed by H-NMR.

[0081] This compound 1 H-NMR and 15 Further analysis was performed by N-NMR, and no peaks for HCSI or other by-products were detected.

[0082] Example 3 (neat conditions) Following the same procedure as disclosed in Example 1 above, SO2Cl2 maintained at its boiling point was reacted with a substoichiometric amount of NH4Cl.

[0083] After 1 hour at 69°C, the reaction medium began to solidify and at the end of the 24 hour reaction a mixture of ammonium-CSI and unreacted solid NH4Cl was recovered.

[0084] Ammonium-CSI was obtained in 48% yield. The product was analyzed and 1 H-NMR and 15 It was characterized by N-NMR.

Claims

1. Formula (I) or (II): 【Chemical 1】 (In the formula, R is a linear or branched alkyl group containing 1 to 10 carbon atoms, and Each X is independently selected from F, Cl, and Br.

1. A method for producing a bis(halogenosulfonyl)imide of the formula: a) Formula X ａ SO ２ X ｂ (In the formula, X ａ and X ｂ are the same or different and are selected from F, Cl and Br. providing a sulfuryl halide of b) providing at least one ammonium salt; c) contacting said sulfuryl halide with said at least one ammonium salt to obtain said bis(halogenosulfonyl)imide of formula (I) or (II). A method comprising:

2. The sulfuryl halide is Cl—SO ２ -Cl, Cl-SO ２ -F and F-SO ２ 2. The method of claim 1, wherein the aryl group is selected from the group consisting of -F.

3. The at least one ammonium salt has the formula (III): 【Chemistry 2】 (In the formula, R is H or a linear or branched alkyl group containing 1 to 10 carbon atoms, and M is selected from the group comprising F, Cl, carboxylate, sulfate, hydrogen-sulfate, carbonate, hydrogen-carbonate, tetrafluoroborate, hexafluorophosphate. The method according to claim 1 or 2,

4. The method according to any one of claims 1 to 3, wherein step c) is carried out at a temperature of from 15°C to 150°C and / or under stirring.

5. The method according to any one of claims 1 to 4, wherein step (c) is carried out in the presence of a solvent.

6. 6. The method of claim 5, wherein the solvent is selected from the group comprising ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, dimethoxymethane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 4-methyl-1,3-dioxolane, methyl formate, methyl acetate, methyl propionate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, 3-methylsulfolane, dimethyl sulfoxide, N,N-dimethylformamide, N-methyloxazolidinone, acetonitrile, valeronitrile, benzonitrile, ethyl acetate, isopropyl acetate, n-butyl acetate, nitromethane, and nitrobenzene.

7. 7. The method according to claim 5 or 6, wherein step c) is carried out at a molar ratio between said sulfuryl halide and said at least one ammonium salt of from 100 to 0.1, preferably from 10 to 1, more preferably from 1.5 to 1.

8. The process according to any one of claims 1 to 4, wherein step c) is carried out in the absence of a solvent and / or at a temperature of from 50°C to 100°C, more preferably from 60°C to 70°C.

9. 9. The method according to any one of claims 1 to 8, wherein the molar ratio between the sulfuryl halide and the at least one ammonium salt is between 100 and 0.1, preferably between 50 and 1, more preferably between 5 and 1.

10. In the bis(halogenosulfonyl)imide of formula (I), each X is chlorine [ammonium-CSI], and the process comprises: a*) Formula ClSO ２ providing a sulfuryl halide of Cl; b) Formula NH ４ ＋ Cl － providing at least one ammonium salt of c*) contacting the sulfuryl halide with the at least one ammonium salt, thereby obtaining the ammonium-CSI. The method according to any one of claims 1 to 9, comprising:

11. 11. The method of claim 10, comprising, after step c*), a step d) of contacting the ammonium-CSI with at least one fluorinating agent to obtain ammonium-FSI.

12. The at least one fluorinating agent is HF, more preferably anhydrous HF or X ｃ F (where X ｃ is NH ４ 12. The method of claim 11 , wherein the metal is selected from the group consisting of: Cs, Li, K.

13. In the bis(halogenosulfonyl)imide of formula (I), each X is fluorine [ammonium-FSI], and the process comprises: a**) Formula ClSO ２ providing a sulfuryl halide of Cl; b) Formula NH ４ ＋ F － providing at least one ammonium salt of c**) contacting said sulfuryl halide with said at least one ammonium salt, thereby obtaining said ammonium-FSI. The method according to any one of claims 1 to 9, comprising:

14. 13. A method for producing lithium bis(fluorosulfonyl)imide (LiFSI), comprising the steps of: after step d) of claim 11 or after step c**) of claim 13, reacting the ammonium-FSI with a compound of formula LiX ｄ with a compound of formula (I), thereby obtaining LiFSI.

15. The formula LiX ｄ The compounds are LiCl, LiF, Li ２ CO ３ , LiOH, LiOH. H ２ O, Li ２ SO ４ , Li ｎ (R.C.O. ２ ) ｎ , Li ２ SiO ３ , Li ２ B ４ O ７ and mixtures thereof.

16. 16. The method of claim 14 or 15, wherein step e) is carried out in the presence of at least one solvent and the LiFSi is obtained as a liquid composition comprising 1 to 70 wt. % LiFSI, based on the total weight of the liquid composition.

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