JP2019069904A - 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 reacting an organic base, ammonia or ammonium halide with perfluoroalkanesulfonyl halide to obtain a mixture containing "a salt or complex consisting of perfluoroalkanesulfonyl imidic acid and the organic base" and "a salt or complex consisting of the organic base and hydrogen fluoride" (first process), then separating and removing "the salt or complex consisting of the organic base and hydrogen fluoride" contained in the mixture by water washing and/or filtering the mixture to obtain "the salt or complex consisting of perfluoroalkanesulfonyl imidic acid and the organic base" (second process), and then combining a process for reacting halide or hydroxide of alkali metals with the mixture in a solvent or a recrystallization process.SELECTED DRAWING: None

Description

  The present invention relates to a method of producing metal salt of perfluoroalkanesulfonylimidate.

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.
On the other hand, in Patent Document 1 and Patent Document 2, a method of producing by reacting trifluoromethanesulfonyl chloride or trifluoromethanesulfonyl fluoride, ammonia, and a tertiary amine or heterocyclic amine is disclosed in Patent Document 3 as a sulfone. An imide acid is reacted with a salt of a tertiary amine or a heterocyclic amine in an aqueous alkali metal hydroxide solution to release the amine, and then the alkali metal salt of sulfonimide is crystallized and separated and purified. Of obtaining a metal salt of perfluoroalkanesulfonylimidate by the method described in Patent Document 4; a method of producing metal salt of perfluoroalkanesulfonylimidate by reacting trifluoromethanesulfonyl fluoride, anhydrous ammonia and potassium fluoride Is disclosed.
In Patent Document 5, as a method for producing a fluorine-containing sulfonylimide compound, after a reaction liquid is obtained by reacting perfluoroalkanesulfonyl fluoride with ammonia, an alkali metal such as an alkali metal hydroxide is added to the reaction liquid. 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 JP 2000-302748 A JP 2001-288193 A JP, 2011-057666, A

Inorganic Chemistry, 23 (23), 372 0-3723 (1984) Inorganic Chemistry, 32 (23), 500 pages 7-5010 (1993).

In the methods of Non-Patent Documents 1 and 2, there are many reaction steps, and expensive compounds such as hexamethyldisilazane must be used, which is disadvantageous for industrial mass production.
On the other hand, in the method of Patent Document 1, it is necessary to add a large amount of alkali metal fluoride.
Furthermore, even in the conventional methods described above other than these, when a perfluoroalkanesulfonylimide lithium salt is formed, it can not be obtained with a good yield, and the sulfoneimide compound obtained by the reaction is an amine salt, potassium After isolation with salt and sodium salt, it is necessary to derive sulfone imide acid with strong acid such as sulfuric acid and neutralize with lithium hydroxide (LiOH) or lithium carbonate (Li ₂ CO ₃ ) to obtain sulfone imide lithium salt was there. 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 that is less waste and efficient than the methods known in the prior art.

Then, in view of the above problems, the inventors of the present invention have intensively studied perfluoroalkanesulfonyl halide with ammonia (NH ₃ ) or the like in the presence of an organic base to obtain “perfluoroalkanesulfonylimide acid and organic base”. After forming a salt or complex comprising the compound in the system, followed by a water washing and / or filtration operation, and then combining the reaction with a metal halide, the recrystallization operation, etc., as compared with the conventional production method The present invention has been accomplished by finding a method for efficiently producing metal salts of perfluoroalkanesulfonylimidates with less waste.

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 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 linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, and X represents a halogen atom]
By reacting an organic base and ammonia or ammonium halide with a perfluoroalkanesulfonyl halide represented by
"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 washing and / or filtration of a mixture containing “a salt or complex consisting of perfluoroalkanesulfonylimide acid and an organic base” obtained in the first step and “a salt or complex consisting of an organic base and hydrogen halide” By doing
Separately remove “the salt or complex consisting of an organic base and hydrogen halide” contained in the mixture,
Obtaining a "salt or complex composed of perfluoroalkanesulfonylimidic acid and an organic base".
[Third step]
The following [A-1 to A-3 steps] or [B-1 to B-3 steps] of the “salt or complex consisting of perfluoroalkanesulfonylimide acid and organic base” obtained in the second step A step of obtaining a perfluoroalkanesulfonylimidic acid metal salt by passing through.
[A-1 process]
The “salt or complex comprising perfluoroalkanesulfonylimidic acid and an organic base” obtained in the second step, a halide of an alkali metal or an alkaline earth metal in a solvent,
Or by reacting alkali metal or alkaline earth metal hydroxides,
A step of obtaining a mixed solution containing the perfluoroalkanesulfonylimidic acid metal salt represented by the formula [1].
[A-2 process]
A step of obtaining a perfluoroalkanesulfonylimidate metal salt by distilling off the solvent from the mixture liquid containing the perfluoroalkanesulfonylimidate metal salt obtained in the step A-1 step.
[A-3 process]
A-2 A step of subjecting the perfluoroalkanesulfonylimidate metal salt obtained in the step 2 to a recrystallization operation using a solvent to obtain a highly pure perfluoroalkanesulfonylimidate metal salt.
[B-1 process]
The “salt or complex consisting of perfluoroalkanesulfonylimide acid and organic base” obtained in the second step is subjected to recrystallization operation using a solvent, and is composed of “highly pure perfluoroalkanesulfonylimide acid and organic base” Obtaining a salt or a complex ".
[B-2 process]
A “salt or complex of“ perfluoroalkanesulfonylimidic acid and an organic base ”of high purity obtained in the step B-1, a halide of an alkali metal or an alkaline earth metal in a solvent,
Or by reacting alkali metal or alkaline earth metal hydroxides,
A step of obtaining a mixed solution containing the perfluoroalkanesulfonylimidic acid metal salt represented by the formula [1].
[B-3 process]
B-2 A step of obtaining a metal salt of perfluoroalkanesulfonylimidate by distilling off the solvent from the mixture liquid containing the metal salt of perfluoroalkanesulfonylimidate obtained in the step S2.
[Invention 2]
The production method according to Invention 1, wherein the organic base used in the first step is a primary amine, a secondary amine, a tertiary amine, a nitrogen-containing aromatic heterocyclic compound or an imine base.
[Invention 3]
The production according to the invention 1 or 2, further comprising the step of reacting with a solvent in the first step, and subsequently concentrating and distilling off the solvent before washing with water and / or filtering in the second step Method.
[Invention 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.
[Invention 5]
In the [A-1 step] or the [B-2 step] of the third step, the solvent used when reacting the halide or hydroxide of an alkali metal is an ester, an amide or a nitrile. The manufacturing method in any one of 4.
[Invention 6]
It contains a perfluoroalkanesulfonylimidic acid metal salt which is produced by carrying out a reaction using an alkali metal or alkaline earth metal halide in the third step [A-1 step] or [A-2 step]. The method according to any one of Inventions 1 to 5, further comprising the step of separating and removing the "salt or complex consisting of an organic base and hydrogen halide" contained in the mixture in the filtration operation of the mixture.
[Invention 7]
It contains a perfluoroalkanesulfonylimidic acid metal salt which is produced by carrying out a reaction using an alkali metal or alkaline earth metal halide in the third step [B-2 step] or [B-3 step]. The method according to any one of Inventions 1 to 5, further comprising the step of separating and removing the "salt or complex consisting of an organic base and hydrogen halide" contained in the mixture in the filtration operation of the mixture.

  The production method according to the present invention has an effect that waste metal is small and perfluoroalkanesulfonylimidic acid metal salt can be efficiently produced.

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. In the first step, "a salt or complex composed of perfluoroalkanesulfonylimidic acid and an organic base" and "organic base" are obtained by reacting a perfluoroalkanesulfonyl halide with an organic base and ammonia or ammonium halide. It is a process of obtaining a mixture containing “a salt or a complex consisting of hydrogen halide” (Scheme 1; the definition of each reactant will be described later).

In perfluoroalkanesulfonyl halide used in this step, R _f is a perfluoroalkyl group having a linear or branched chain having 1 to 6 carbon atoms, preferably one R _f is from 1 to 4 carbon atoms, R _f is carbon The number 1 (trifluoromethyl group) is 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 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

[Wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom (except when R ¹ , R ² and R ³ are hydrogen atoms (ammonia)), an alkyl group, a substituted alkyl group, Represents an aryl group or a substituted aryl group. ]
A primary amine, a secondary amine or a tertiary amine represented by
Nitrogen-containing aromatic heterocyclic compounds,
Or the following imine skeleton -C = N-C-
Is an imine base having
The alkyl group is a linear or branched alkyl group having 1 to 12 carbon atoms or a cyclic alkyl group having 3 to 12 carbon atoms. The aryl group represents a phenyl group, a naphthyl group, an anthranyl group or the like.
The substituent in the substituted alkyl group is halogen (fluorine, chlorine, bromine, iodine), an amino group, an alkyl group having 1 to 12 carbon atoms (when substituted by a cyclic alkyl group), a haloalkyl group having 1 to 12 carbon atoms When it is substituted with an alkyl group), a nitro group, an acetyl group, a cyano group, an aryl group or a hydroxyl group, and the substituent in the substituted aryl group is a halogen (fluorine, chlorine, bromine, iodine), an amino group 10 alkyl group, haloalkyl group having 1 to 10 carbon atoms, nitro group, acetyl group, cyano group, aryl group or hydroxyl group.

Among these organic bases, a primary amine, a secondary amine or a tertiary amine, and R ¹ , R ² and R ^{3 in the} amine are each independently a hydrogen atom and having 1 to 8 carbon atoms. A linear or branched alkyl group, a cyclic alkyl group having 3 to 8 carbon atoms or an aryl group is preferable. Furthermore, among these, those which are tertiary amines and in which R ¹ , R ² and R ³ in the amine each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms are particularly preferable. .

  Specific examples of the organic base include methylamine, ethylamine, isopropylamine, n-butylamine, N-benzylamine, diethylamine, dipropylamine, trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine , Tri-n-butylamine, trioctylamine, tridecylamine, triphenylamine, tribenzylamine, tris (2-ethylhexyl) amine, N, N-dimethyldecylamine, N-benzyldimethylamine, N-butyl Dimethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N-dimethylaniline, N, N -Djec Aniline, 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, N-methyl morpholine, N-ethyl morpholine, N, N'-dimethyl piperazine, N-methyl pipecoline, N-methyl pyrrolidone, N-vinyl-pyrrolidone, bis (2 -Dimethylamino-ethyl) ether, N, N, N, N ', N' '-pentamethyl-diethylene triamine, triethanolamine, tripropanolamine, dimethylethanolamine, dimethylaminoethoxyethanol, N, N-dimethylaminopropylamine , N, N, N ', N', N ''-pentamethyldipropylene triamine, tris (3 Dimethylaminopropyl) amine, tetramethylimino-bis (propylamine), N-diethyl-ethanolamine, pyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, 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'-bipyridyl, 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 etc., among which trimethylamine, triethylamine, diisopropylethylamine , Tri-n-propylamine, triisopropylamine, tri-n-butylamine, trioctylamine, triphenylamine, N-butyldimethylamine or N, N-dimethylcyclohexylamine are preferred, among which triethylamine, diisopropylethylamine, triethylamine Particular preference is given to n-butylamine. 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 in the case of using ammonia and 4 moles in the case of using ammonium halide per mole of the perfluoroalkanesulfonyl halide. The amount is usually 3 to 10 moles, preferably 3 to 5 moles. If the amount is less than 3 moles, the reaction yield may be reduced. There is no problem with the progress of the reaction even if it is used in excess of 10 moles, but there is no particular merit 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 this step, the reaction can also be performed in the presence of an organic solvent or water. Here, the organic solvent refers to an inert organic compound not directly involved in the reaction of the present 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 or dimethyl sulfoxide and the like 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. 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. The second step is water washing of a mixture containing the “salt or complex consisting of perfluoroalkanesulfonylimide acid and organic base” obtained in the first step and the “salt or complex consisting of organic base and hydrogen halide” And / or by filtering
In this step, “a salt or complex consisting of an organic base and hydrogen halide” contained in the mixture is separated and removed to obtain “a salt or complex consisting of a perfluoroalkanesulfonylimidic acid and an organic base” (Scheme 2).

There is no restriction | limiting in particular as an embodiment implementing water washing and / or filtration, It may carry out with normal operation 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 divide the water of the above amount into several times and repeat washing and separation.
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 following [A-1 to A-3 step] or [B-1 to B] is performed on the “salt or complex consisting of perfluoroalkanesulfonylimidic acid and organic base” obtained in the second step: 3) is a step of obtaining perfluoroalkanesulfonylimidic acid metal salt by passing through (3) (Scheme 3).

First, the steps [A-1 to A-3] will be described in order.
[A-1 process]
Step A-1 comprises the “salt or complex comprising perfluoroalkanesulfonylimidic acid and an organic base” obtained in the second step, a halide or hydroxide of an alkali metal, or an alkaline earth metal in a solvent In this step, a halide or a hydroxide is reacted to obtain a mixed solution containing 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

  Moreover, these compounds can also be used 1 type or in combination of 2 or more types. 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 a hydroxide or an alkaline earth metal halide is used in this step, it is preferable to use an organic base and hydrogen halide in a mixed solution containing a metal salt of perfluoroalkanesulfonylimidate. In order to form the following salt or complex as a solid, it is preferable to separate and remove the "salt or complex consisting of an organic base and hydrogen halide" by carrying out the filtering operation on the liquid mixture. In this case, the reaction may be performed immediately after the reaction in this step, or may be performed immediately after distilling off the solvent in the subsequent [A-2 step]. 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.
[A-2 process]
A-2 processes distills a solvent off with respect to the liquid mixture containing the metal salt of perfluoro alkane sulfonyl imide obtained by A-1 process, and "a salt or complex which consists of an organic base and hydrogen halide" It is the process of obtaining the perfluoro alkane sulfonyl imidic acid metal salt by this. The embodiment of the solvent evaporation is not particularly limited, and may be carried out by the usual operation of organic chemistry.
[A-3 process]
Step A-3 is a step of subjecting the perfluoroalkanesulfonylimidate metal salt obtained in step A-2 to a recrystallization operation using a solvent to obtain a highly pure perfluoroalkanesulfonylimidate metal salt. .

As a solvent used for recrystallization, an organic solvent or water is mentioned. Examples of the organic solvent include ethers, alcohols, carbonates, aliphatic hydrocarbons, ketones, halogenated hydrocarbons, aromatic hydrocarbons and the like.
Specific compounds of these organic solvents are diethyl ether, tetrahydrofuran, dioxane, butyl methyl ether, diisopropyl ether, methyl tert-butyl ether ethylene glycol dimethyl ether, methanol, ethanol, n-propyl alcohol, iso-propyl alcohol, n- Butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, n-pentane, n-hexane, n-heptane, n-octane, With acetone, methyl ethyl ketone, methyl isobutyl ketone, dichloromethane, chloroform, benzene, toluene, xylene, etc. That. Each of these organic solvents may be used alone, or a plurality of organic solvents may be combined.

By recrystallization, a metal salt of perfluoroalkanesulfonylimidate is precipitated. In order to isolate this, it may be carried out by ordinary organic chemical operation, and "filtration operation" (note that "filtration operation" mentioned here indicates filtration operation in the recrystallization step. The same applies hereinafter). Further, a highly pure perfluoroalkanesulfonylimidic acid metal salt can be obtained.
Further, since the metal salt of perfluoroalkanesulfonylimidic acid is partially dissolved in the filtrate obtained by the filtration operation, the present inventors recover the obtained filtrate, and re-use as a solvent in recrystallization. We obtained the finding that it can be used (see Table 1 below). Since the yield of metal salts of perfluoroalkanesulfonylimidates can be further improved by reusing, and the waste liquid of the waste organic solvent can be largely reduced compared with the comparative examples described later, the productivity is remarkably improved. It will be improved.

Next, the [B-1 to B-3 steps] will be described in order.
[B-1 process]
In step B-1, the “salt or complex comprising perfluoroalkanesulfonylimidic acid and an organic base” obtained in the second step is subjected to a recrystallization operation using a solvent to obtain high purity “perfluoroalkanesulfonylimide” It is a process of obtaining "a salt or complex consisting of an acid and an organic base".

As a solvent used for recrystallization, an organic solvent or water is mentioned.
The specific type of the organic solvent, the conditions for the recrystallization operation, and the embodiment such as the post-treatment are the same as those in the above-mentioned A-3 step and the conditions described in the step are the B-1 step. Can be applied as it is.

By the recrystallization, "a salt or complex composed of perfluoroalkanesulfonylimide acid and an organic base" is precipitated. In order to isolate this, it may be carried out by the usual operation of organic chemistry, and by carrying out the filtration operation, “perfluoroalkanesulfonyl imide acid and organic base” having higher purity compared with the above-mentioned second step Salts or complexes can be obtained.
Moreover, since "a salt or complex consisting of perfluoroalkanesulfonylimidic acid and an organic base" is partially dissolved in the filtrate obtained by the filtration operation, the present inventors recovered the obtained filtrate. And it has been found that it is possible to reuse as a solvent in recrystallization (see Table 1 below). By further improving the yield of “a salt or complex comprising perfluoroalkanesulfonylimide acid and an organic base” by reusing it, the waste liquid of the waste organic solvent is significantly reduced even compared to the comparative example described later. The ability to do so has significantly improved productivity.
[B-2 process]
Process B-2 is a high purity "salt or complex consisting of perfluoroalkanesulfonylimidic acid and an organic base" obtained in process B-1, a halide of an alkali metal or alkaline earth metal in a solvent, or In this step, a hydroxide of an alkali metal or an alkaline earth metal is reacted to obtain a liquid mixture containing a metal salt of perfluoroalkanesulfonylimidate.

Step B-2 is the same as Step A-1 described above except for the starting materials, and the reaction reagent, reaction conditions, and embodiment used, and the conditions described in Step A-1 can be applied as they are in Step B-2. . The case of using an alkali metal or alkaline earth metal halide in this step is also the same as step A-1, and it is composed of “organic base and hydrogen halide in a mixed solution containing metal salt of perfluoroalkanesulfonylimidate. Since a salt or complex is formed, the “salt or complex consisting of an organic base and hydrogen halide” can be separated and removed from the liquid mixture by carrying out the filtering operation on the liquid mixture.
[B-3 process]
B-3 process is a process of obtaining the perfluoro alkane sulfonyl imide metal salt by distilling a solvent off with respect to the liquid mixture containing the perfluoro alkane sulfonyl imide acid metal salt obtained at B-2 process.

There is no restriction | limiting in particular as an aspect of solvent distillation, It may carry out by normal operation of organic chemistry.
[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).

[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 92% (0.35 mol) and the purity was 95.7% based on the starting material ammonia. .
[Second step]
After distilling off the solvent of the reaction solution obtained in the above reaction step, the residue is washed with water to obtain 136 g of a crude product of bistrifluoromethanesulfonylimidotriethylammonium salt (here, 132 g of waste organic solvent and 520 g of waste water Living). The crude product was quantified by ¹⁹ F-NMR, and the yield relative to the starting material ammonia was 87% (0.33 mol).
[Third step]
The crude body 136g obtained at the said 2nd process was put into a 500 ml four necked flask, and 100 g of water was added. 17 g (0.40 mol) of lithium hydroxide monohydrate was added, and the mixture was heated to 60 ° C. and concentrated to obtain lithium bistrifluoromethanesulfonylimide as a crude product of 98 g (here, 153 g of wastewater was by-produced).
Next, 98 g of the crude product was put into a 500 ml four-necked flask, and dissolved in 100 g of methyl-tert-butyl ether, and then 1000 g of chloroform was dropped to precipitate white crystals. After filtering the crystals and drying, 76 g of lithium trifluoromethanesulfonylimide having a purity of 97.8% was obtained in a yield of 69% (0.26 mol) (the filtrate was 1114 g as a by-product).

[First step]
In a 500 ml autoclave, 120 g of acetonitrile and 222 g (1.20 mol) of tri-n-butylamine 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. After the completion of the introduction of anhydrous ammonia, the reactor was warmed to room temperature and stirred for 13 hours. After 13 hours, as a result of quantifying the reaction liquid by ¹⁹ F-NMR, the yield of bis trifluoromethanesulfonyl imide tri-n-butyl ammonium salt is 90% (0.34 mol) and purity 96% with respect to the starting material ammonia. The
[Second step]
After distilling off the solvent of the reaction solution obtained in the above first step, the residue is washed with water, and the resulting white crystals are filtered under reduced pressure using a Kiriyama funnel to obtain bis-trifluoromethanesulfonylimide tri-n-butylammonium. 134 g of a crude salt was obtained (here, 144 g of the waste organic solvent and 243 g of the waste water). The crude product was quantified by ¹⁹ F-NMR to find that the yield relative to the starting material ammonia was 88% (0.33 mol).
[Third step]
Next, 134 g of this crude product was placed in a 500 ml four-necked flask, and 100 g of dimethyl carbonate was added. The mixture was heated to 50 ° C. to completely dissolve the crystals, and then cooled to 5 ° C. or less to precipitate crystals. The precipitated crystals were filtered under reduced pressure using a Kiriyama funnel to obtain 124 g of bis (trifluoromethanesulfonylimide) tri-n-butylammonium salt (here, 117 g of the filtrate was by-produced). The crude product was quantified by ¹⁹ F-NMR, and as a result, the yield of the starting material to ammonia was 67% (0.26 mol), and the purity was 99% or more.
Furthermore, 70 g (0.15 mol) of bistrifluoromethanesulfonylimide tri-n-butylammonium salt obtained in the second step, 150 g of dimethyl carbonate, and 7.6 g (0.18 mol) of lithium chloride are added to a 500 ml four-necked flask The mixture was stirred for 15 hours at room temperature. The reaction mixture was filtered, and the obtained filtrate was concentrated and dried (here, 150 g of the waste organic solvent was by-produced). After drying, 41 g of lithium bistrifluoromethanesulfonylimide having a purity of 99% or more was obtained in a yield of 64% (0.14 mol).

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 relative to the starting material ammonia was 91.0% (0.346 mol), and the purity was 95.7%. 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.

[Step 1 to Step 2]
In the same manner as in Example 1, 120 g of crude trifluoromethanesulfonylimidotriethylammonium salt was obtained. The crude product was quantified by ¹⁹ F-NMR to find that the yield relative to the starting material ammonia was 87% (0.29 mol).
[Third step]
130 g of the crude product obtained in the second step was placed in a 500 ml four-necked flask, and 100 g of water was added. 13 g (0.17 mol) of calcium hydroxide was added, and the mixture was heated to 60 ° C. and concentrated to obtain 105 g of calcium bistrifluoromethanesulfonylimide as a crude product.
Next, 105 g of a crude body was put into a 500 ml four-necked flask, and dissolved in 100 g of methyl-t-butyl ether, and then 1000 g of chloroform was dropped to precipitate white crystals. After filtering the crystals and drying, 74 g (0.25 mol) of calcium bistrifluoromethanesulfonylimide having a purity of 99.2% was obtained in a yield of 65%.

The metal salt of perfluoroalkanesulfonylimidate targeted by the present invention can be used as an intermediate for medicine and agricultural chemicals, battery electrolyte, and acid catalyst.

Claims (7)

Formula [1]:

[Wherein, each R _f independently represents a linear or branched 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 linear or branched perfluoroalkyl group having 1 to 6 carbon atoms, and X represents a halogen atom]
By reacting an organic base and ammonia or ammonium halide with a perfluoroalkanesulfonyl halide represented by
"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 washing and / or filtration of a mixture containing “a salt or complex consisting of perfluoroalkanesulfonylimide acid and an organic base” obtained in the first step and “a salt or complex consisting of an organic base and hydrogen halide” By doing
Separately remove “the salt or complex consisting of an organic base and hydrogen halide” contained in the mixture,
Obtaining a "salt or complex composed of perfluoroalkanesulfonylimidic acid and an organic base".
[Third step]
The following [A-1 to A-3 steps] or [B-1 to B-3 steps] of the “salt or complex consisting of perfluoroalkanesulfonylimide acid and organic base” obtained in the second step A step of obtaining a perfluoroalkanesulfonylimidic acid metal salt by passing through.
[A-1 process]
The “salt or complex comprising perfluoroalkanesulfonylimidic acid and an organic base” obtained in the second step, a halide of an alkali metal or an alkaline earth metal in a solvent,
Or by reacting alkali metal or alkaline earth metal hydroxides,
A step of obtaining a mixed solution containing the perfluoroalkanesulfonylimidic acid metal salt represented by the formula [1].
[A-2 process]
A step of obtaining a perfluoroalkanesulfonylimidate metal salt by distilling off the solvent from the mixture liquid containing the perfluoroalkanesulfonylimidate metal salt obtained in the step A-1 step.
[A-3 process]
A-2 A step of subjecting the perfluoroalkanesulfonylimidate metal salt obtained in the step 2 to a recrystallization operation using a solvent to obtain a highly pure perfluoroalkanesulfonylimidate metal salt.
[B-1 process]
The “salt or complex consisting of perfluoroalkanesulfonylimide acid and organic base” obtained in the second step is subjected to recrystallization operation using a solvent, and is composed of “highly pure perfluoroalkanesulfonylimide acid and organic base” Obtaining a salt or a complex ".
[B-2 process]
A “salt or complex of“ perfluoroalkanesulfonylimidic acid and an organic base ”of high purity obtained in the step B-1, a halide of an alkali metal or an alkaline earth metal in a solvent,
Or by reacting alkali metal or alkaline earth metal hydroxides,
A step of obtaining a mixed solution containing the perfluoroalkanesulfonylimidic acid metal salt represented by the formula [1].
[B-3 process]
B-2 A step of obtaining a metal salt of perfluoroalkanesulfonylimidate by distilling off the solvent from the mixture liquid containing the metal salt of perfluoroalkanesulfonylimidate obtained in the step S2. The method according to claim 1, wherein the organic base used in the first step is a primary amine, a secondary amine, a tertiary amine, a nitrogen-containing aromatic heterocyclic compound or an imine base. The method according to claim 1 or 2, further comprising the step of carrying out the reaction using a solvent in the first step, followed by concentration and distilling off the solvent before washing with water and / or filtering in the 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 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 solvent used in reacting the halide or hydroxide of an alkali metal in the third step [A-1 step] or [B-2 step] is an ester, an amide or a nitrile. The manufacturing method according to any one of 1 to 4. “Salt or complex comprising an organic base and hydrogen halide” formed by the reaction using an alkali metal or alkaline earth metal halide in the third step [A-1 step] or [A-2 step] The method according to any one of claims 1 to 5, further comprising the step of separating and removing by a filtering operation. “Salt or complex consisting of an organic base and hydrogen halide” formed by the reaction using an alkali metal or alkaline earth metal halide in the third step [B-2 step] or [B-3 step] The method according to any one of claims 1 to 5, further comprising the step of separating and removing by a filtering operation.