WO2019044286A1 - Procédé de production de sel métallique d'acide perfluoroalcane sulfonylimide - Google Patents

Procédé de production de sel métallique d'acide perfluoroalcane sulfonylimide Download PDF

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WO2019044286A1
WO2019044286A1 PCT/JP2018/027795 JP2018027795W WO2019044286A1 WO 2019044286 A1 WO2019044286 A1 WO 2019044286A1 JP 2018027795 W JP2018027795 W JP 2018027795W WO 2019044286 A1 WO2019044286 A1 WO 2019044286A1
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salt
carbon atoms
organic base
hydroxide
fluoride
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PCT/JP2018/027795
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Japanese (ja)
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岡田　卓也
真太朗 佐々木
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セントラル硝子株式会社
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Priority to CN201880055768.5A priority Critical patent/CN111051278B/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
    • C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives
    • C07C303/44—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom

Definitions

  • the present invention relates to a method of producing metal salt of perfluoroalkanesulfonylimidic acid.
  • Perfluoroalkanesulfonylimidic acid metal salts are compounds useful as battery electrolyte solvents, ionic liquids, and antistatic agents.
  • perfluoroalkanesulfonylimidic acid compound perfluoroalkylsulfonyl fluoride and an alkali metal salt of a trimethylsilyl group-containing perfluoroalkylsulfonamide are reacted with Non-Patent Documents 1 and 2 to obtain perfluoroalkanesulfonylimidic acid. Methods of obtaining are disclosed.
  • Non-Patent Document 3 discloses a method of reacting trifluoromethanesulfonyl fluoride with triethylamine and ammonia as a method for producing lithium salt of perfluoroalkanesulfonylimidate and the like.
  • Patent Document 1 discloses a method of producing by reacting trifluoromethanesulfonyl chloride or trifluoromethanesulfonyl fluoride, ammonia, and tertiary amine or heterocyclic amine. ing. Moreover, after making a salt with a tertiary amine or a heterocyclic amine react with a tertiary amine or a heterocyclic amine in Patent Document 4 in an aqueous solution of an alkali metal hydroxide to liberate an amine, an alkali metal salt of a sulfone imide is crystallized.
  • Patent Document 5 The method of obtaining a metal salt of perfluoroalkanesulfonylimidate by separating out and separating and purifying is described in Patent Document 5 by reacting trifluoromethanesulfonyl fluoride, anhydrous ammonia and potassium fluoride with perfluoroalkanesulfonylimide. Methods of making acid metal salts are disclosed.
  • Patent Document 6 as a method for producing a fluorine-containing sulfonylimide compound, after a perfluoroalkanesulfonyl fluoride and ammonia are reacted to obtain a reaction solution, an alkali metal such as an alkali metal hydroxide is added to the reaction solution. Also disclosed is a method of preparation by reacting a compound with a subsequent reaction with a perfluoroalkanesulfonyl halide.
  • JP-A-8-081436 JP-A-11-209338 China Publication No. 101456832 JP 2000-302748 A JP, 2001-288193, A JP 2011-057666 A
  • Non-Patent Documents 1 and 2 are disadvantageous for industrial mass production because there are many reaction steps and expensive compounds such as hexamethyldisilazane must be used.
  • the method described in Non-patent Document 3 is an efficient method for producing perfluoroalkanesulfonylimide lithium salt with few by-products, it is industrially adopted because it is distilled using benzene at the time of purification. Had trouble.
  • Patent Document 1 it is necessary to add a large amount of alkali metal fluoride. Furthermore, even in conventional methods other than these, it is not possible to obtain a perfluoroalkanesulfonylimide lithium salt with a good yield, and after isolating a sulfoneimide compound obtained by the reaction with an amine salt, a potassium salt or a sodium salt It has been necessary to derive sulfone imide acid with a strong acid such as sulfuric acid, and neutralize with lithium hydroxide (LiOH) or lithium carbonate (Li 2 CO 3 ) to obtain a sulfone imide lithium salt. Therefore, there is a problem that the number of processes is increased and the amount of waste is increased.
  • LiOH lithium hydroxide
  • Li 2 CO 3 lithium carbonate
  • An object of the present invention is to provide a method for producing a perfluoroalkanesulfonylimidic acid metal salt which is less in waste, high in purity and efficient than the methods known in the prior art.
  • the present invention provides the inventions described in [Invention 1] to [Invention 7] below.
  • each R f independently represents a linear C 1 to C 6 or branched C 3 to C 6 perfluoroalkyl group
  • M represents an alkali metal or an alkaline earth metal
  • n represents an integer equal to the valence number of the corresponding metal.
  • R f represents a straight chain having 1 to 6 carbon atoms or a branched perfluoroalkyl group having 3 to 6 carbon atoms
  • X represents a halogen atom
  • R 1 and R 2 each independently represent a hydrogen atom, a straight chain having 1 to 8 carbon atoms, or a branched alkyl group having 3 to 8 carbon atoms
  • R 3 represents a linear or branched alkyl group having 1 to 8 carbon atoms, or a cyclic alkyl group having 3 to 8 carbon atoms.
  • the linear or branched alkyl group having 1 to 8 carbon atoms in R 3 at least one hydrogen atom of the alkyl group is substituted by a substituent, and the substituent is a halogen (Fluorine, chlorine, bromine, iodine), alkylamino group (-NR 4 R 5 ; R 4 and R 5 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms , An alkoxy group (a linear or branched alkyloxy group having 1 to 6 carbon atoms), an aryl group or a hydroxyl group.
  • halogen Fluorine, chlorine, bromine, iodine
  • alkylamino group -NR 4 R 5 ;
  • R 4 and R 5 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or 1 to 6 carbon atoms ,
  • An alkoxy group a linear or branched alkyloxy group having
  • An imine base having By reacting ammonia or ammonium halide in the presence of an organic base selected from the group consisting of: “a salt or complex consisting of perfluoroalkanesulfonylimidic acid and an organic base”; “a salt or complex consisting of an organic base and a hydrogen halide” Obtaining a mixture containing [Second step] Water is added to a mixture containing the "salt or complex consisting of the perfluoroalkanesulfonylimidic acid and the organic base" obtained in the first step and the "salt or complex consisting of the organic base and the hydrogen halide" By precipitating the “salt or complex consisting of the perfluoroalkanesulfonylimide acid and the organic base” as crystals and subsequently filtering it out, the salt or
  • the amine used in the first step is N-benzyldimethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine Or the preparation method according to Invention 1, which is N, N-dimethylaniline, N, N-diethylaniline.
  • the imine base used in the first step is 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene or 1,4-
  • the halide of the alkali metal or alkaline earth metal or the hydroxide of the alkali metal or alkaline earth metal used in the third step is lithium fluoride, sodium fluoride, potassium fluoride, lithium chloride, sodium chloride, potassium chloride Magnesium fluoride, calcium fluoride, barium fluoride, strontium fluoride, magnesium chloride, calcium chloride, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, The manufacturing method as described in any.
  • the production method of the present invention has the effect of being able to efficiently produce high-purity perfluoroalkanesulfonylimidic acid metal salt with less waste.
  • the first step is to react perfluoroalkanesulfonylimidic acid and perfluoroalkanesulfonylimidic acid by reacting perfluoroalkanesulfonyl halide with ammonia or ammonium halide in the presence of an organic base selected from an amine, a heterocyclic compound and an imine base.
  • the step is to obtain a mixture containing a salt or complex consisting of an organic base and a salt or complex consisting of an organic base and hydrogen halide (Scheme 1; the definition of each reactant will be described later).
  • R f is a perfluoroalkyl group having a linear or branched chain having 3 to 6 carbon atoms having 1 to 6 carbon atoms, R f is a straight chain having 1 to 4 carbon atoms Are preferred, and those in which R f has 1 carbon atom (a trifluoromethyl group) are particularly preferred.
  • perfluoroalkanesulfonyl halides include trifluoromethanesulfonyl fluoride, pentafluoroethanesulfonyl fluoride, heptafluoropropanesulfonyl fluoride, nonafluorobutanesulfonyl fluoride, trifluoromethanesulfonyl chloride, pentafluoroethane sulfonyl chloride Heptafluoropropanesulfonyl chloride, nonafluorobutanesulfonyl chloride, trifluoromethanesulfonyl bromide, pentafluoroethanesulfonyl bromide, heptafluoropropanesulfonyl bromide, nonafluorobutanesulfonyl bromide, trifluoromethanesulfonyl iodide, pentafluoroethane
  • trifluoromethanesulfonyl fluoride pentafluoroethanesulfonyl fluoride, heptafluoropropanesulfonyl fluoride, trifluoromethanesulfonyl chloride, pentafluoroethane sulfonyl chloride, heptafluoropropane sulfonyl chloride, trifluoromethanesulfonyl bromide, pentafluoroethane sulfonyl bromide , Heptafluoropropanesulfonyl bromide, trifluoromethanesulfonyl iodide, pentafluoroethanesulfonyl iodide, heptafluoropropanesulfonyl iodide is preferable, and trifluoromethanesulfonyl fluoride, pentafluoroethanesulf
  • the perfluoroalkanesulfonyl halide used in this step is usually 1 to 10 moles, preferably 1 to 8 moles, more preferably 1 to 5 moles per mole of ammonia or ammonium halide.
  • the organic base used in this step has the following formula: An amine represented by Heterocyclic compounds, And the following skeleton: It is selected from imine bases having
  • R 1 and R 2 each independently represent a hydrogen atom, a straight chain having 1 to 8 carbon atoms, or a branched alkyl group having 3 to 8 carbon atoms.
  • R 3 represents a linear or branched alkyl group having 1 to 8 carbon atoms or a cyclic alkyl group having 3 to 8 carbon atoms.
  • at least one hydrogen atom of the alkyl group in the alkyl group (linear or branched alkyl group) in R 3 is substituted by a substituent, and the substituent is halogen (fluorine, chlorine, bromine, iodine) ,
  • An alkylamino group (-NR 4 R 5 ; R 4 and R 5 each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms), an alkoxy group (carbon It is a straight chain having 1 to 6 or a branched alkyloxy group having 3 to 6 carbon atoms), an aryl group or a hydroxyl group.
  • At least one hydrogen atom of the alkyl group is substituted with a halogen (fluorine, chlorine, bromine, iodine), an alkyl group having 1 to 6 carbon atoms, or a haloalkyl group having 1 to 6 carbon atoms It may be done.
  • at least one of hydrogen atoms of the alkyl group portion in the alkylamino group or alkoxy group described above is an alkylamino group (-NR 5 R 6 ; the definition of R 5 and R 6 is R 4 in the alkylamino group described above, The same as R 5 ) may be substituted.
  • R 1 and R 2 each independently represent a hydrogen atom, a linear C 1-6 alkyl group or a branched C 3-6 alkyl group
  • R 3 is carbon A linear or branched alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, and the linear or C 3 to 6 carbon atoms having 1 to 6 carbon atoms
  • a substituent of the branched alkyl group (-NR 4 R 5 ; R 4 and R 5 each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms or 1 to 4 carbon atoms)
  • the amine in which the aryl group is substituted is preferable.
  • tertiary amines that is, R 1 and R 2 in the amine are each independently a linear alkyl group having 1 to 4 carbon atoms, and R 3 is a straight chain having 1 to 4 carbon atoms
  • R 1 and R 2 in the amine are each independently a linear alkyl group having 1 to 4 carbon atoms
  • R 3 is a straight chain having 1 to 4 carbon atoms
  • organic base examples include N-benzyldimethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl Propylenediamine, N, N-dimethylaniline, N, N-diethylaniline, N, N, N, N ′, N ′ ′, N ′ ′-pentamethyl-diethylene triamine, triethanolamine, tripropanolamine, dimethylethanolamine, dimethylaminoethoxyethanol N, N-dimethylaminopropylamine, N, N, N ', N', N ''-pentamethyldipropylenetriamine, tris (3-dimethylaminopropyl) amine, tetramethylimino-bis (propylamine), N-diethyl-ethanolamine, N-methylpyrrolidine, N-methylpi Peridine, N-methylp
  • the “salt or complex of“ perfluoroalkanesulfonylimidic acid and an organic base ”obtained in this step is the final target product of the present invention to be efficiently precipitated as crystals in the second step to be described later. It is extremely important in producing perfluoroalkanesulfonylimidic acid metal salts in high purity.
  • organic bases mentioned above in this step among others, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, N-methylpyrrolidine, N-methylpiperidine is particularly preferably used because it easily precipitates efficiently as crystals with perfluoroalkanesulfonylimide acid.
  • an organic base can be used individually or in combination.
  • the amount of the organic base used in this step is 3 moles stoichiometrically when using ammonia, and 4 moles when using ammonium halide per mole of the perfluoroalkanesulfonyl halide Is usually 3 to 10 moles, preferably 3 to 5 moles. If the amount is less than 3 moles, the reaction yield may be lowered, and if it exceeds 10 moles, there is no problem with the progress of the reaction, but there is no particular advantage in terms of reaction rate, yield or economy.
  • Ammonia used in this step can be used either in a gaseous state (for example, anhydrous ammonia or the like) or in a liquid state (water, one dissolved in a solvent or the like). Further, specific examples of the ammonium halide used in this step include ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide and the like.
  • this step can also be carried out in the presence of an organic solvent.
  • the organic solvent said here means the inactive organic compound which is not directly involved in the reaction of this invention.
  • aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters, amides, nitriles or sulfoxides and the like can be mentioned.
  • esters, amides, nitriles or sulfoxides are preferable, and nitriles are more preferable.
  • organic solvent examples include n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene, mesitylene, methylene chloride, chloroform, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, tert-butyl methyl ether, Ethyl acetate, butyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, dimethyl sulfoxide, dimethyl carbonate, ethyl methyl carbonate Or diethylene carbonate and the like.
  • reaction solvents can be used alone or in combination.
  • the amount of the organic solvent or water used is not particularly limited, but 0.1 L (liter) or more per 1 mol of ammonia may be used, usually 0.1 to 20 L is preferable, and particularly 0.1 to 20 L is preferable. 10 L is more preferable.
  • the organic solvent is a water-soluble organic solvent
  • it is removed by a general organic chemical operation such as distillation after the reaction of this step, and after removal Performing the second step is one of the particularly preferable embodiments also from the viewpoint of operation.
  • the second step can be carried out as it is without performing an operation of removing the solvent after the reaction of this step.
  • the temperature condition of this step is not particularly limited, but generally, it may be in the range of -50 to 200 ° C., preferably 0 to 100 ° C., particularly preferably 0 to 70 ° C. If the temperature is lower than -50.degree. C., the reaction rate becomes slow, and if the temperature exceeds 200.degree. C., decomposition of the product may occur.
  • reaction vessel used in the present process stainless steel, Monel TM, Hastelloy TM, nickel, or these metals or polytetrafluoroethylene, etc. lined pressure-resistant reaction vessel with a fluororesin such as perfluoropolyether resins .
  • the reaction time of this step is not particularly limited, but may be in the range of 0.1 to 240 hours, and varies depending on the substrate and reaction conditions, so analysis means such as gas chromatography, liquid chromatography, NMR, etc. It is preferable to follow the progress of the reaction and use as the end point the point when the raw material perfluoroalkanesulfonyl halide has almost disappeared.
  • the amount of water used in the water washing is not particularly limited, but generally, it is preferable to use about 50 to 300% by mass with respect to "a salt or complex composed of an imidic acid and an organic base" in the reaction mixture. It is also one of the preferable operations to repeat the washing by dividing the above amount of water into several times.
  • the temperature condition is not particularly limited, and heating may be performed.
  • the reaction vessel used for water washing is not particularly limited, stainless steel, Monel TM, Hastelloy TM, nickel, or these metals or polytetrafluoroethylene, lined with a fluorine resin such as perfluoro polyether resin A reaction container etc. are mentioned.
  • the separation operation after the water washing is not particularly limited as long as it is a method in which the organic mixture and the aqueous layer containing a salt or a complex can be separated. Generally, it can be carried out by simple liquid separation, filtration, centrifugation or the like.
  • the third step Next, the third step will be described.
  • the “salt or complex consisting of perfluoroalkanesulfonylimidic acid and an organic base” obtained in the second step, a halide or a hydroxide of an alkali metal, or a halogen of an alkaline earth metal in a solvent And reacting the hydroxide or hydroxide to obtain a mixture containing a metal salt of perfluoroalkanesulfonylimidate, and subsequently concentrating the mixture to obtain a metal salt of perfluoroalkanesulfonylimidate .
  • halides of alkali metals or alkaline earth metals or hydroxides of alkali metals or alkaline earth metals are preferable, and as the halides of alkali metals, lithium fluoride (LiF), sodium fluoride (NaF) Potassium fluoride (KF), lithium chloride (LiCl), sodium chloride (NaCl) or potassium chloride (KCl), and as halides of alkaline earth metals, magnesium fluoride (MgF 2 ), calcium fluoride ( CaF 2 ), barium fluoride (BaF 2 ), strontium fluoride (SrF 2 ), magnesium chloride (MgCl 2 ) or calcium chloride (CaCl 2 ), and as a hydroxide of an alkali metal, lithium hydroxide (LiOH) , Sodium hydroxide (NaOH) or potassium hydroxide (KOH) is, as the hydroxide of an alkaline earth metal, magnesium hydroxide (M
  • halides of alkali metals or alkaline earth metals or hydroxides of alkali metals or alkaline earth metals can also be used alone or in combination of two or more.
  • a combination of the same alkali metal hydroxide and halide eg, potassium hydroxide and potassium chloride
  • the same alkali earth metal hydroxide and halide eg, hydroxide
  • the use of a combination of magnesium and magnesium chloride is one of the preferred embodiments.
  • about these compounds although it may be in the form of a hydrate by a kind, even if it is a form of a hydrate, it can utilize suitably at this process.
  • the amount of the halide of an alkali metal or alkaline earth metal or the hydroxide of an alkali metal or alkaline earth metal is preferably 1 to 5 moles per mole of “a salt or complex composed of an imidic acid and an organic base”, More preferably, it is 1 to 3 moles.
  • a salt or complex composed of an imidic acid and an organic base may be decomposed to lower the yield.
  • it is less than 1 mole it is not preferable because the conversion rate is lowered.
  • This step can be reacted using an organic solvent or water as a solvent.
  • organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, ethers, carbonates, esters, amides, nitriles, sulfoxides and the like. Among these, esters, amides, nitriles or sulfoxides are preferable, and nitriles are more preferable.
  • organic solvent examples include n-hexane, cyclohexane, n-heptane, benzene, toluene, xylene, mesitylene, methylene chloride, chloroform, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, tert-butyl methyl ether, Dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethyl acetate, butyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, propionitrile, butyronitrile, iso Butyronitrile, valeronitrile or dimethyl sulfoxide etc.
  • reaction solvents can be mentioned. Among them, ethyl acetate, butyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, propionitrile or dimethyl sulfoxide is preferable, and acetonitrile or propionitrile is more preferable.
  • reaction solvents can be used alone or in combination.
  • reaction temperature is not particularly limited, it is usually -10 ° C to + 110 ° C, preferably +25 to + 80 ° C. If the temperature is lower than -10 ° C, the reaction does not proceed sufficiently to cause a decrease in yield, which is economically disadvantageous or causes a problem such as slowing of the reaction rate and requiring a long time to complete the reaction. There is a case. On the other hand, if it exceeds + 110 ° C., by-products are easily generated, and excessive heating is not energy efficient.
  • the reaction time is not particularly limited, but it is usually within 24 hours, and the progress of the reaction is followed by analytical means such as ion chromatography, NMR, etc. It is preferable to
  • the reactor used in this process include stainless steel, Hastelloy TM, or metal container such as Monel TM, tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, polypropylene resin, polyethylene resin, And the reactor which can fully react under normal pressure or pressurization, such as what lined glass etc. inside, can be used.
  • organic base and hydrogen halide in a reaction mixture containing a perfluoroalkanesulfonylimidic acid metal salt Since insolubles such as “salts or complexes comprising the compound” are formed as a solid, they are separated and removed by filtering the mixture.
  • the reaction may be performed immediately after the reaction in this step, or may be performed immediately before distilling off the solvent.
  • the metal salt of perfluoroalkanesulfonylimidate can be obtained by evaporating the solvent, but the solvent
  • the embodiment of is not particularly limited, and may be carried out by the usual operation of organic chemistry.
  • the metal salt of imidic acid which has intrinsically high hygroscopic properties and is very difficult to purify with high purity even in operations such as recrystallization, is simply distilled off as a solvent. It is possible to obtain only high purity. As shown in the following examples, very small amounts of by-products are contained in addition to the desired product, and it can be said that the method is very useful compared to the prior art.
  • the quantification of the product was calculated based on “mol%” of the composition obtained by measuring the reaction mixture by a nuclear magnetic resonance analyzer (NMR). Further, with respect to the crystals obtained in the third step, trifluoromethanesulfonic acid ion concentration (CF 3 SO 3 ⁇ ), trifluoromethanesulfonamide ion concentration (CF 3 SO 2 NH ⁇ ) and fluorine ion concentration (F - ) was quantified.
  • NMR nuclear magnetic resonance analyzer
  • Example 1 [First step] 250 g of acetonitrile and 162 g (1.33 mol) of N, N-dimethyl-4-aminopyridine were charged into a 1000 ml autoclave, cooled to 5 ° C. with ice water, and 122 g (0.80 mol) of trifluoromethanesulfonyl fluoride was introduced. After introducing trifluoromethanesulfonyl fluoride, 6.5 g (0.38 mol) of anhydrous ammonia was subsequently introduced over 1 hour while maintaining the internal temperature at 0 ° C. to 5 ° C. When the introduction of anhydrous ammonia was completed, the reactor was warmed to room temperature and stirred for 14 hours.
  • Example 2 [Step 1 to Step 2] In the same manner as in Example 1, 142 g of bistrifluoromethanesulfonylimide-N, N-dimethyl-4-aminopyridinium salt was obtained. The crystals were quantified by 19 F-NMR, and the yield for the starting material to ammonia was 85% (0.32 mol). [Third step] Next, 142 g of this crystal was placed in a 500 ml four-necked flask, 250 g of methyl-t-butyl ether and 15.3 g (0.36 mol) of lithium chloride were added, and the mixture was stirred at room temperature for 15 hours.
  • the reaction mixture was filtered, and the obtained filtrate was concentrated and dried (here, 320 g of the trapped organic solvent is reused in the third step). After drying, 89 g of lithium bistrifluoromethanesulfonylimide having a purity of 99% or more, a yield of 82% (0.31 mol), and a purity of 99.9% were obtained.
  • the trifluoromethanesulfonic acid ion concentration was 5 ppm
  • the trifluoromethanesulfonamide ion concentration was 19 ppm
  • the fluorine ion concentration was 1 ppm.
  • Comparative Example 1 [First step] A 500 ml autoclave was charged with 120 g of acetonitrile and 120 g (1.19 mol) of triethylamine, cooled to 5 ° C. with ice water, and 122 g (0.80 mol) of trifluoromethanesulfonyl fluoride was introduced. After introducing trifluoromethanesulfonyl fluoride, 6.5 g (0.38 mol) of anhydrous ammonia was subsequently introduced over 1 hour while maintaining the internal temperature at 0 ° C. to 5 ° C. When the introduction of anhydrous ammonia was completed, the reactor was warmed to room temperature and stirred for 14 hours.
  • the precipitated crystals were filtered under reduced pressure using a Kiriyama funnel, and washed with 600 g of a 20% aqueous solution of potassium hydroxide to obtain 109 g (0.33 mol) of crude potassium bistrifluoromethanesulfonylimide (here, 1168 g of wastewater) By-product).
  • 109 g (0.33 mol) of a crude substance of potassium bistrifluoromethanesulfonylimide and 200 g of concentrated sulfuric acid were charged into a four-necked flask, and the mixture was stirred at an internal temperature of 60 ° C. for 1 hour.
  • the metal salt of perfluoroalkanesulfonylimidate targeted by the present invention can be used as an intermediate for medicines and pesticides, a battery electrolyte, and an acid catalyst.

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Abstract

L'invention concerne un procédé efficace destiné à la production d'un sel métallique d'acide perfluoroalcane sulfonylimide. Le sel métallique d'acide perfluoroalcane sulfonylimide est produit selon les étapes consistant à : faire réagir un halogénure de perfluoroalcane sulfonyle avec une base organique et de l'ammoniac ou de l'ammoniac halogéné pour obtenir un mélange contenant "un sel ou un complexe comprenant un acide perfluoroalcane sulfonylimide et une base organique" (première étape) ; puis ajouter de l'eau au mélange afin de précipiter le "sel ou complexe comprenant un acide perfluoroalcane sulfonylimide et une base organique" en tant que cristal et procéder à la filtration de celui-ci (seconde étape) ; puis faire réagir, par exemple, un hydroxyde de métal alcalin ou de métal alcalino-terreux avec le "sel ou complexe comprenant un acide perfluoroalcane sulfonylimide et une base organique" dans un solvant, filtrer la matière insoluble à partir de la solution mélangée obtenue, et concentrer celle-ci (troisième étape).
PCT/JP2018/027795 2017-08-29 2018-07-25 Procédé de production de sel métallique d'acide perfluoroalcane sulfonylimide WO2019044286A1 (fr)

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