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    • 专利摘要:
    The invention relates to a process for the preparation of a fluorinated compound of formula: (III) R2- (SO2) -NX- (SO2) -F, comprising: (a) a first step for obtaining the chlorinated compound of formula: (II) R1- (SO2) -NX- (SO2) -Cl; this first step comprising reacting the sulfonamide of formula: (I) R0- (SO2) -NH2 with a sulfur acid and a chlorinating agent; and (b) a second step for obtaining the fluorinated compound of formula (III), said second step comprising reacting the chloro compound of formula (II) with anhydrous hydrofluoric acid in at least one organic solvent; wherein: - X represents either a hydrogen atom or a monovalent cation M; R1 represents an electroattractor group having a positive Hammett parameter σp; if R1 represents Cl, then R0 represents OH; otherwise, R0 is identical to R1; and - if R1 is Cl, then R2 is F; otherwise, R2 is identical to R1.
    公开号:FR3020060A1
    申请号:FR1453523
    申请日:2014-04-18
    公开日:2015-10-23
    发明作者:Gregory Schmidt；Sophie Audureau
    申请人:Arkema France SA；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to a process for the preparation of imides containing a fluorosulfonyl group.
    [0002] TECHNICAL BACKGROUND Sulfonylimide anions, by their very low basicity, are increasingly used in the field of energy storage in the form of inorganic salts in batteries, or organic salts in supercapacitors or in the field of ionic liquids. As the battery market is booming and the reduction of battery manufacturing costs becomes a major issue, a large-scale and low-cost synthesis process for this type of anion is necessary. In the specific field of Li-ion batteries, the salt currently used most is LiPF6 but this salt shows many disadvantages such as limited thermal stability, instability to hydrolysis and therefore lower battery safety. Recently, new salts having the FSO 2 group have been studied and have demonstrated many advantages such as better ionic conductivity and resistance to hydrolysis. One of these salts, LiFSI (LiN (FSO2) 2) has shown very interesting properties that make it a good candidate to replace LiPF6. Few processes for synthesizing LiFSI or its corresponding acid have been described, but it is clear that in all these processes the key step is the formation step of the S-F bond. A first synthetic route described (Appel & Eisenbauer, Chem. Ber. 95, 246-8, 1962) consists of the reaction of fluorosulfonic acid (FSO3H) with urea. However, the corrosive and toxic nature of this compound does not allow industrialization of the process. EP 2415709 discloses a process based on this route, in which the products of the reaction of fluorosulfonic acid with urea are dissolved in water and bis (fluorosulfonyl) imide is precipitated in salt form with tetrabutylammonium . This synthetic route is not viable on a large scale because the overall yield is very low.
    [0003] Another way is to react difluorosulfoxide with ammonia: see WO 2010/113835 in this regard. But this method also forms many secondary products, which requires expensive purification steps.
    [0004] Another way (Ruff & Lustig, Inorg, Synth, 1968, 11, 138-43) is to synthesize in a first step a dichlorinated compound of formula (CISO 2) 2 NH and then to carry out a chlorine / fluorine exchange with AsF 3. However, this process is not industrializable because of the high price and toxicity of AsF3. WO 02/053494 describes another route which consists of a Cl / F exchange on (CISO2) 2NH using a monovalent cation fluoride which can be alkaline or of onium type (NR4 +), in a solvent aprotic. However, according to this document, the reaction is very slow. Example 10 of WO 2007/068822 describes the synthesis of bis (fluorosulfonyl) imide in hydrofluoric acid (HF) anhydrous. Thus, the reaction is carried out in an autoclave with 1 g of bis (chlorosulfonyl) imide and 4 g of anhydrous HF at different temperatures and reaction times. The document teaches that even at temperatures of 130 ° C, the reaction yield does not exceed 55%. In addition, he teaches that the presence of impurities makes separation difficult on an industrial scale. It is concluded that synthesis of bis (fluorosulfonyl) imide by HF is unsatisfactory, and the use of lithium fluoride is recommended. WO 2009/123328 describes the manufacture of sulfonylimide compounds, with a reaction between amidosulphuric acid and thionyl chloride, then with chlorosulfonic acid, to form bis (chlorosulfonyl) imide, which is then subjected to a step fluoridation. The fluorination is carried out with a fluorinated compound such as CuF2, ZnF2, SnF2, PbF2 or BiF3. These fluorinated compounds are however of a high cost, making it difficult to operate the process on an industrial scale. There is therefore still a need to produce imides containing a sulfonyl group (such as LiFSI), especially according to a process that can be carried out on an industrial scale. SUMMARY OF THE INVENTION The invention firstly relates to a process for the preparation of a fluorinated compound of formula: (III) R2- (SO2) -NX- (SO2) -F, comprising: (a) a first step allowing obtain the chlorinated compound of formula: (II) R 1 - (SO 2) -NX- (SO 2) -CI; this first step comprising reacting the sulfonamide of the formula: (I) Ro- (SO 2) -NH 2 with a sulfuric acid and a chlorinating agent; and (b) a second step for obtaining the fluorinated compound of formula (III), said second step comprising reacting the chloro compound of formula (II) with anhydrous hydrofluoric acid in at least one organic solvent; wherein: - X represents either a hydrogen atom or a monovalent cation M - R1 represents an electron-withdrawing group having a positive Hammett parameter a; if R1 represents Cl, then Ro represents OH; otherwise, Ro is identical to R1; and - if R1 is Cl, then R2 is F; otherwise, R2 is the same as in one embodiment, R1 is selected from Cl, F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C3HF6, C4F9, C4H2F7, C4H4F5, C5F11, C3F6OCF3, C2F4OCF3, C2H2F2OCF3, CF2OCF3, C6F13, C7F15, C8F17 or C9F19.
    [0005] According to one embodiment, M represents an alkali metal or alkaline earth metal cation or a quaternary ammonium cation, and preferably M represents a lithium or sodium cation, and more preferably a lithium cation. According to one embodiment, the sulfur acid used in the first step is selected from chlorosulfonic acid, sulfuric acid, oleum and mixtures thereof. According to one embodiment, the chlorinating agent used in the first step is chosen from thionyl chloride, oxalyl chloride, phosphorus pentachloride, phosphonyl trichloride, phosphoryl trichloride and mixtures thereof. .
    [0006] According to one embodiment: a catalyst is used for the reaction of the sulfonamide with the sulfuric acid and the chlorinating agent in the first step, which is preferably chosen from a tertiary amine such as methylamine, triethylamine or diethylmethylamine or pyridine and its derivatives such as 2,6-lutidine; and / or - the reaction of the sulfonamide with the sulfuric acid and the chlorinating agent in the first stage is carried out at a temperature between 30 and 150 ° C; and / or - the reaction of the sulfonamide with the sulfuric acid and the chlorinating agent in the first stage is carried out at a pressure of between 1 and 7 bars absolute. According to one embodiment: the molar ratio between the sulfuric acid and the sulfamide involved in the first step is between 1 and 5; and / or the molar ratio between the chlorinating agent and the sulphonamide used in the first stage is between 1 and 10. According to one embodiment, the organic solvent in the second stage has a donor number of between 1 and 70, and advantageously between 5 and 65. According to one embodiment, the organic solvent in the second step is chosen from esters, nitriles, dinitriles, ethers, diethers, amines and phosphines, and mixtures of them. According to one embodiment: the reaction of the chlorinated compound of formula (II) with the anhydrous hydrofluoric acid of the second step is carried out at a temperature of between 0 ° C. and the boiling point of the organic solvent, preferably between 5 ° C and the boiling temperature of the organic solvent; and / or the reaction of the chlorinated compound of formula (II) with the anhydrous hydrofluoric acid of the second stage is carried out at a pressure of between 0 and 16 bars absolute. According to one embodiment, the chlorinated compound of formula (II) is dissolved in the organic solvent prior to the second reaction step.
    [0007] According to one embodiment: the mass ratio between the chlorinated compound of formula (II) and the organic solvent involved in the reaction of the chlorinated compound of formula (II) with the anhydrous hydrofluoric acid of the second stage is between 0.001 and 10 and preferably between 0.005 and 5; and / or the molar ratio between the chlorinated compound of formula (II) and the hydrofluoric acid involved in the reaction of the chlorinated compound of formula (II) with the anhydrous hydrofluoric acid of the second stage is between 0, 01 and 0.5 and preferably between 0.05 and 0.5. According to one embodiment, the reaction of the sulfonamide with the sulfuric acid and the chlorinating agent of the first step provides the chlorinated compound of formula: (11a) R1- (SO2) -NH- (SO2) -CI; the first step further comprising reacting the chlorinated compound of formula (IIa) with a base to obtain the chlorinated compound of the formula: (11b) Ri (502) -NM- (502) -CI; in which M represents a monovalent cation. According to one embodiment, said base is chosen from alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydroxides, alkaline earth metal hydroxides, tertiary amines in a polar organic solvent, and mixtures of these. this.
    [0008] According to one embodiment, the process comprises, after the second step: (c) a third neutralization step of the compound of formula (III), preferably by addition of a base selected from alkali metal carbonates, carbonates of alkaline earth metal, alkali metal hydroxides, alkaline earth metal hydroxides and mixtures thereof. According to one embodiment, the fluorinated compound of formula (III) obtained in the second step is a compound of formula: (IIIa) R2- (502) -NH- (502) -F and the third neutralization stage makes it possible to convert the compound of formula (111a) to a compound of formula: (IIIb) R2- (502) -NM- (502) -F where M is a monovalent cation. According to one embodiment, the process comprises, after the second step or, as the case may be, the third step, a final cation exchange step, preferably by contacting with a fluoride, chloride, carbonate, hydroxide, sulfate, chlorate, perchlorate, nitrite or nitrate of alkali or alkaline earth metal or quaternary ammonium. According to one embodiment, the process makes it possible to obtain LiN (FSO2) 2, LiN (SO2CF3) (SO2F), LiN (SO2C2F5) (SO2F), LiN (SO2CF20CF3) (SO2F), LiN (SO2C3HF6). ) (SO2F), LiN (SO2C4F9) (SO2F), LiN (502C5F11) (502F), LiN (SO2C6F13) (SO2F), LiN (5O2C7F15) (5O2F), LiN (5O2C8F17) (50F) or LiN (SO2C9F19) (SO2F), and preferably LiN (FSO2) 2. The invention also relates to a method for producing an electrolyte, comprising preparing an imide salt of formula (IIIb) R2- (502) -NM- (502) -F, where M represents a monovalent cation and R2 represents an electron-withdrawing group having a positive Hammett parameter a, by the method described above, and dissolving it in a solvent, said imide salt being preferably a lithium or sodium salt.
    [0009] The invention also relates to a method of manufacturing a battery or a battery cell, comprising the manufacture of an electrolyte according to the above method and the insertion of this electrolyte between an anode and a cathode. The invention also relates to a composition comprising at least 99.9% by weight of an imide salt of the formula: (IIIb) R2- (502) -NM- (502) -F wherein M represents a monovalent cation and R2 represents an electron-withdrawing group having a positive Hammett parameter a, the composition comprising a mass content of total alkali or alkaline earth metal fluorides of 1 to 500 ppm, and / or a mass content of alkali or alkaline earth metal chlorides; totals from 1 to 200 ppm. According to one embodiment, the mass content of total alkali or alkaline earth metal fluorides is from 1 to 250 ppm and / or the mass content of total alkali or alkaline earth metal chlorides is from 1 to 100 ppm.
    [0010] According to one embodiment, the composition comprises a mass content of nitrates of less than or equal to 250 ppm, preferably less than or equal to 150 ppm; and / or a sulphate mass content less than or equal to 250 ppm, preferably less than or equal to 150 ppm. According to one embodiment: - M represents Li or Na; and / or - R2 represents F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C3H4F3, C3HF6, C4F9, C4H2F7, C4H4F5, C3F6OCF3, C2F4OCF3, C2H2F2OCF3, CF2OCF3, C6F13, C7F15, CaF17 or C9F19, F being preferred. According to one embodiment, the imide salt is LiN (FSO2) 2, LiN (SO2CF3) (SO2F), LiN (SO2C2F5) (SO2F), LiN (SO2CF20CF3) (SO2F), LiN (SO2C3HF6). ) (SO2F), LiN (SO2C4F9) (SO2F), LiN (SO2C5F11) (SO2F), LiN (SO2C6F13) (SO2F), LiN (SO2C7F15) (SO2F), LiN (SO2C8F17) (SO2F) or LiN (SO2C9F19) (SO2F), and preferably LiN (FSO2) 2. The present invention overcomes the disadvantages of the state of the art. More particularly, it provides a process for producing imides containing a sulphonyl group (such as LiFSI) which can be used on an industrial scale, and without entailing an excessive cost. This is accomplished primarily by the fluorination reaction of a chlorinated bis (sulfonyl) imide compound with anhydrous hydrofluoric acid in an organic solvent. It has been surprisingly observed that this fluorination reaction provides an almost quantitative yield. Thus, the applicant has reversed the prejudice illustrated in WO 2007/068822.
    [0011] DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention is now described in more detail and in a nonlimiting manner in the description which follows. The invention provides for preparing a compound comprising at least one fluorosulfonyl group according to a general scheme in at least two steps: (a) Preparation of a compound comprising at least one chlorosulfonyl group. (b) Fluorination of the compound of step (a). In addition, a third step may optionally be provided: (c) Neutralization of the compound of step (b).
    [0012] In addition, a fourth step may be optionally provided, either after the third step or directly after the second step: (d) Exchange of cations.
    [0013] Step (a) In step (a), the sulphonamide of formula (I) Ro- (SO2) -NH2 is reacted with a sulfuric acid and a chlorinating agent, so as to obtain a chlorinated compound of formula (II) R1 (S02) -NX- (S02) Cl. X represents either a hydrogen atom or a monovalent cation denoted M. When X represents a hydrogen atom, the chlorinated compound above is the compound of formula (IIa) R1- (SO2) -NH- (SO2) Cl.
    [0014] When X represents a monovalent cation, the chlorinated compound is the salt of formula (11b) R1- (SO2) -NM- (SO2) -Cl, which can also be written R1- (SO2) -N- (SO2) - As a monovalent cation, an alkali metal, alkaline earth metal or quaternary ammonium cation may be used. Sodium and especially lithium are preferred. When the chlorinated compound (II) obtained at the end of the first step is the compound of formula (IIa), the reaction of the sulfonamide with sulfuric acid and the chlorinating agent makes it possible to obtain the chlorinated compound directly. When the chlorinated compound (II) obtained at the end of the first step is the compound of formula (11b), the reaction is carried out in two stages: firstly, the reaction of the sulphonamide with the sulfuric acid and the agent chlorinator, which makes it possible to obtain the chlorinated compound of formula (11a); - In a second step, the conversion of the chlorinated compound of formula (IIa) to the chlorinated compound of formula (11b) by reaction with a base. In all cases, R1 represents an electron-withdrawing group having a positive Hammett parameter a. R 1 may in particular represent Cl, F, or an alkyl or alkoxyalkyl group comprising from 1 to 9 carbon atoms, and substituted in whole or in part by fluorine. Examples of such groups are the groups: CF3, CHF2, CH2F, C2HF4, C2H2F3, C3H4F3, C3HF6, C4F9, C4H2F5, C4H4F5, C5F11, C3F6OCF3, C2F4OCF3, C2H2F2OCF3, CF2OCF3, , C8F17 and C9F19.
    [0015] When R 1 represents Cl, then the starting sulfamide is amidosulfonic acid of formula (I ') OH- (SO 2) -NH 2 (Ro represents OH).
    [0016] When R1 represents another group, then the starting sulfamide has the formula (I ") R1- (SO2) -NH2 (Ro is identical to R1) The sulfur acid used for the reaction may be CISO3H chlorosulfonic acid, or alternatively sulfuric acid or oleum Combinations of these reagents may also be used The chlorinating agent used for the reaction may be selected from thionyl chloride SOCl 2, oxalyl chloride (COCl) 2, phosphorus pentachloride PCI5, phosphonyl trichloride PCI3 or phosphoryl trichloride POCl 3. Combinations of these reagents can also be used.
    [0017] It is also possible to use a catalyst to accelerate the reaction, for example chosen from a tertiary amine such as methylamine, triethylamine or diethylmethylamine. Pyridine or a derivative thereof such as 2,6-lutidine can also be used. The molar ratio between the sulfuric acid and the sulphonamide is advantageously between 1 and 5. The molar ratio between the chlorinating agent and the sulphonamide is advantageously between 1 and 10, and more particularly: between 1 and 5 when the acid sulfur is chlorosulfonic acid; and between 2 and 10 when the sulfuric acid is sulfuric acid or oleum. The reaction temperature is advantageously between 30 and 150 ° C. The reaction time is advantageously between 1 hour and 7 days. The reaction may advantageously be carried out under a pressure of between 1 bar absolute and 7 bar absolute. The reaction leads to a gaseous release of HCl, as well as other gases which may be, for example, depending on the chlorinating agent used, CO, CO2 or SO2. Any unreacted reagents or degraded products in solution can be removed by a purification step by filtration or by recrystallization in an apolar solvent such as pentane, toluene or cyclohexane.
    [0018] With regard to the optional conversion reaction of the chlorinated compound of formula (IIa) to the chlorinated compound (salt) of formula (11b), the reaction is carried out by reacting the chlorinated compound of formula (IIa) with a base which may be, for example an alkali or alkaline earth metal carbonate, an alkali or alkaline earth metal hydroxide or a mixture thereof, or at least one tertiary amine in a polar-type organic solvent.
    [0019] As an organic solvent of the polar type, use may especially be made of acetonitrile, dioxane, tetrahydrofuran, ethyl acetate, butyl acetate and combinations thereof. This reaction can be carried out by dissolving the chlorinated compound of formula (IIa) in the organic solvent, for example at a concentration of 10-3 to 10 mol / L. The base can be added in liquid or solid form. The base / chlorine compound molar ratio of formula (IIa) can be for example 1 when the base is a hydroxide or an amine, or 2 when the base is a carbonate. The temperature of the reaction may for example be between -10 and 40 ° C. At the end of the reaction, the excess of base can be filtered, and the solution can be evaporated. Step (b) In step (b), the chlorination compound of formula (IIa) or of formula (IIb) obtained at the end of step (a) is fluorinated so as to obtain the compound fluorinated compound of formula (III) R1- (SO2) -NX- (SO2) -F. When the fluorination involves a chlorinated compound of formula (IIa), the fluorinated compound obtained is the compound of formula (IIIa) R2- (SO2) -NH- (SO2) -F.
    [0020] When the fluorination involves a chlorinated compound of formula (11b), the fluorinated compound obtained is the salt of formula (IIIb) R2- (SO2) -NM- (SO2) -F, which can also be written R2- ( When R1 is Cl, R2 is F. In all other cases, R2 is the same as R1 as defined above.
    [0021] Preferably, R2 is F, CF3, CHF2, CH2F or CF2OCF3. It is particularly preferred that R2 is F. The fluorination reaction utilizes anhydrous hydrofluoric acid (HF) in an organic solvent. The organic solvent preferably has a donor number of between 1 and 70 and advantageously of between 5 and 65. The donor index of a solvent represents the value -AH, where AH is the enthalpy of the interaction between the solvent and the solvent. antimony pentachloride (according to the method described in Journal of Solution Chemistry, Vol.13, No. 9, 1984). As organic solvent, there may be mentioned in particular esters, nitriles or dinitriles, ethers or diethers, amines or phosphines. Combinations thereof can also be used as the organic solvent.
    [0022] Methyl acetate, ethyl acetate, butyl acetate, acetonitrile, propionitrile, isobutyronitrile, glutaronitrile, dioxane, tetrahydrofuran, triethylamine, tripropylamine, diethylisopropylamine, pyridine trimethylphosphine, triethylphosphine, diethylisopropylphosphine and mixtures thereof may especially be suitable as organic solvents. The reaction with anhydrous HF can be carried out at a temperature preferably between 0 ° C and the boiling temperature of the organic solvent used. Advantageously, this temperature is between 5 ° C and the boiling temperature of the organic solvent.
    [0023] According to the present invention, the reaction step with anhydrous HF is carried out at a pressure which is preferably between 0 and 16 bar absolute. The chlorinated compound of formula (II) is preferably dissolved in the organic solvent prior to the reaction step with anhydrous HF.
    [0024] The weight ratio between the chlorinated compound of formula (II) and the organic solvent is preferably between 0.001 and 10, and advantageously between 0.005 and 5. HF is introduced into the reaction medium, preferably in gaseous form.
    [0025] The molar ratio between the chlorinated compound of formula (II) and the HF used is preferably between 0.01 and 0.5 and advantageously between 0.05 and 0.5. The reaction step with HF can be carried out in a closed medium or in an open medium.
    [0026] Without wishing to be bound by theory, the Applicant believes that the use of a donor organic solvent makes it possible to form a solvent-HF complex and thus to exalt the nucleophilia of the fluorine atom. The use of such a complex allows a gentle fluorination of the chlorinated compound of formula (II) thus avoiding parasitic cut-off reactions.
    [0027] The process according to the present invention makes it possible to obtain fluorination yields of between 85 and 100%, which represents a clear increase in comparison with the processes of the prior art. The fluorination reaction leads to the formation of HCl, the majority of which can be degassed from the reaction medium (just like the excess HF), for example by bubbling a neutral gas (such as nitrogen, helium or water). 'argon). However, residual HF and / or HCl may be dissolved in the reaction medium.
    [0028] Step (c) After step (b), the reaction medium is preferably neutralized, for example using an aqueous solution of alkali metal or alkaline earth metal carbonate M'CO3, nH2O or hydroxide alkali metal or alkaline earth metal M'OH, nH2O to obtain preferably a pH greater than 4. It is also possible to use mixtures of carbonates and / or hydroxides above. In the foregoing, M 'denotes a monovalent cation of alkali metal or alkaline earth metal.
    [0029] Residual HF and / or residual HCl dissolved in the solvent reacts with the above carbonate or hydroxide to form an alkaline or alkaline earth metal fluoride M'F (or a mixture of M'F fluorides). ), respectively an alkali metal or alkaline earth metal chloride M'Cl (or a mixture of chlorides M'Cl).
    [0030] The neutralization reaction may be carried out for example by adding an aqueous solution of the chosen base. The basic molar ratio / fluorinated compound of formula (III) may for example be 1 to 5 when the base is a hydroxide, or 2 to 10 when the base is a carbonate. The temperature of the reaction may for example be between -10 and 40 ° C.
    [0031] At the end of the reaction, the excess of base can be filtered, and the solution can be evaporated. This also largely eliminates the fluorides and chlorides formed. The solution may then be extracted with an organic solvent which may be, for example, dichloromethane, acetonitrile, ethyl acetate, butyl acetate, diethyl ether, terrahydrofuran, toluene or a mixture of them. This extraction can be performed several times to maximize the recovery yield. The organic phase obtained can then be extracted several times with water to purify the product. The organic solution can then be evaporated to provide the imide salt containing a desired fluorosulfonyl group. The imide salt thus obtained preferably has a mass content of fluorides of less than 500 ppm, and more preferably less than 250 ppm.
    [0032] And the imide salt thus obtained preferably has a mass content of chlorides of less than 200 ppm, and more preferably less than 100 ppm.
    [0033] It should be noted that, in the particular case where, after the second step, the fluorinated compound of formula (IIIa) R2- (SO2) -NH- (SO2) -F is obtained, the third neutralization stage such as as described above, also leads to converting this compound to the fluorinated compound (salt) of formula (IIIb) R2- (SO2) - NM- (SO2) -F, M being equal to M '. Step (d) Optionally, a cation exchange step may be provided at the end of the process. This step makes it possible to convert a fluorinated compound of formula (IIIb) R2- (SO2) -NM- (SO2) -F into a fluorinated compound of formula (WC) R2- (SO2) -NM "- (SO2) -F, where M "represents a monovalent cation. M "may especially represent an alkali metal or alkaline earth metal cation or a quaternary ammonium cation, for example, lithium or sodium cation, and more particularly lithium.
    [0034] This cation exchange step is carried out by placing the fluorinated compound of formula (IIIb) in the presence of a salt of the M "cation, which may be a fluoride, chloride, carbonate, hydroxide, sulfate, chlorate, perchlorate or nitrite salt. The reaction may be carried out, for example, in water or in a polar organic solvent such as in particular acetonitrile, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide or nitromethane. , dioxane, tetrahydrofuran, ethyl acetate, butyl acetate and mixtures thereof The reaction may be carried out for example at a temperature between 0 ° and the boiling point of the solvent used The reaction time may be, for example, between 1 hour and 5 days, the molar ratio between the salt of the cation M "and the salt of imide may be, for example, between 0.9 and 5. The concentration of 'imide d the water or the organic solvent may for example be between 0.001 and 5 mol / L. In the particular case where the solvent used is water, the reaction medium may then be extracted with an organic solvent which may be in particular dichloromethane, acetonitrile, ethyl acetate, butyl acetate or diethyl ether. , tetrahydrofuran, toluene or mixtures thereof. This extraction can be performed several times to maximize the recovery yield. The organic phase is then evaporated to give the imide salt of formula (IIIc).
    [0035] The process according to the present invention is particularly advantageous for producing the following imide salts: LiN (SO2F) 2, LiNSO2CF3SO2F, LiNSO2C2F5SO2F, LiNSO2CF2OCF3SO2F, LiNSO2C3HF6SO2F, LiNSO2C4F9SO2F, LiNSO2C5F11S02F, LiNSO2C6F13S02F, LiNSO2C7F15S02F, LiNSO2C8F17S02F and LiNSO2C9F19S02F. Preferably, these salts are obtained with a purity of at least 99.5% by weight, advantageously at least equal to 99.9% by weight. The impurities, such as LiCl, LiF and FSO3Li or NaCl, NaF and FSO3Na, optionally present in the imide salt, each preferably represent less than 1000 ppm, advantageously less than 500 ppm. The FSO3Li impurity is optionally present at a concentration of less than 5 ppm. The nitrates and sulphates, optionally present in the imide salt, are advantageously respectively present at a mass concentration of less than 250 ppm, and preferably of less than 150 ppm. As indicated above, the fluoride content that may be present is preferably less than 500 ppm, and more preferably less than 250 ppm. As indicated above, the chloride content that may be present is preferably less than 200 ppm, and more preferably less than 100 ppm. These impurity concentrations are mass concentrations relative to the desired imide salt mass. The imide salt obtained is preferably substantially free of water and impurities consisting of salts formed of a cation from groups 11 to 15 and periods 4 to 6 of the periodic table (for example Zn, Cu, Sn, Pb , Bi). These impurities are detrimental to the performance of Li-ion or Na-ion batteries by their electrochemical activity.
    [0036] Preparation of an Electrolyte The imide salt prepared as described above can be used for the preparation of an electrolyte, dissolving it in a suitable solvent. For example, as described in J. Electrochemical Society, 2011, 158, A74-82, LiFSI can be dissolved at a concentration of 1 mol / L in a mixture of ethylenecarbonate (EC), dimethylcarbonate ( DMC) and ethylmethylcarbonate (EMC) at 5 to 2 to 3 by volume; such electrolyte present shows very good conductivity, good stability in cycling and corrosion of aluminum above 4.2 V. This electrolyte can then be used for the manufacture of batteries or battery cells, by disposed between a cathode and an anode, in a manner known per se. EXAMPLES The following examples illustrate the invention without limiting it.
    [0037] Example 1 Sulfamic acid (1 eq, 0.515 mol, 50 g) is placed in a flask with thionyl chloride (3.75 eq, 1.93 mol, 229.8 g) and acid is poured in. 95% sulfuric acid (1 eq, 0.515 mol, 53.1 g) at room temperature. Thionyl chloride is refluxed for 24 hours with stirring. The dichloride finally obtained is light yellow in appearance, with residual sulfamic acid not solubilized. It is filtered to remove sulfamic acid (23.6 g) and the thionyl chloride is evaporated in vacuo. EXAMPLE 2 1 eq of sulfamic acid (0.25 mol, 24.25 g) and then thionyl chloride (2.75 eq, 0.69 mol, 81.9 g) are introduced into a glass flask or reactor. boy Wut). Then, with stirring, chlorosulfonic acid (2 eq, 0.5 mol, 58.25 g) is run at ambient temperature very slowly. Thionyl chloride (oil bath at 90 ° C.) is gradually refluxed and the mixture is left stirring for 24 hours. A gas evolution is observed which is trapped in the water at the outlet of the reactor. In the end, the product recovered in the balloon is liquid, slightly orange, very smoking. Example 3 In an 800 mL autoclave, 28 g of (CISO2) 2 NH are dissolved in 50 mL of acetonitrile. 10 g of HF are then added. The pressure is then 0.34 bar absolute and the temperature is maintained at 10 ° C. The reaction is left stirring in a closed medium for 18 hours. HF, in excess, is pumped off. The reaction medium is then treated with lithium carbonate. The solution is filtered and evaporated and the residue is analyzed by 19F NMR. The analysis shows the presence of 85% fully fluorinated product (FSO2) 2NLi, 7.5% FSO3Li and 7.5% FSO2NH2. These last two are the compounds formed during the degradation of the starting material. Example 4 In an 800 mL autoclave, 31.7 g of (CISO 2) 2 NH are dissolved in 50 mL of acetonitrile. 10 g of HF are then added. The pressure is then 0.75 bar absolute and the temperature is maintained at 20 ° C. The reaction is left stirring in a closed medium for 18 hours. HF, in excess, is pumped off. The reaction medium is then treated with lithium carbonate. The solution is filtered and evaporated and the residue is analyzed by 19F NMR. The analysis shows the presence of 100% fully fluorinated product (FSO2) 2NLi and the absence of FSO3Li and FSO2NH2 degradation products. Example 5 In an 800 mL autoclave, 61 g of (CISO 2) 2 NH are dissolved in 50 mL of 1,4-dioxane. 20 g of HF are then added. The pressure is then 2.3 bars absolute and the temperature is maintained at 25 ° C. The reaction is left stirring in a closed medium for 18 hours. HF, in excess, is pumped off. The reaction medium is then treated with lithium carbonate. The solution is filtered and evaporated and the residue is analyzed by 19F NMR. The analysis shows the presence of 100% fully fluorinated product (FSO2) 2NLi and the absence of FSO3Li and FSO2NH2 degradation products.
    权利要求:
    Claims (25)
    [0001]
    REVENDICATIONS1. A process for the preparation of a fluorinated compound of the formula: (III) R2- (SO2) -NX- (SO2) -F comprising: (a) a first step for obtaining the chlorinated compound of the formula: (SO2) -NX- (SO2) -CI; this first step comprising reacting the sulfonamide of the formula: (I) Ro- (SO 2) -NH 2 with a sulfuric acid and a chlorinating agent; and (b) a second step for obtaining the fluorinated compound of formula (III), said second step comprising reacting the chloro compound of formula (II) with anhydrous hydrofluoric acid in at least one organic solvent; wherein: - X represents either a hydrogen atom or a monovalent cation M; - R1 represents an electroattractor group having a positive Hammett parameter a; if R1 represents Cl, then Ro represents OH; otherwise, Ro is identical to R1; and - if R1 is Cl, then R2 is F; otherwise, R2 is identical to R1.
    [0002]
    2. Process according to claim 1, in which R1 is chosen from Cl, F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C3HF6, C4F9, C4H2F7, C4H4F5, C5F11, C3F6OCF3. C2F40CF3, C2H2F20CF3, CF20CF3, C6F13, C7F15, C8F17 or C9F19.
    [0003]
    3. The process as claimed in claim 1, wherein M represents an alkali metal or alkaline earth metal cation or a quaternary ammonium cation, and in which M preferably represents a lithium or sodium cation, and more preferably a cation. lithium.
    [0004]
    4. Method according to one of claims 1 to 3, wherein the sulfuric acid used in the first step is selected from chlorosulfonic acid, sulfuric acid, oleum and mixtures thereof.
    [0005]
    5. Method according to one of claims 1 to 4, wherein the chlorinating agent used in the first step is selected from thionyl chloride, oxalyl chloride, phosphorus pentachloride, phosphonyl trichloride, trichloride phosphoryl and mixtures thereof.
    [0006]
    6. Method according to one of claims 1 to 5, wherein: - a catalyst is used for the reaction of the sulfonamide with sulfuric acid and the chlorinating agent in the first step, which is preferably selected from a tertiary amine such as methylamine, triethylamine or diethylmethylamine, or pyridine and its derivatives such as 2,6-lutidine; and / or - the reaction of the sulfonamide with the sulfuric acid and the chlorinating agent in the first stage is carried out at a temperature between 30 and 150 ° C; and / or - the reaction of the sulfonamide with the sulfuric acid and the chlorinating agent in the first stage is carried out at a pressure of between 1 and 7 bars absolute.
    [0007]
    7. Method according to one of claims 1 to 6, wherein: - the molar ratio between the sulfuric acid and the sulfamide involved in the first step is between 1 and 5; and / or - the molar ratio between the chlorinating agent and the sulfamide used in the first stage is between 1 and 10.
    [0008]
    8. Method according to one of claims 1 to 7, wherein the organic solvent in the second step has a donor number between 1 and 70, and preferably between 5 and 65.
    [0009]
    9. Method according to one of claims 1 to 8, wherein the organic solvent in the second step is selected from esters, nitriles, dinitriles, ethers, diethers, amines and phosphines, and mixtures of them.
    [0010]
    10. Process according to one of Claims 1 to 9, in which: the reaction of the chlorinated compound of formula (II) with the anhydrous hydrofluoric acid of the second stage is carried out at a temperature of between 0 ° C. and the boiling temperature of the organic solvent, preferably between 5 ° C and the boiling temperature of the organic solvent; and / or the reaction of the chlorinated compound of formula (II) with the anhydrous hydrofluoric acid of the second stage is carried out at a pressure of between 0 and 16 bars absolute.
    [0011]
    11. Method according to one of claims 1 to 10, wherein the chlorinated compound of formula (II) is dissolved in the organic solvent prior to the second reaction step.
    [0012]
    12. Method according to one of claims 1 to 11, wherein: - the mass ratio between the chlorinated compound of formula (II) and the organic solvent involved in the reaction of the chlorinated compound of formula (II) with the anhydrous hydrofluoric acid of the second step is between 0.001 and 10 and preferably between 0.005 and 5; and / or the molar ratio between the chlorinated compound of formula (II) and the hydrofluoric acid involved in the reaction of the chlorinated compound of formula (II) with the anhydrous hydrofluoric acid of the second stage is between 0, 01 and 0.5 and preferably between 0.05 and 0.5.
    [0013]
    13. Process according to one of Claims 1 to 12, in which the reaction of the sulphonamide with the sulfuric acid and the chlorinating agent of the first step provides the chlorinated compound of formula: (IIa) Ri (SO 2) -NH - (SO2) -CI; the first step further comprising reacting the chlorinated compound of formula (IIa) with a base to obtain the chlorinated compound of formula: (11b) R1- (SO2) -NM- (SO2) -CI wherein M represents a monovalent cation.
    [0014]
    The process according to claim 13, wherein said base is selected from alkali metal carbonates, alkaline earth metal carbonates, alkali metal hydroxides, alkaline earth metal hydroxides, tertiary amines in a polar organic solvent, and mixtures thereof.
    [0015]
    15. Method according to one of claims 1 to 14, comprising, after the second step: (c) a third neutralization step of the compound of formula (III), preferably by adding a base selected from metal carbonates alkali metal carbonates, alkali metal hydroxides, alkali metal hydroxides, alkaline earth metal hydroxides, and mixtures thereof.
    [0016]
    The process according to claim 15, wherein the fluorinated compound of formula (III) obtained in the second step is a compound of the formula: (IIIa) R2- (SO2) -NH- (SO2) -F and wherein the third Neutralization step makes it possible to convert the compound of formula (IIIa) into a compound of formula: (IIIb) R2- (SO2) -NM- (SO2) -F where M represents a monovalent cation.
    [0017]
    17. Method according to one of claims 1 to 16, comprising, after the second step or optionally the third step, a final cation exchange step, preferably by contacting with a fluoride, chloride, carbonate, hydroxide, sulphate, chlorate, perchlorate, nitrite or nitrate of alkali or alkaline earth metal or quaternary ammonium.
    [0018]
    18. Method according to one of claims 1 to 17, for obtaining LiN (SO2F) 2, LiN (SO2CF3) (SO2F), LiN (SO2C2F5) (SO2F), LiN (SO2CF2OCF3) (SO2F). , LiNi (SO2C3HF6) (SO2F), LiN (SO2C4F9) (SO2F), LiN (SO2C5F11) (SO2F), LiN (SO2C6F13) (SO2F), LiN (SO2C7F15) (SO2F), LiN (SO2C8F17) (SO2F) or LiN (SO2C9F19) (SO2F), and preferably LiN (SO2F) 2.
    [0019]
    19. A process for producing an electrolyte, comprising preparing an imide salt of formula (IIIb) R2- (SO2) -NM- (SO2) -F, where M represents a monovalent cation and R2 represents a grouping electroattractant having a positive Hammett parameter a, by the method of one of claims 1 to 18, and dissolving it in a solvent, said imide salt being preferably a lithium or sodium salt.
    [0020]
    20. A method of manufacturing a battery or a battery cell, comprising the manufacture of an electrolyte according to claim 19 and the insertion of this electrolyte between an anode and a cathode.
    [0021]
    21. Composition comprising at least 99.9% by weight of an imide salt of formula: (IIIb) R2- (SO2) -NM- (SO2) -F in which M represents a monovalent cation and R2 represents a grouping an electroattractor exhibiting a positive Hammett parameter a, the composition comprising a mass content of total alkali or alkaline earth metal fluorides of 1 to 500 ppm, and / or a mass content of total alkali or alkaline earth metal chlorides of 1 to 500 ppm; 200 ppm.
    [0022]
    The composition of claim 21, wherein the mass content of total alkali or alkaline earth metal fluorides is from 1 to 250 ppm and / or the mass content of total alkali or alkaline earth metal chlorides is from 1 to 100 ppm.
    [0023]
    23. Composition according to claim 21 or 22, comprising a mass content of nitrates of less than or equal to 250 ppm, preferably less than or equal to 150 ppm; and / or comprising a mass content of sulphates of less than or equal to 250 ppm, preferably less than or equal to 150 ppm.
    [0024]
    24. Composition according to one of Claims 21 to 23, in which: M represents Li or Na and / or R2 represents F, CF3, CHF2, CH2F, C2HF4, C2H2F3, C2H3F2, C2F5, C3F7, C3H2F5, C3H4F3, C3HF6, C4F9, C4H2F7, C4H4F5, C5F11, C3F6OCF3, C2F4OCF3, C2H2F2OCF3, CF2OCF3, C6F13, C7F15, C8F17 or C9F19, F being preferred.
    [0025]
    25. Composition according to one of claims 21 to 24, wherein the imide salt is LiN (SO2F) 2, LiN (SO2CF3) (SO2F), LiN (SO2C2F5) (SO2F), LiN (SO2CF2OCF3). ) (SO2F), LiN (SO2C3HF6) (SO2F), LiN (SO2C4F9) (SO2F), LiN (SO2C5F11) (SO2F), LiN (SO2C6F13) (SO2F), LiN (SO2C7F15) (SO2F), LiN (SO2C8F17) (SO2F) or LiN (SO2C9F19) (SO2F), and preferably LiN (SO2F) 2.
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    同族专利:
    公开号 | 公开日
    EP3131847A1|2017-02-22|
    FR3020060B1|2016-04-01|
    HUE048047T2|2020-05-28|
    CN107074543B|2020-01-17|
    US20170047607A1|2017-02-16|
    CN111498819A|2020-08-07|
    EP3131847B1|2020-01-01|
    US10128525B2|2018-11-13|
    WO2015158979A1|2015-10-22|
    JP2020100548A|2020-07-02|
    KR20160146796A|2016-12-21|
    JP6694394B2|2020-05-13|
    CA2945872A1|2015-10-22|
    US20180366764A1|2018-12-20|
    JP2017514779A|2017-06-08|
    CN107074543A|2017-08-18|
    PL3131847T3|2020-05-18|
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1453523A|FR3020060B1|2014-04-18|2014-04-18|PREPARATION OF IMIDES CONTAINING FLUOROSULFONYL GROUP|FR1453523A| FR3020060B1|2014-04-18|2014-04-18|PREPARATION OF IMIDES CONTAINING FLUOROSULFONYL GROUP|
    CN202010081633.5A| CN111498819A|2014-04-18|2015-04-01|Preparation of imides containing fluorosulfonyl groups|
    US15/304,577| US10128525B2|2014-04-18|2015-04-01|Preparation of imides containing a fluorosulfonyl group|
    HUE15725713A| HUE048047T2|2014-04-18|2015-04-01|Preparation of imides containing a fluorosulphonyl group|
    EP15725713.0A| EP3131847B1|2014-04-18|2015-04-01|Preparation of imides containing a fluorosulphonyl group|
    PCT/FR2015/050845| WO2015158979A1|2014-04-18|2015-04-01|Preparation of imides containing a fluorosulphonyl group|
    CA2945872A| CA2945872A1|2014-04-18|2015-04-01|Preparation of imides containing a fluorosulphonyl group|
    CN201580020209.7A| CN107074543B|2014-04-18|2015-04-01|Preparation of imides containing fluorosulfonyl groups|
    JP2016563023A| JP6694394B2|2014-04-18|2015-04-01|Preparation of imide containing fluorosulfonyl group|
    KR1020167031296A| KR20160146796A|2014-04-18|2015-04-01|Preparation of imides containing a fluorosulphonyl group|
    PL15725713T| PL3131847T3|2014-04-18|2015-04-01|Preparation of imides containing a fluorosulphonyl group|
    US16/111,327| US20180366764A1|2014-04-18|2018-08-24|Preparation of imides containing a fluorosulfonyl group|
    JP2019233852A| JP2020100548A|2014-04-18|2019-12-25|Preparation of imides containing fluorosulfonyl group|
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