JP2019043849A - Manufacturing method of perfluoroalkanesulfonyl imidic acid metal salt - Google Patents

Abstract

To provide a method for manufacturing a perfluoroalkanesulfonyl imidic acid metal salt at good efficiency.SOLUTION: A perfluoroalkanesulfonyl imidic acid metal salt is manufactured by obtaining a mixture containing "salt or a complex consisting of perfluoroalkanesulfonyl imidic acid and organic base" by reacting the organic base, ammonia or ammonium halide with perfluoroalkanesulfonyl halide (first process), then depositing the "salt or a complex consisting of perfluoroalkanesulfonyl imidic acid and organic base" by adding water to the mixture as a crystal and then conducting filtration (second process), then reacting hydroxide or the like of alkali metal or alkali earth metal with the "salt or a complex consisting of perfluoroalkanesulfonyl imidic acid and organic base" in a solvent, filtering an insoluble matter from the resulting mixture and then concentrating the same (third process).SELECTED DRAWING: None

Description

  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. As a method for producing a 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.

  Further, 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.

  On the other hand, Patent Document 1, Patent Document 2 and Patent Document 3 disclose 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. 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.

  Furthermore, in 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 Unexamined-Japanese-Patent No. 11-209338 China Publication No. 101456832 JP 2000-302748 A JP 2001-288193 A JP, 2011-057666, A

Inorganic Chemistry, 23 (23), 3720-3723 (1984) Inorganic Chemistry, 32 (23), 5007-5010 (1993). Journal of Fluorine Chemistry, 125, 243-252 (2004)

  The methods described in 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. Although 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.

On the other hand, in the method described in 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.

  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.

Then, in view of the above problems, the inventors of the present invention intensively studied, and reacted perfluoroalkanesulfonyl halide with ammonia (NH ₃ ) etc. in the presence of a specific organic base such as N, N-dimethylaminopyridine. Thus, it was found that the “salt or complex composed of perfluoroalkanesulfonylimidic acid and an organic base” formed was crystallized. Therefore, we decided to use this property. That is, water is added to the reaction solution after completion of the reaction obtained by the above reaction to precipitate "salt or complex composed of perfluoroalkanesulfonylimidic acid and organic base" as crystals, and then the filtration operation is performed. By removing the dissolved impurities and subjecting the obtained crystals to a reaction with metal halides or metal hydroxides, there are less waste and high purity compared to the conventional production method. The inventors have found a method for efficiently producing a perfluoroalkanesulfonylimidic acid metal salt and completed the present invention.

That is, the present invention provides the inventions described in the following [Invention 1]-[Invention 7].
[Invention 1]
Formula [1]:

[Wherein, each R _f independently represents a linear or branched C 1-6 perfluoroalkyl group having 1 to 6 carbon atoms, and M represents an alkali metal or an alkaline earth metal. n represents an integer equal to the valence number of the corresponding metal. ]
A manufacturing method of perfluoro alkane sulfonyl imide acid metal salt characterized by including the following processes in manufacturing method of perfluoro alkane sulfonyl imide acid metal salt represented by these.
[First step]
Formula [2]:

[Wherein, R _f represents a straight chain having 1 to 6 carbon atoms or a branched perfluoroalkyl group having 3 to 6 carbon atoms, and X represents a halogen atom]
In the perfluoroalkanesulfonyl halide represented by the following formula:

[In formula, R < ¹ >, R < ² > represents a hydrogen atom, a C1-C8 linear, or a C3-C8 branched alkyl group each independently. 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. Here, in 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 , R ⁵ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or 3 to 6 carbon atoms And an alkoxy group (a linear or branched alkyloxy group having 1 to 6 carbon atoms), an aryl group or a hydroxyl group. ]
An amine represented by
Heterocyclic compounds,
And the following skeleton:

[In Formula, "-" in "-C" or "-C-" represents a bond. ]
An imine base having
By reacting ammonia or ammonium halide in the presence of an organic base selected from
"A salt or complex composed of perfluoroalkanesulfonylimidic acid and an organic base";
Obtaining a mixture containing "an organic base and a salt or complex consisting of hydrogen halide".
[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 salt consisting of the organic base and the hydrogen halide contained in the mixture The step of separating and removing the complex to obtain the “salt or complex consisting of the perfluoroalkanesulfonylimidic acid and the organic base”.
[Third step]
The “salt or complex comprising perfluoroalkanesulfonylimidic acid and an organic base” obtained in the second step, the halide of an alkali metal or alkaline earth metal, or the hydroxide of an alkali metal or alkaline earth metal in a solvent The reaction mixture is reacted to obtain a reaction mixture containing a metal salt of perfluoroalkanesulfonylimidate represented by the formula [1] and an insoluble matter, and the insoluble matter is subsequently filtered off from the reaction mixture, and the mixture is then mixed. A step of obtaining a metal salt of perfluoroalkanesulfonylimidate by concentrating
[Invention 2]
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.
[Invention 3]
The production method according to Invention 1, wherein the heterocyclic compound used in the first step is N-methyl pyrrolidine, N-methyl piperidine, 2,4,6-trimethylpyridine or 4-dimethylaminopyridine.
[Invention 4]
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 production method according to Invention 1, which is diazabicyclo [2.2.2] octane.
[Invention 5]
In the first step, the reaction is carried out using a solvent, and in the subsequent second step, the process according to any one of Inventions 1 to 4, further comprising the step of concentrating and distilling off the solvent before addition of water. Method.
[Invention 6]
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.
[Invention 7]
The method according to any one of Inventions 1 to 6, wherein in the third step, a solvent used when reacting an alkali metal halide or hydroxide is an ester, an amide or a nitrile.

  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.

Hereinafter, the present invention will be described in detail. Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments, and can be appropriately carried out based on the ordinary knowledge of the person skilled in the art within the scope of the present invention. can do.
The details will be described below.
[First step]
First, the first step will be described. 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).

In the perfluoroalkanesulfonyl halide used in this step, R _f is a linear C 1 to C 6 or branched C 3 to C 6 perfluoroalkyl group, and R _f is a linear C 1 to C 4 straight chain _Are preferred, and those in which R _f has 1 carbon atom (a trifluoromethyl group) are particularly preferred. Specific compounds include trifluoromethanesulfonyl fluoride, pentafluoroethanesulfonyl fluoride, heptafluoropropanesulfonyl fluoride, nonafluorobutanesulfonyl fluoride, trifluoromethanesulfonyl chloride, pentafluoroethane sulfonyl chloride, heptafluoropropane sulfonyl chloride Nonafluorobutanesulfonyl chloride, trifluoromethanesulfonyl bromide, pentafluoroethanesulfonyl bromide, heptafluoropropanesulfonyl bromide, nonafluorobutanesulfonyl bromide, trifluoromethanesulfonyl iodide, pentafluoroethanesulfonyl iodide, heptafluoropropanesulfonyl iodide, Nonafluorobutanesulfonyl iodide etc. And the like.

  Among them, 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, pentafluoroethanesulfonyl fluoride, trifluoromethanesulfonyl chloride, pentafluoroethane Sulfonyl chloride, Trifluoromethane sulfonyl bromide, pentafluoroethanesulfonyl bromide, trifluoromethanesulfonyl iodide and pentafluoroethanesulfonyl iodide particularly preferred.

  The amount of 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 >, R < ² > respectively independently represents a hydrogen atom, a C1-C8 linear, or a C3-C8 branched alkyl group among the said amines.

On the other hand, among the above-mentioned amines, 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. In addition, 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 A linear or branched alkyloxy group having 3 to 6 carbon atoms, an aryl group or a hydroxyl group.

In the cyclic alkyl group for R ³ , 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. Note that at least one of the 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 above alkylamino group, The same as R ⁵ ) may be substituted.

Among these amines, those in which R ¹ and R ² each independently represent a hydrogen atom, a linear C ¹ to C 6 or branched C ³ to C 6 alkyl group, and R ³ is carbon 1 to 6 linear or branched alkyl having 3 to 6 carbon atoms, cyclic alkyl having 3 to 6 carbon atoms,
And the alkylamino group (—NR ⁴ R ⁵ ; R ⁴ and R ⁵ each independently represents a carbon atom as a substituent of the linear or branched alkyl group having 1 to 6 carbon atoms). A linear or branched alkyl group having 1 to 4 carbon atoms or a branched chain having 3 to 4 carbon atoms is preferred), and amines in which an aryl group is substituted. Furthermore, among these, 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. A chain alkyl group, wherein the alkyl group has a substituent that is an alkylamino group (-NR ⁴ R ⁵ ; R ⁴ and R ⁵ each independently represent a linear alkyl group having 1 to 4 carbon atoms) Or those in which the aryl group is substituted are particularly preferred.

  Specific examples of the organic base 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-methylpipe Lysine, N-methylmorpholine, N-ethylmorpholine, N, N'-dimethylpiperazine, N-methylpipecoline, N-methylpyrrolidone, N-vinyl-pyrrolidone, pyridine, 2,4,6-trimethylpyridine, N, N-dimethyl-4-aminopyridine, lutidine, pyrimidine, pyridazine, pyrazine, oxazole, isoxazole, thiazole, isothiazole, imidazole, 1,2-dimethylimidazole, 3- (dimethylamino) propylimidazole, pyrazole, furazan, pyrazine Quinoline, isoquinoline, purine, 1H-indazole, quinazoline, cinnoline, quinoxaline, phthalazine, pteridine, phenanthridine, 2,6-di-t-butylpyridine, 2,2'-bipyridine, 4,4'-dimethyl- 2, 2'- Pyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 5,5'-dimethyl-2,2'-bipyridyl, 6,6'-t-butyl-2,2'-dipyridyl, 4,4 ' -Diphenyl-2,2'-bipyridyl, 1,10-phenanthroline, 2,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 4,7-diphenyl-1,10- Phenanthroline, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] And octane, bis (2-dimethylaminoethyl) ether, etc., among which N-benzyldimethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylene Diamines, N, N, N ', N'-tetramethylpropylenediamine or N, N-dimethylaniline, N, N-diethylaniline, N-methylpyrrolidine, N-methylpiperidine, 2,4,6-trimethylpyridine or N, N-dimethyl-4-aminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4 -Diazabicyclo [2.2.2] octane, N-methyl pyrrolidine, N-methyl piperidine are preferred.

  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. Among the organic bases mentioned above in this step, among them, 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 perfluoroalkanesulfonylimidic acid. In addition, 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.

In addition, 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. As a reaction solvent, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters, amides, nitriles or sulfoxides and the like can be mentioned.
Among these, esters, amides, nitriles or sulfoxides are preferable, and nitriles are more preferable.

Specific examples of the organic solvent 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.
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. These 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 preferably 0.1 to 20 L. 10 L is more preferable.

  In the case where an organic solvent is used in this step, if 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. On the other hand, when an organic solvent is not used or a non-water-soluble organic solvent is used, the second step can be carried out as it is without performing an operation of removing the solvent after the reaction of this step.

  Although there is no restriction | limiting in particular as temperature conditions of this process, Although what is necessary is just to usually carry out in -50-200 degreeC, 0-100 degreeC is preferable, and especially 0-70 degreeC is more preferable. If the temperature is lower than -50 ° C, the reaction rate will be slow, and if the temperature exceeds 200 ° C, decomposition of the product may occur.

The 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.
[Second step]
Next, the second step will be described. In the second step, water is added to a mixture containing the “salt or complex consisting of perfluoroalkanesulfonylimidic acid and organic base” obtained in the first step and the “salt or complex consisting of organic base and hydrogen halide” While being added, the “salt or complex consisting of an organic base and hydrogen halide” contained in the mixture is dissolved in water, while the “salt or complex consisting of a perfluoroalkanesulfonylimidic acid and an organic base” is crystallized. Followed by filtration to separate and remove "salt or complex consisting of organic base and hydrogen halide" to obtain "salt or complex consisting of perfluoroalkanesulfonylimidic acid and organic base" (Scheme 2).

  There is no restriction | limiting in particular as an embodiment which implements this process, What is necessary is just to carry out by operation, such as normal filtration of organic chemistry. 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.

It is preferable to carry out the water washing usually at normal temperature, but the temperature condition is not particularly limited, and heating may be performed. Further, as 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.

In the second step, 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. If a non-water-soluble organic solvent is used subsequently to the first step, it is preferable to remove it by general organic chemistry operations such as distillation after separation, but it is also possible to use it as it is in the third step is there.
[Third step]
Next, the third step will be described. In the third step, 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 .

As hydroxides of alkali metals, lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH), halides of alkali metals And lithium fluoride (LiF), sodium fluoride (NaF), potassium fluoride (KF), rubidium fluoride (RbF), cesium fluoride (CsF), lithium chloride (LiCl), sodium chloride (NaCl), Potassium chloride (KCl), rubidium chloride (RbCl), cesium chloride (CsCl), lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr), rubidium bromide (RbBr), cesium bromide CsBr), lithium iodide (LiI), sodium iodide (NaI), iodine Potassium (KI), rubidium iodide (RbI), cesium iodide (CsI) as the hydroxide of an alkaline earth metal, magnesium hydroxide (Mg (OH) _2), calcium hydroxide (Ca (OH) ₂ ), barium hydroxide (Ba (OH) ₂ ), strontium hydroxide (Sr (OH) ₂ ) as the 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 ), calcium chloride (CaCl ₂ ), barium chloride (BaCl ₂ ), strontium chloride (SrCl ₂ ), magnesium bromide (MgBr) _2), calcium bromide (CaBr _2), barium bromide (BaBr _2), strontium bromide (SrBr ₂ ), Magnesium iodide (MgI _2), calcium iodide (CaI _2), barium iodide (BaI _2), include strontium iodide (SrI _2), preferably lithium hydroxide (LiOH), sodium hydroxide ( NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH), lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), rubidium chloride (RbCl), cesium chloride (CsCl), magnesium hydroxide (Mg (OH) ₂ ), calcium hydroxide (Ca (OH) ₂ ), barium hydroxide (Ba (OH) ₂ ), strontium hydroxide (Sr (OH) ₂ ), magnesium chloride (MgCl ₂ ), calcium chloride (CaCl ₂ ), barium chloride (BaCl ₂ ), chloride chloride Troronium (SrCl ₂ ) is mentioned.

Among these, 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 (Mg (OH) ₂₎ or calcium hydroxide (Ca (OH) ₂₎ is preferably used in view of ease of inexpensive and available Be

  Further, 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. When two or more are used, a combination of the same alkali metal hydroxide and halide (eg, potassium hydroxide and potassium chloride), or 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. In addition, 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. When more than 5 moles, ie, an excess amount of a base is reacted, the reaction proceeds, but "a salt or complex composed of an imidic acid and an organic base" may be decomposed to lower the yield. For some reasons, it is not preferable to use an excessive amount of base. Moreover, when 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. Examples of the 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.

  Specific examples of the organic solvent 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. may 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. These reaction solvents can be used alone or in combination.

  While the reaction temperature is not particularly limited, it is generally -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.

  When an alkali metal halide or hydroxide or an alkaline earth metal halide is used in this step, “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. In this case, the reaction may be performed immediately after the reaction in this step, or may be performed immediately before distilling off the solvent. In addition, there is no restriction | limiting in particular as an embodiment which implements filter separation operation, What is necessary is just to carry out by normal operation of organic chemistry.

  Subsequently, with respect to the reaction mixture containing the metal salt of perfluoroalkanesulfonylimidate from which the obtained insoluble matter has been removed, 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.

As described above, by adopting the method of this step, 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.
[Example]
Next, the present invention will be described in detail based on examples. The present invention is not limited to the embodiments. Here, 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 fluoride ion concentration (F ^- ) Was quantified.

[First step]
In a 1000 ml autoclave, 250 g of acetonitrile and 162 g (1.33 mol) of N, N-dimethyl-4-aminopyridine were charged, cooled to 5 ° C. with ice water, and 122 g (0.80 mol) of trifluoromethanesulfonyl fluoride was introduced. After trifluoromethanesulfonyl fluoride was introduced, 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. After 14 hours, as a result of quantifying the reaction liquid by ¹⁹ F-NMR, the yield of bis (trifluoromethanesulfonylimide) N, N-dimethyl-4-aminopyridinium salt relative to ammonia as a starting material is 92% (0.35 mol), purity Was 95.7%.
[Second step]
The solvent of the reaction solution obtained in the above reaction step is distilled off (concentrated solvent is reused in the first step), then water is added to the residue, and the precipitated white crystals are filtered under reduced pressure using a Kiriyama funnel. There were obtained 149 g of bis (trifluoromethanesulfonylimide) -N, N-dimethyl-4-aminopyridinium salt (wherein 389 g of wastewater was by-produced). The crystals were quantified by ¹⁹ F-NMR to find that the yield of the starting material to ammonia was 87% (0.33 mol).
[Third step]
149 g of the crystals obtained in the second step were placed in a 500 ml four-necked flask, and 150 g of water was added. 17 g (0.40 mol) of lithium hydroxide monohydrate is added, and after stirring for 30 minutes, insolubles are filtered off by filtration under reduced pressure, and the filtrate is heated to 60 ° C. and concentrated to give bistrifluoromethanesulfonylimide lithium Were obtained in a yield of 84% (0.32 mol) and a purity of 99.9% (whereby 220 g of wastewater was by-produced). As a result of measuring the obtained crystals by ion chromatography, the trifluoromethanesulfonate ion concentration was 3 ppm, the trifluoromethanesulfonamide ion concentration was 11 ppm, and the fluorine ion concentration was 10 ppm.

[Step 1 to Step 2]
In the same manner as in Example 1, 142 g of bis (trifluoromethanesulfonylimide) -N, N-dimethyl-4-aminopyridinium salt was obtained. The crystals were quantified by ¹⁹ F-NMR to find that the yield of 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 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. As a result of measuring the obtained crystals by ion chromatography, the trifluoromethanesulfonic acid ion concentration was 5 ppm, the trifluoromethanesulfonamide ion concentration was 19 ppm, and 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 trifluoromethanesulfonyl fluoride was introduced, 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. After 14 hours, the reaction liquid was quantified by ¹⁹ F-NMR, and as a result, the yield of bistrifluoromethanesulfonylimidotriethylammonium salt was 91.0% (0.346 mol) and the purity was 95.7% with respect to the starting material ammonia there were.
[Purification process]
After distilling off the solvent of the reaction solution obtained in the above first step, 330 g of a 48% aqueous potassium hydroxide solution and 250 g of water were added to the residue, and triethylamine in the reaction system was distilled off under reduced pressure with an evaporator (here waste organic solvent 157g by-product). 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). Next, 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. After stirring, flash distillation was performed under reduced pressure to obtain 84 g (0.30 mol) of bistrifluoromethanesulfonylimidic acid (225 g of by-produced waste acid as residue).
[Cation exchange process]
Next, 84 g (0.30 mol) of bistrifluoromethanesulfonylimidic acid obtained in the above purification step, 36 g of water and 24 g (0.33 mol) of lithium carbonate are added to a 500 ml four-necked flask, and the internal temperature is 60 ° C. Stir for hours. The excess lithium carbonate was filtered off, and the obtained filtrate was concentrated and dried (here, 41 g of wastewater was by-produced). After drying, 82 g of lithium bistrifluoromethanesulfonylimide having a purity of 99% or more was obtained in a yield of 76% (0.29 mol).
Here, comparisons of the amounts of waste liquids of Examples 1 and 2 and Comparative Example 1 are summarized below as Table 1.

  As shown in Table 1, it is understood that Examples 1 and 2 can significantly reduce the amount of waste liquid as compared with Comparative Example 1.

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.

Claims (7)

Formula [1]:

[Wherein, each R _f independently represents a linear or branched C 1-6 perfluoroalkyl group having 1 to 6 carbon atoms, and M represents an alkali metal or an alkaline earth metal. n represents an integer equal to the valence number of the corresponding metal. ]
A manufacturing method of perfluoro alkane sulfonyl imide acid metal salt characterized by including the following processes in manufacturing method of perfluoro alkane sulfonyl imide acid metal salt represented by these.
[First step]
Formula [2]:

[Wherein, R _f represents a straight chain having 1 to 6 carbon atoms or a branched perfluoroalkyl group having 3 to 6 carbon atoms, and X represents a halogen atom]
In the perfluoroalkanesulfonyl halide represented by the following formula:

[In formula, R < ¹ >, R < ² > represents a hydrogen atom, a C1-C8 linear, or a C3-C8 branched alkyl group each independently. 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. Here, in 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 , R ⁵ each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms or 3 to 6 carbon atoms And an alkoxy group (a linear or branched alkyloxy group having 1 to 6 carbon atoms), an aryl group or a hydroxyl group. ]
An amine represented by
Heterocyclic compounds,
And the following skeleton:

[In Formula, "-" in "-C" or "-C-" represents a bond. ]
An imine base having
By reacting ammonia or ammonium halide in the presence of an organic base selected from
"A salt or complex composed of perfluoroalkanesulfonylimidic acid and an organic base";
Obtaining a mixture containing "an organic base and a salt or complex consisting of hydrogen halide".
[Second step]
Water is added to a mixture containing the "salt or complex consisting of the perfluoroalkanesulfonylimide 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 perfluoroalkanesulfonylimide acid and organic base” as crystals, and then filtering off, “salt or complex consisting of organic base and hydrogen halide contained in the mixture” Separating and removing to obtain the “salt or complex comprising the perfluoroalkanesulfonylimidic acid and the organic base”.
[Third step]
The “salt or complex comprising perfluoroalkanesulfonylimidic acid and an organic base” obtained in the second step, the halide of an alkali metal or alkaline earth metal, or the hydroxide of an alkali metal or alkaline earth metal in a solvent The reaction mixture is reacted to obtain a reaction mixture containing a metal salt of perfluoroalkanesulfonylimidate represented by the formula [1] and an insoluble matter, and the insoluble matter is subsequently filtered off from the reaction mixture, and then the mixture is mixed. A step of obtaining a metal salt of perfluoroalkanesulfonylimidate by concentrating The amine used in the first step is N-benzyldimethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine The production method according to claim 1, which is N, N-dimethylaniline or N, N-diethylaniline. The process according to claim 1, wherein the heterocyclic compound used in the first step is N-methyl pyrrolidine, N-methyl piperidine, 2,4,6-trimethylpyridine or 4-dimethylaminopyridine. 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 production method according to claim 1, wherein it is diazabicyclo [2.2.2] octane. 5. The method according to any one of claims 1 to 4, further comprising the step of carrying out the reaction using a solvent in the first step, and concentrating and distilling off the solvent prior to the addition of water in the subsequent second step. Production method. 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 Or 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 in any one of. The production method according to any one of claims 1 to 6, wherein in the third step, the solvent used when reacting the halide or hydroxide of an alkali metal is an ester, an amide or a nitrile.