Method for producing imidic acid or imidic acid salt

Abstract

This method for producing an imidic acid represented by general formula [1] or an imidic acid salt has a reaction step in which a phosphoryl isocyanate represented by general formula [2] and a compound represented by general formula [3] are reacted with each other, and a basic compound is present during the reaction step and / or after the reaction step.

Description

Method for producing imide acid or imide salt

[0001] The present disclosure relates to a method for producing various imide acids or imide salts having a phosphoryl group.

[0002] Bis(phosphoryl)imide (HN(POX ２ ) ２ ) and asymmetric phosphoryl imide (HN(POX ２ ) (SO ２ In recent years, various imide acids having a phosphoryl group such as X) and their metal salts and onium salts have been known to be useful substances as ion-conductive materials, anion sources for ionic liquids, electrolytes for non-aqueous electrolyte batteries such as lithium ion batteries, lithium batteries, lithium ion capacitors, and sodium ion batteries, and as additives.

[0003] Patent Document 1 discloses a method for producing an asymmetric phosphoryl imide acid compound, which comprises reacting a phosphonitrile compound with triethylamine trihydrofluoride to prepare a phosphoryl compound, and then reacting the phosphoryl compound with lithium carbonate (see reaction formula (1) below).

[0004]

[0005] Patent Document 2 discloses a method for producing a fluororesin by the synthesis of potassium (difluorophosphoryl) (fluorosulfonyl) imine and lithium perchlorate (LiClO ４ ) and potassium perchlorate (KClO ４ ) was removed, and Li[N(POF ２ ) (SO ２ A method for obtaining [F)] is disclosed.

[0006] Patent Document 3 describes a method for obtaining an asymmetric phosphoryl imide by reacting a silazane derivative containing a sulfonyl group with phosphorus oxychloride (reaction formula (3) below).

[0007]

[0008] Patent Document 4 describes a method for obtaining an asymmetric phosphoryl imide by reacting a siloxane compound, a chlorosulfonimide compound, and an alkali metal hexafluorophosphate to synthesize a phosphoryl imine alkali metal salt, and then fluorinating the obtained metal salt with lithium fluoride (reaction formula (4) below).

[0009]

[0010] Patent Document 5 describes a method for obtaining an asymmetric phosphoryl imide salt by reacting trifluoromethanesulfonamide with phosphorus oxydifluorochloride in the presence of triethylamine (reaction formula (5) below).

[0011]

[0012] Chinese Patent Publication No. CN109705156A Chinese Patent Publication No. CN101654229A Chinese Patent Publication No. CN102617414A Chinese Patent Publication No. CN109422252A International Publication No. 2018 / 190304

[0013] However, the target product (imidic acid or imidic acid salt) obtained by the conventional production method may gradually decompose during storage at room temperature, and there is room for improvement in the stability of the target product. The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a novel synthesis method for obtaining imidic acid or imidic acid salt by reacting an isocyanate compound with various acid salts, which can improve the storage stability of the target product.

[0014] The present inventors have discovered a new method for producing an imide acid or an imide salt having a phosphoryl group represented by the general formula [1] or [4] below, and have come to the present disclosure.

[0015] [1] A method for producing an imidic acid or imidic acid salt represented by the following general formula [1], comprising a reaction step of reacting phosphoryl isocyanate represented by the following general formula [2] with a compound represented by the following general formula [3], wherein a basic compound is allowed to be present in the reaction step and / or after the reaction step. [In general formula [1], X １ , X２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may contain at least one selected from a fluorine atom, an oxygen atom, a nitrogen atom, and an unsaturated bond. Z is -P(=O)-, -S(=O) ２ When Z is -P(=O)-, a is 1, and when Z is -S(=O) ２ When it is - or -C(=O)-, a is 0. １ , R ２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may also contain at least one type selected from a fluorine atom, an oxygen atom, and an unsaturated bond. ｍ＋ represents a proton, an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation. [In general formula [2], X １ , X ２are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may also contain at least one type selected from a fluorine atom, an oxygen atom, a nitrogen atom, and an unsaturated bond. [In the general formula [3], Z is -P(=O)-, -S(=O) ２ -, or -C(=O)-. When Z is -P(=O)-, a is 1. When Z is -S(=O) ２ When Z is -, a is 0. When Z is -C(=O)-, a is 0. R １ , R ２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may also contain at least one type selected from a fluorine atom, an oxygen atom, and an unsaturated bond. ｍ＋is a proton, an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m is an integer equal to the valence of the corresponding cation.] [2] The method for producing an imidic acid or an imidic acid salt according to [1], wherein the basic compound comprises one or more compounds selected from the group consisting of amine compounds, nitrogen-containing heterocyclic compounds, carbodiimide group-containing compounds, phosphite compounds, alkali metal compounds, and alkaline earth metal compounds. [3] The method for producing an imidic acid or an imidic acid salt according to [1] or [2], wherein the basic compound is present in an amount of 0.01 to 30 mol % relative to the compound represented by general formula [3] during the reaction step and / or after the reaction step. [4] The method for producing an imidic acid or an imidic acid salt according to any of [1] to [3], wherein the amount of phosphoryl isocyanate represented by general formula [2] used is 0.1 to 10 mol per mol of the compound represented by general formula [3]. [5] The method for producing an imidic acid or an imidic acid salt according to any of [1] to [4], wherein the reaction temperature in the reaction step is −20 to 200° C. [6] The method for producing an imidic acid or an imidic acid salt according to any one of [1] to [5], wherein the reaction step is carried out in a reaction solvent. [7] The method for producing an imidic acid or an imidic acid salt according to [6], wherein the reaction solvent is at least one solvent selected from the group consisting of nitriles, chain ethers, cyclic ethers, chain esters, cyclic esters, chain carbonates, cyclic carbonates, and sulfur-containing solvents. [8] The method for producing an imidic acid or an imidic acid salt according to [6], wherein the M ｍ＋ [9] The method for producing an imidic acid or an imidic acid salt according to any one of [1] to [7], wherein X is a proton, a lithium ion, a sodium ion, a potassium ion, a trialkylammonium ion, or a tetraalkylammonium ion. １ , X ２are each independently selected from a chlorine atom, a fluorine atom, a methyl group, a trifluoromethyl group, a phenyl group, a fluorophenyl group, a vinyl group, a thienyl group, and a pyridinyl group.

[10] The method for producing an imidic acid or an imidic acid salt according to any one of [1] to [9], wherein the reaction solution after the reaction step is degassed and concentrated.

[11] A method for producing an imidic acid or an imidic acid salt represented by the following general formula [4], comprising a reaction step of reacting a sulfonyl isocyanate represented by the following general formula [5] with a compound represented by the following general formula [6], wherein a basic compound is present during the reaction step and / or after the reaction step. [In general formula [4], X １ , X ２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may contain at least one selected from a fluorine atom, an oxygen atom, a nitrogen atom, and an unsaturated bond. １ is an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and at least one type selected from a fluorine atom, an oxygen atom, and an unsaturated bond may be present in the organic group. ｍ＋represents a proton, an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation. [In general formula [5], R １ is an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may also contain at least one type selected from a fluorine atom, an oxygen atom, and an unsaturated bond.] [In general formula [6], X １ , X ２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may contain at least one selected from a fluorine atom, an oxygen atom, a nitrogen atom, and an unsaturated bond. ｍ＋is a proton, an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m is an integer equal to the valence of the corresponding cation.]

[12] The method for producing an imidic acid or an imidic acid salt according to

[11] , wherein the basic compound comprises one or more compounds selected from the group consisting of amine compounds, nitrogen-containing heterocyclic compounds, carbodiimide group-containing compounds, phosphite compounds, alkali metal compounds, and alkaline earth metal compounds.

[13] The method for producing an imidic acid or an imidic acid salt according to

[11] or

[12] , wherein the basic compound is present in an amount of 0.01 to 30 mol % relative to the compound represented by general formula [6] during the reaction step and / or after the reaction step.

[14] The method for producing an imidic acid or an imidic acid salt according to any one of

[11] to

[13] , wherein the amount of the sulfonyl isocyanate represented by general formula [5] used is 0.1 to 10 mol relative to 1 mol of the compound represented by general formula [6].

[15] The method for producing an imidic acid or an imidic acid salt according to any one of

[11] to

[14] , wherein the reaction temperature in the reaction step is 0 to 150°C.

[16] The method for producing an imidic acid or an imidic acid salt according to any one of

[11] to

[15] , wherein the reaction step is carried out in a reaction solvent.

[17] The method for producing an imidic acid or an imidic acid salt according to

[16] , wherein the reaction solvent is at least one solvent selected from the group consisting of nitriles, linear ethers, cyclic ethers, linear esters, cyclic esters, linear carbonates, cyclic carbonates, and sulfur-containing solvents.

[18] The method for producing an imidic acid or an imidic acid salt according to any one of

[11] to

[14] , wherein the reaction temperature in the reaction step is 0 to 150°C. ｍ＋

[19] The method for producing an imidic acid or an imidic acid salt according to any one of

[11] to

[17] , wherein X is a proton, a lithium ion, a sodium ion, a potassium ion, a trialkylammonium ion, or a tetraalkylammonium ion. １ , X ２are each independently selected from a chlorine atom, a fluorine atom, a methyl group, a trifluoromethyl group, a phenyl group, a fluorophenyl group, a vinyl group, a thienyl group, and a pyridinyl group.

[20] The method for producing an imidic acid or an imidic acid salt according to any one of

[11] to

[19] , wherein the reaction solution after the reaction step is degassed and concentrated.

[0016] In the production method of the present disclosure, when obtaining an imide acid or an imide salt having a phosphoryl group represented by the above general formula [1] or [4], a solid by-product is hardly produced, but carbon dioxide is produced as a by-product. Carbon dioxide is a gas at room temperature and normal pressure, and can be easily separated from the reaction solution. In addition, no special treatment is required for the carbon dioxide after separation, making the production method of the present disclosure industrially suitable.

[0017] According to the production method of the present invention, it is possible to obtain an imide acid or an imide salt having a phosphoryl group, which has excellent storage stability.

[0018] The present disclosure will be described in detail below, but the following description of the constituent elements is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific details. Various modifications can be made within the scope of the gist of the disclosure. Furthermore, for example, "1 to 10" means "1 or more" to "10 or less" unless otherwise specified.

[0019] <Method for producing imidic acid or imidic acid salt> The method for producing imidic acid or imidic acid salt represented by the above general formula [1] according to invention 1 includes a reaction step of reacting phosphoryl isocyanate represented by the above general formula [2] with a compound represented by the above general formula [3], and a basic compound is made present during and / or after the reaction step.

[0020] The method for producing an imidic acid or an imidic acid salt represented by the general formula [4] according to the second aspect of the present invention comprises a reaction step of reacting a sulfonyl isocyanate represented by the general formula [5] with a compound represented by the general formula [6], and a basic compound is allowed to be present during and / or after the reaction step.

[0021] As described above, in the methods for producing imidic acids or imidic acid salts according to Inventions 1 and 2, a basic compound is made to be present at least either during the reaction step of reacting an isocyanate compound represented by general formula [2] (or general formula [5]) with a compound (acid salt) represented by general formula [3] (or general formula [6]) and after the reaction step.

[0022] The present inventors have confirmed that in a method for producing imidic acid or imidic acid salts by reacting an isocyanate compound with various acid salts, the target product tends to gradually decompose during storage at room temperature due to the acid content contained in the product, although the details are unknown. Further investigation has revealed that this acid content may be derived from trace amounts of acid present in the raw materials. Therefore, when a basic compound was added during or after the reaction step, it was presumed that the basic compound captured the acid content, although the details are unknown. As a result, the storage stability of the target imidic acid or imidic acid salt was improved, and the present invention was completed.

[0023] That is, according to the present invention, the presence of a basic compound in the reaction step and / or after the reaction step can improve the storage stability of the target product (imidic acid or imidic acid salt). Furthermore, since the basic compound is presumed to capture the acid in the reaction step, the risk of the acid complicating the reaction between the isocyanate compound and various acid salts is reduced, and as a result, the yield after the preparation step described below (hereinafter also simply referred to as "yield") can also be improved.

[0024] In Inventions 1 and 2, allowing a basic compound to be present in the reaction step refers to the following aspects (A) to (C): (A) adding the basic compound to raw materials used in the reaction step (such as an isocyanate compound represented by general formula [2] (or general formula [5]), a compound (acid salt) represented by general formula [3] (or general formula [6]), and other reaction solvents), and reacting the isocyanate compound with the compound (acid salt) in the presence of the basic compound; (B) adding the raw materials used in the reaction step to a basic compound, and reacting the isocyanate compound with the compound (acid salt) in the presence of the basic compound; (C) adding the basic compound to the reaction product produced during the reaction between the isocyanate compound and the compound (acid salt), and further reacting the isocyanate compound with the compound (acid salt) in the presence of the basic compound. In Inventions 1 and 2, allowing a basic compound to be present after the reaction step refers to the following aspect (D). (D) After the reaction between the isocyanate compound and the compound (acid salt) is completed (before the preparation step described below), the basic compound is added to the obtained reaction liquid to allow the basic compound to be present. Note that in the above embodiments (A) to (D), from the viewpoints of handleability and dispersibility, the basic compound may also be used in the form of a dispersion in which it is dispersed in a reaction solvent.

[0025] Inventions 1 and 2 involve making the basic compound present during the reaction step and / or after the reaction step, and specifically, the basic compound can be made present at one or more of the timings of any one of the above-mentioned modes (A) to (D). From the viewpoint of suppressing the generation of acids and further improving at least one of the storage stability and yield of the target product, it is preferable to add the basic compound at least before the reaction (mode (A) or mode (B), preferably mode (A)), and it is more preferable to add the basic compound at least before and after the reaction (a combination of mode (A) or mode (B) and mode (D), preferably a combination of mode (A) and mode (D)).

[0026] (Basic Compound) The basic compound has a pKa of the proton form falling within the range of 0 to 40. Examples of the basic compound include amine compounds, nitrogen-containing heterocyclic compounds, carbodiimide group-containing compounds, phosphite ester compounds, alkali metal compounds, and alkaline earth metal compounds, and the basic compound may contain one or more compounds selected from these.

[0027] Examples of the amine compound include ammonia, triethylamine, and amine group-containing styrene-based anion exchange resins. Examples of the amine group-containing styrene-based anion exchange resin include Amberlite B20-HG DRY and Amberlite IRA96SB (both manufactured by Organo Corporation). Examples of the nitrogen-containing heterocyclic compound include pyridine and 2-ethylimidazole.

[0028] Examples of carbodiimide group-containing compounds include N,N-dicyclohexylcarbodiimide. Examples of phosphite ester compounds include triphenyl phosphite. Examples of alkali metal compounds include lithium hydroxide, lithium carbonate, lithium acetate, lithium fluoride, and lithium phosphate. Examples of alkaline earth metal compounds include magnesium hydroxide and calcium oxide.

[0029] (Reaction Raw Materials) In the production method according to the first invention, the preferred groups of the compound represented by the general formula [2] or [3], which is the reaction raw material, are as follows. The same applies to the preferred groups of the compound represented by the general formula [1], which is the target product. In the general formula [2], X １ , X ２ are each independently preferably a chlorine atom, a fluorine atom, or a linear or branched alkoxy group having 1 to 5 carbon atoms, more preferably a chlorine atom or a fluorine atom.

[0030] In the general formula [3], Z is preferably —P(═O)— or —C(═O)—.

[0031] In general formula [3], R １ , R２ are each independently preferably a chlorine atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched fluoroalkyl group having 1 to 5 carbon atoms, or a linear or branched alkoxy group having 1 to 5 carbon atoms, and more preferably a linear or branched fluoroalkyl group having 1 to 3 carbon atoms, or a linear or branched alkoxy group having 1 to 3 carbon atoms.

[0032] In general formula [3], M ｍ＋ is preferably a proton, an alkali metal cation, or an onium cation, more preferably a proton or an alkali metal cation, and even more preferably an alkali metal cation. Examples of the alkali metal cation include a lithium ion, a sodium ion, and a potassium ion. Examples of the onium cation include a trialkylammonium ion and a tetraalkylammonium ion.

[0033] In the production method according to the second invention, the preferred groups of the compound represented by the general formula [5] or [6], which is the raw material for the reaction, are as follows. The preferred groups of the compound represented by the general formula [4], which is the target, are also as follows. In the general formula [6], X １ , X ２ are each independently preferably a chlorine atom, a fluorine atom, or a linear or branched alkoxy group having 1 to 5 carbon atoms, and more preferably a fluorine atom, or a linear or branched alkoxy group having 1 to 3 carbon atoms. １ is preferably a chlorine atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a linear or branched fluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom or a linear or branched fluoroalkyl group having 1 to 3 carbon atoms. ｍ＋is preferably a proton, an alkali metal cation, or an onium cation, more preferably a proton or an alkali metal cation, and even more preferably an alkali metal cation. Examples of the alkali metal cation include a lithium ion, a sodium ion, and a potassium ion. Examples of the onium cation include a trialkylammonium ion and a tetraalkylammonium ion.

[0034] In Inventions 1 and 2, the water content in the compound represented by the general formula [3] or [6] used as a reaction raw material may be 1000 ppm by mass or less. If the water content is 1000 ppm by mass or less, the compound represented by the general formula [2] or [5], which is the reaction partner, is unlikely to be hydrolyzed. From the above viewpoint, the smaller the water content, the better.

[0035] (Reaction Conditions) In Inventions 1 and 2, from the viewpoint of suppressing solvolysis or hydrolysis of the compound represented by the general formula [2] or [5], which is a reaction raw material in the reaction step, the reaction solvent that may be used in the reaction step may be an aprotic solvent such as a nitrile, a chain ether, a cyclic ether, a chain ester, a cyclic ester, a chain carbonate, a cyclic carbonate, or a sulfur-containing solvent. Furthermore, the water content in the aprotic solvent may be 1000 ppm by mass or less, or 100 ppm by mass or less. From the viewpoint of suppressing hydrolysis of the compound represented by the general formula [2] or [5], the smaller the water content, the better.

[0036] Specific examples of the aprotic solvent include nitriles such as acetonitrile, propionitrile, and valeronitrile; chain ethers such as diethyl ether, diisopropyl ether, and 1,2-dimethoxyethane; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, and tetrahydropyran; chain esters such as ethyl acetate, butyl acetate, and isopropyl acetate; cyclic esters such as γ-butyrolactone and γ-valerolactone; chain carbonates such as diethyl carbonate, dimethyl carbonate, and ethyl methyl carbonate; cyclic carbonates such as propylene carbonate, ethylene carbonate, and butylene carbonate; and sulfur-containing solvents such as sulfolane, 3-methylsulfolane, and dimethyl sulfoxide. These aprotic solvents may be dehydrated. The dehydration method is not particularly limited, and for example, a method in which water is adsorbed by synthetic zeolite or the like can be used. The above aprotic solvents may be used singly or in any combination of two or more in any ratio depending on the application.

[0037] The amount of the reaction solvent may be in the range of 0.1 to 100 parts by mass per part by mass of the compound represented by the general formula [3] or [6]. If the amount is 0.1 part by mass or more, the increase in viscosity due to the imidic acid or imidic acid salt having a phosphoryl group represented by the general formula [1] produced by the reaction is likely to be suppressed, and the subsequent reaction is likely to proceed smoothly. If the amount is 100 parts by mass or less, the reaction itself will not be problematic and it is economical. From the above viewpoint, the amount of the reaction solvent may be in the range of 0.1 to 20 parts by mass, or may be in the range of 1 to 10 parts by mass per part by mass of the compound represented by the general formula [3] or [6].

[0038] The amount of the isocyanate compound represented by the general formula [2] or [5] used in the reaction step of Invention 1 and Invention 2 may be 0.1 to 10 moles relative to 1 mole of the corresponding reaction partner, the compound represented by the general formula [3] or [6]. If the amount is 0.1 mole or more, a large amount of imidic acid or imidic acid salt having a phosphoryl group is obtained, which is economical. Furthermore, if the amount is 10 moles or less, the amount of excess isocyanate compound is small, which is economical. From the above perspective, the amount of the isocyanate compound represented by the general formula [2] or [5] used may be 0.5 to 2 moles relative to 1 mole of the compound represented by the general formula [3] or [6]. Furthermore, if the compound represented by the general formula [3] or [6] is in excess, a step of filtering and removing the excess from the reaction solution is required. Therefore, from the perspective of simplifying the process, an excess of the isocyanate compound that can be removed by degassing and concentration may be acceptable. In this case, the amount of the isocyanate compound represented by the general formula [2] or [5] used may be 1.01 to 2 moles per mole of the compound represented by the general formula [3] or [6].

[0039] In the reaction step of Invention 1 and / or after the reaction step, the basic compound can be present in an amount of preferably 0.01 to 30 mol %, more preferably 0.02 to 25 mol %, and even more preferably 0.05 to 20 mol %, relative to the compound represented by General Formula [3]. In the reaction step of Invention 2 and / or after the reaction step, the basic compound can be present in an amount of preferably 0.01 to 30 mol %, more preferably 0.02 to 25 mol %, and even more preferably 0.05 to 20 mol %, relative to the compound represented by General Formula [6]. Here, "presence" of a predetermined amount of the basic compound means that the predetermined amount is present at least at one point during the step, and the "presence" amount typically refers to the amount added. Presence of the basic compound in this amount is presumed to effectively capture acid, resulting in superior storage stability of the target product. Furthermore, addition of the basic compound in the reaction step is presumed to further suppress the effect of acid on the reaction, resulting in improved yield.

[0040] In Invention 1, the amount of the basic compound added in the reaction step can be preferably 0.01 to 20 mol %, more preferably 0.02 to 15 mol %, and even more preferably 0.05 to 12 mol %, relative to the compound represented by General Formula [3], and the amount of the basic compound added after the reaction step can be preferably 0.01 to 20 mol %, more preferably 0.02 to 15 mol %, and even more preferably 0.05 to 12 mol %, relative to the compound represented by General Formula [3]. In Invention 1, when the basic compound is added both in the reaction step and after the reaction step, the respective amounts added can be combined so as to fall within the above-mentioned range of the amount present.

[0041] In Invention 2, the amount of the basic compound added in the reaction step can be preferably 0.01 to 20 mol %, more preferably 0.02 to 15 mol %, and even more preferably 0.05 to 12 mol %, relative to the compound represented by General Formula [6], and the amount of the basic compound added after the reaction step can be preferably 0.01 to 20 mol %, more preferably 0.02 to 15 mol %, and even more preferably 0.05 to 12 mol %, relative to the compound represented by General Formula [6]. In Invention 2, when the basic compound is added both in the reaction step and after the reaction step, the respective amounts added can be combined so as to fall within the above-mentioned range of the amount present.

[0042] In Inventions 1 and 2, by setting the amount of the basic compound added in the reaction step or after the reaction step within the above range, it is presumed that the acid content can be more effectively captured, resulting in even better storage stability of the target product. Furthermore, by adding the basic compound in the reaction step (particularly before the reaction), it is presumed that the effect of the acid content on the reaction can be further suppressed, resulting in even better yield. Note that, although the details are unknown, if the amount of the basic compound in the reaction step exceeds the upper limit of the above range, the yield may be reduced due to moisture contained in the basic compound, etc.

[0043] When a basic compound is present in the reaction step, the basic compound can be added multiple times before and during the reaction, and the total amount added can be within the above range. The basic compound can be added directly to the raw materials before the reaction, and directly to the reaction solution during and after the reaction. A dispersion of the basic compound in a reaction solvent can also be added. The basic compound can be added all at once or gradually.

[0044] The temperature of the reaction step in Inventions 1 and 2 may be adjusted appropriately taking into consideration the thermal stability of the raw material compounds and the resulting imidic acid or imidic acid salt, and may be, for example, in the range of -20 to 200°C. If the reaction temperature is -20°C or higher, the reaction time tends to be shorter. If the reaction temperature is 200°C or lower, decomposition of the raw material compounds and the resulting imidic acid or imidic acid salt is unlikely to occur. The reaction temperature may be in the range of 0 to 150°C, or in the range of 10 to 120°C.

[0045] The reaction time of the reaction steps of Invention 1 and Invention 2 is not particularly limited, but may be terminated after it has been confirmed by techniques such as NMR, gas chromatography, and high performance liquid chromatography that the raw materials have been sufficiently consumed and the reaction no longer proceeds, and the reaction time can be appropriately adjusted by a person skilled in the art.

[0046] In Inventions 1 and 2, the raw material isocyanate compound and its reaction product are easily hydrolyzed by moisture, so the reaction may be carried out in a moisture-free atmosphere, for example, in an inert gas atmosphere such as nitrogen.

[0047] The reactor used in the reaction steps of Inventions 1 and 2 is not particularly limited in material as long as it is not corroded by the raw materials or reaction products. Reactors lined with tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass, or the like, or glass containers can be used. Metal containers such as stainless steel, Hastelloy, and Monel can also be used. In addition, the by-product CO ２In order to suppress foaming due to the reaction, a foam-suppressing blade may be provided on the inner wall of the reactor used, on the agitator, or on both.

[0048] In the reaction steps of Inventions 1 and 2, the order in which the reaction materials are added is not particularly limited. However, because of the risk of rapid generation of carbon dioxide gas as a by-product and foaming, a procedure may be adopted in which the reaction solvent and the compound represented by general formula [3] or [6] are added in that order, followed by stirring, and then gradually adding the corresponding reaction partner, the isocyanate compound represented by general formula [2] or [5]. When the basic compound is added before the reaction, the order in which the basic compound is added is not particularly limited. However, from the viewpoint of suppressing acid generation, it is preferable to add the basic compound all at once before adding the isocyanate compound represented by general formula [2] or [5]. The addition time is not particularly limited and can be any time, but the isocyanate compound may be added over a period of 0.5 to 10 hours. Addition times exceeding 10 hours are uneconomical due to the long time required. After adding the isocyanate compound represented by general formula [2] or [5] as described above, the reaction may be continued with stirring for an additional 1 to 15 hours.

[0049] [Preparation Step] After the reaction steps of Inventions 1 and 2, a preparation step can be carried out. The preparation step is a step of preparing imidic acid or imidic acid salt in the form of a final product. The form of the final product refers to a liquid in which imidic acid or imidic acid salt is dissolved or dispersed, a powder of imidic acid or imidic acid salt, etc. In the case of a liquid, the process of preparing the final product refers to processes such as concentration adjustment by degassing concentration or dilution, filtration, and blending of additives. In the case of a powder, the process refers to processes such as isolation, drying, particle size adjustment, impurity removal, and blending of additives.

[0050] The degassing and concentration step is a step in which the gas phase containing volatile components from the reaction solution is reduced in pressure or a carrier gas substantially free of moisture, such as an inert gas such as nitrogen or argon or dry air, is passed through to discharge the volatile components outside the system, thereby increasing the concentration of solutes in the reaction solution. This operation also allows for the removal of dissolved carbon dioxide as a by-product. The lower limit temperature during degassing and concentration may be set to -20°C or 10°C. The upper limit temperature during degassing and concentration may be set to 90°C or 60°C. When the temperature during degassing and concentration is -20°C or higher, the concentration efficiency is high. Furthermore, when the temperature is 90°C or lower, the reaction solution is less likely to become discolored. In the filtration step, particles such as basic compounds and impurities can be removed from the reaction solution.

[0051] The reaction solution containing the imidic acid, imidic acid salt, and solvent obtained by the production method of the present disclosure can be used, for example, as an anion source for an ionic liquid, an electrolyte or additive for a non-aqueous electrolyte, an antistatic agent, etc. The reaction solution may be further filtered, concentrated, or diluted before use for the above-mentioned applications. Furthermore, the imidic acid or imidic acid salt can be precipitated and isolated by concentrating the reaction solution, etc.

[0052] The yield in invention 1 is calculated based on the molar amount of the compound that is charged in a smaller amount between the phosphoryl isocyanate represented by general formula [2] and the compound represented by general formula [3]. The yield in invention 2 is calculated based on the molar amount of the compound that is charged in a smaller amount between the sulfonyl isocyanate represented by general formula [5] and the compound represented by general formula [6].

[0053] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0054] [Comparative Example 1-1] In a 50 mL glass reactor equipped with a stirrer and a thermometer, 20.00 g of propionitrile (water content: 40 ppm by mass) as a reaction solvent and 0.44 g (3.7 mmol) of lithium trifluoroacetate (water content: 90 ppm by mass) as a compound represented by general formula [3] were added under a nitrogen atmosphere and stirred at a liquid temperature of 23°C. While maintaining the liquid temperature at 23°C, 0.70 g (4.4 mmol) of dichlorophosphoryl isocyanate as the phosphoryl isocyanate represented by general formula [2] was added dropwise over 10 minutes. After completion of the dropwise addition, the liquid temperature was raised to 60°C and stirring was continued for an additional 8 hours to carry out the reaction. The reaction liquid was concentrated under reduced pressure to remove dissolved carbon dioxide and dichlorophosphoryl isocyanate, yielding [(dichlorophosphoryl)(trifluoromethanecarbonyl)imide] lithium salt. The resulting target product (concentrated liquid) was 19 Analysis and quantification by F-NMR revealed that the yield of [(dichlorophosphoryl)(trifluoromethanecarbonyl)imide]lithium salt was 64% based on lithium trifluoroacetate. The concentrated solution was placed in a vial and stored at room temperature (25°C) for one week, and the residual rate of the target substance was calculated using the following formula. The results are shown in Table 1. Residual rate of target substance (%) = [mass of target substance after storage / mass of target substance before storage] x 100

[0055] Examples 1-1 to 1-16, Comparative Examples 1-2 to 1-6 Concentrated solutions were obtained in the same manner as in Comparative Example 1-1, except that basic compounds or comparative compounds (hereinafter, these may be collectively referred to as "additives") of the types shown in Table 1 below were added initially (before the reaction) together with propionitrile and lithium trifluoroacetate. The amounts of the additives added were the amounts shown in Table 1 in terms of mol % relative to lithium trifluoroacetate. The results are shown in Table 1.

[0056]

[0057] [Comparative Example 2-1] In a 50 mL glass reactor equipped with a stirrer and a thermometer, 10 g of tetrahydrofuran (water content 50 mass ppm) as a reaction solvent and 1.46 g (9.8 mmol) of dimethyl sodium phosphate (water content 120 mass ppm) as a compound represented by general formula [3] were added under a nitrogen atmosphere, and the mixture was stirred at a liquid temperature of 23 ° C. While maintaining the liquid temperature at 23 ° C, 2.48 g (19.6 mmol) of difluorophosphoryl isocyanate as the phosphoryl isocyanate represented by general formula [2] was added dropwise over 10 minutes. After completion of the dropwise addition, the liquid temperature was raised to 60 ° C. and stirring was continued for another 5 hours to carry out the reaction. The reaction liquid was concentrated under reduced pressure to remove dissolved carbon dioxide and difluorophosphoryl isocyanate, and [(difluorophosphoryl)(dimethylphosphoryl)imide] sodium salt was obtained. The resulting target product (concentrated liquid) was 19 Analysis and quantification by F-NMR revealed that the yield of [(difluorophosphoryl)(dimethylphosphoryl)imide] sodium salt was 63% based on sodium dimethylphosphate. Furthermore, in this vacuum concentration operation, tetrahydrofuran and difluorophosphoryl isocyanate were almost entirely recovered as fractions. The residual rate of the target product after storage at room temperature (25°C) for one week was calculated in the same manner as in Comparative Example 1-1. The results are shown in Table 2.

[0058] Examples 2-1 to 2-13, Comparative Examples 2-2 to 2-6 Concentrated solutions were obtained in the same manner as in Comparative Example 2-1, except that the types of additives shown in Table 2 below were added initially (before the reaction) along with tetrahydrofuran and sodium dimethyl phosphate. The amounts of the additives added were the amounts shown in Table 2 in terms of mol % relative to sodium dimethyl phosphate. The results are shown in Table 2.

[0059]

[0060] [Comparative Example 3-1] In a nitrogen atmosphere, 25 g of ethylene carbonate (water content 20 ppm by mass) as a reaction solvent and 2.50 g (23.0 mmol) of lithium difluorophosphate (water content 100 ppm by mass) as a compound represented by general formula [6] were added to a 50 mL glass reactor equipped with a stirrer and a thermometer, and the mixture was stirred at a liquid temperature of 50°C. While maintaining the liquid temperature at 50°C, 3.10 g (25.0 mmol) of fluorosulfonyl isocyanate as the sulfonyl isocyanate represented by general formula [5] was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was continued with stirring for an additional 4 hours at a liquid temperature of 50°C. The reaction solution was concentrated under reduced pressure to remove dissolved carbon dioxide and fluorosulfonyl isocyanate, yielding an ethylene carbonate solution of [(fluorosulfonyl)(difluorophosphoryl)imide] lithium salt. The resulting target product (concentrated liquid) was 19 Analysis and quantification by F-NMR revealed that the yield of [(fluorosulfonyl)(difluorophosphoryl)imide]lithium salt was 68% based on lithium difluorophosphate. The residual rate of the target product after storage at room temperature (25°C) for one week was calculated in the same manner as in Comparative Example 1-1. The results are shown in Table 3.

[0061] Examples 3-1 to 3-13, Comparative Examples 3-2 to 3-6 Concentrated solutions were obtained in the same manner as in Comparative Example 3-1, except that the types of additives shown in Table 3 below were added initially (before the reaction) together with ethylene carbonate and lithium difluorophosphate. The amounts of the additives added were the amounts shown in Table 3 as mol % relative to lithium difluorophosphate. The results are shown in Table 3.

[0062]

[0063] [Comparative Example 4-1] In a 50 mL glass reactor equipped with a stirrer and a thermometer, 25 g of ethyl acetate (water content 30 mass ppm) as a reaction solvent and 1.74 g (13.0 mmol) of (fluoro)monoethyl lithium phosphate (water content 120 mass ppm) as a compound represented by general formula [6] were added under a nitrogen atmosphere and stirred at a liquid temperature of 50 ° C. While maintaining the liquid temperature at 50 ° C, 1.46 g (11.0 mmol) of fluorosulfonyl isocyanate as the sulfonyl isocyanate represented by general formula [5] was added dropwise over 30 minutes. After completion of the dropwise addition, the reaction was continued by stirring for another 5 hours at a liquid temperature of 50 ° C. The reaction liquid was concentrated under reduced pressure to remove dissolved carbon dioxide and fluorosulfonyl isocyanate, and insoluble matter was removed by filtration to obtain an ethyl acetate solution of {[fluorosulfonyl][(fluoro)(ethyl)phosphoryl]imide} lithium salt. The resulting target product (concentrated liquid) was 19 Analysis and quantification by F-NMR revealed that the yield of {[fluorosulfonyl][(fluoro)(ethyl)phosphoryl]imide} lithium salt was 63% based on fluorosulfonyl isocyanate. The residual rate of the target product after storage at room temperature (25°C) for one week was calculated in the same manner as in Comparative Example 1-1. The results are shown in Table 4.

[0064] Examples 4-1 to 4-13, Comparative Examples 4-2 to 4-6 Concentrated solutions were obtained in the same manner as in Comparative Example 4-1, except that the types of additives shown in Table 4 below were added first together with ethyl acetate and lithium (fluoro)monoethyl phosphate. The amounts of the additives added were the amounts shown in Table 4 in terms of mol % relative to lithium (fluoro)monoethyl phosphate. The results are shown in Table 4.

[0065]

[0066] In the comparative examples shown in Tables 1 to 4, when a basic compound was not added or water, hydrogen chloride, or a neutral salt was added in the reaction step between an isocyanate compound and its corresponding nucleophile, the residual rate of the resulting imide salt after one week of storage at room temperature was low. Furthermore, the yield was also low. In contrast, in the examples, when a basic compound was added in the reaction step, the resulting imide salt showed a residual rate of nearly 100% after one week of storage. Furthermore, the yield was also high. From this, it is believed that trace amounts of acid contained in the raw materials cause decomposition of the product after the reaction, thereby reducing stability and further complicating the reaction and reducing the yield, whereas the addition of a basic compound scavenged the acid, thereby avoiding decomposition of the product after the reaction and adverse effects on the reaction.

[0067] [Examples 1A-1 to 1A-16, Comparative Examples 1A-2 to 1A-6] After the dropwise addition of dichlorophosphoryl isocyanate was completed, the liquid temperature was raised to 60°C and stirring was continued for 3 hours, at which point additives of the types shown in Table 5 below were added to the liquid during the reaction, and stirring was continued for an additional 5 hours to carry out the reaction. Concentrated liquids were obtained in the same manner as in Comparative Example 1-1. The amounts of the additives added were the amounts shown in Table 5 in terms of mol % relative to lithium trifluoroacetate. The results are shown in Table 5.

[0068]

[0069] [Examples 2A-1 to 2A-13, Comparative Examples 2A-2 to 2A-6] After the dropwise addition of difluorophosphoryl isocyanate was completed, the liquid temperature was raised to 60°C and stirring was continued for 2 hours, at which point additives of the types shown in Table 6 below were added to the liquid during the reaction, and stirring was continued for an additional 3 hours to carry out the reaction. Concentrated liquids were obtained in the same manner as in Comparative Example 2-1, except that the amounts of the additives added were the amounts shown in Table 6 in terms of mol % relative to sodium dimethyl phosphate. The results are shown in Table 6.

[0070]

[0071] Examples 3A-1 to 3A-13, Comparative Examples 3A-2 to 3A-6 After the dropwise addition of fluorosulfonyl isocyanate was completed, the liquid temperature was raised to 50°C and stirring was continued for 2 hours. At this point, additives of the types shown in Table 7 below were added to the liquid during the reaction, and stirring was continued for another 2 hours to carry out the reaction. Concentrated liquids were obtained in the same manner as in Comparative Example 3-1. The amounts of the additives added were the amounts shown in Table 7 in terms of mol % relative to lithium difluorophosphate. The results are shown in Table 7.

[0072]

[0073] [Examples 4A-1 to 4A-13, Comparative Examples 4A-2 to 4A-6] After the dropwise addition of fluorosulfonyl isocyanate was completed, the liquid temperature was raised to 50°C and stirring was continued for 2 hours, at which point additives of the types shown in Table 8 below were added to the liquid during the reaction, and stirring was continued for an additional 3 hours to carry out the reaction. Concentrated liquids were obtained in the same manner as in Comparative Example 4-1. The amounts of the additives added were the amounts shown in Table 8 in terms of mol % relative to lithium (fluoro)monoethylphosphate. The results are shown in Table 8.

[0074]

[0075] [Examples 1B-1 to 1B-16, Comparative Examples 1B-2 to 1B-6] After the dropwise addition of dichlorophosphoryl isocyanate was completed, the liquid temperature was raised to 60°C and stirring was continued for 8 hours, and then a concentrated liquid was obtained in the same manner as in Comparative Example 1-1, except that additives shown in Table 9 below were added. The amounts of the additives added were the amounts shown in Table 9 in terms of mol % relative to lithium trifluoroacetate. The results are shown in Table 9.

[0076]

[0077] [Examples 2B-1 to 2B-13, Comparative Examples 2B-2 to 2B-6] After the dropwise addition of difluorophosphoryl isocyanate was completed, the liquid temperature was raised to 60°C and stirring was continued for 5 hours, and then a concentrated liquid was obtained in the same manner as in Comparative Example 2-1, except that additives shown in Table 10 below were added. The amounts of the additives added were the amounts shown in Table 10 in terms of mol % relative to sodium dimethyl phosphate. The results are shown in Table 10.

[0078]

[0079] [Examples 3B-1 to 3B-13, Comparative Examples 3B-2 to 3B-6] After the dropwise addition of fluorosulfonyl isocyanate was completed, the liquid temperature was raised to 50°C and stirring was continued for 4 hours, and then a concentrated liquid was obtained in the same manner as in Comparative Example 3-1, except that additives shown in Table 11 below were added. The amounts of the additives added were the amounts shown in Table 11 in terms of mol % relative to lithium difluorophosphate. The results are shown in Table 11.

[0080]

[0081] [Examples 4B-1 to 4B-13, Comparative Examples 4B-2 to 4B-6] After the dropwise addition of fluorosulfonyl isocyanate was completed, the liquid temperature was raised to 50°C and stirring was continued for 5 hours, and then a concentrated liquid was obtained in the same manner as in Comparative Example 4-1, except that additives shown in Table 12 below were added. The amounts of the additives added were the amounts shown in Table 12 in terms of mol % relative to lithium (fluoro)monoethylphosphate. The results are shown in Table 12.

[0082]

[0083] Examples 1C-1 to 1C-16, Comparative Examples 1C-2 to 1C-6 Concentrated solutions were obtained in the same manner as in Comparative Example 1-1, except that additives shown in Table 13 below were added before the reaction (hereinafter referred to as "first" in the tables), and after completion of the dropwise addition of dichlorophosphoryl isocyanate, the solution temperature was raised to 60°C and stirring was continued for 8 hours (hereinafter referred to as "last" in the tables). The amounts of the additives added were the amounts shown in Table 13 in terms of mol % relative to lithium trifluoroacetate. The results are shown in Table 13.

[0084]

[0085] Examples 2C-1 to 2C-13, Comparative Examples 2C-2 to 2C-6 Concentrated solutions were obtained in the same manner as in Comparative Example 2-1, except that before the reaction and after the completion of the dropwise addition of difluorophosphoryl isocyanate, the liquid temperature was raised to 60°C, stirring was continued for 5 hours, and then the types of additives shown in Table 14 below were added. The amounts of the additives added were the amounts shown in Table 14 in terms of mol % relative to sodium dimethyl phosphate. The results are shown in Table 14.

[0086]

[0087] Examples 3C-1 to 3C-13, Comparative Examples 3C-2 to 3C-6 Concentrated solutions were obtained in the same manner as in Comparative Example 3-1, except that before the reaction and after the completion of the dropwise addition of fluorosulfonyl isocyanate, the liquid temperature was raised to 50°C, stirring was continued for 4 hours, and then the types of additives shown in Table 15 below were added. The amounts of the additives added were the amounts shown in Table 15 in terms of mol % relative to lithium difluorophosphate. The results are shown in Table 15.

[0088]

[0089] Examples 4C-1 to 4C-13, Comparative Examples 4C-2 to 4C-6 Concentrated solutions were obtained in the same manner as in Comparative Example 4-1, except that before the reaction and after the completion of the dropwise addition of fluorosulfonyl isocyanate, the liquid temperature was raised to 50°C, stirring was continued for 5 hours, and then the types of additives shown in Table 16 below were added. The amounts of the additives added were the amounts shown in Table 16 in terms of mol % relative to lithium (fluoro)monoethylphosphate. The results are shown in Table 16.

[0090]

[0091] The results in Tables 5 to 8, where an additive was added during the reaction, the results in Tables 9 to 12, where an additive was added after the reaction, and the results in Tables 13 to 16, where an additive was added both at the beginning and after the reaction, also show that the residual rates of the obtained imide salts after one week of storage at room temperature tended to be similar to the results in Tables 1 to 4. Among these, adding a basic compound before the reaction and adding a basic compound before and after the reaction were found to be preferable from the perspective of suppressing acid generation and further improving at least one of the storage stability and yield of the target product. Furthermore, from the results in each table, in terms of yield, the example in which an additive was added both at the beginning and after the reaction was most preferable, followed by the example in which an additive was added only at the beginning, then the example in which an additive was added only during the reaction, and then the example in which an additive was added only after the reaction tended to be preferable. The yield of Example 1C-5, in which an additive was added both at the beginning and after the reaction, was lower than the yield of Example 1-5, in which an additive was added only at the beginning. Although the details are unknown, it is presumed that the total amount of additive added in Example 1C-5 was large, which may have affected the moisture content of the additive.

[0092] According to the present disclosure, a new method for producing an imide acid or an imide salt having a phosphoryl group, which has excellent storage stability, can be provided.

[0093] This application claims priority based on Japanese Patent Application No. 2024-061590, filed April 5, 2024, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A method for producing an imidic acid or imidic acid salt represented by the following general formula [1], comprising a reaction step of reacting phosphoryl isocyanate represented by the following general formula [2] with a compound represented by the following general formula [3], wherein a basic compound is present during and / or after the reaction step. [In general formula [1], X １ , X ２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may contain at least one selected from a fluorine atom, an oxygen atom, a nitrogen atom, and an unsaturated bond. Z is -P(=O)-, -S(=O) ２ When Z is -P(=O)-, a is 1, and when Z is -S(=O) ２ When it is - or -C(=O)-, a is 0. １ , R ２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may also contain at least one type selected from a fluorine atom, an oxygen atom, and an unsaturated bond. ｍ＋ represents a proton, an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation. [In general formula [2], X １ , X ２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may also contain at least one type selected from a fluorine atom, an oxygen atom, a nitrogen atom, and an unsaturated bond. [In the general formula [3], Z is -P(=O)-, -S(=O) ２ -, or -C(=O)-. When Z is -P(=O)-, a is 1. When Z is -S(=O) ２ When Z is -, a is 0. When Z is -C(=O)-, a is 0. R １ , R ２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may also contain at least one type selected from a fluorine atom, an oxygen atom, and an unsaturated bond. ｍ＋ represents a proton, an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation.

2. The method for producing an imide acid or an imide salt according to claim 1, wherein the basic compound comprises one or more compounds selected from the group consisting of amine compounds, nitrogen-containing heterocyclic compounds, carbodiimide group-containing compounds, phosphite ester compounds, alkali metal compounds, and alkaline earth metal compounds.

3. The method for producing an imidic acid or an imidic acid salt according to claim 1 or 2, wherein the basic compound is present in an amount of 0.01 to 30 mol % relative to the compound represented by general formula [3] during the reaction step and / or after the reaction step.

4. The method for producing an imidic acid or an imidic acid salt according to claim 1 or 2, wherein the amount of phosphoryl isocyanate represented by the general formula [2] used is 0.1 to 10 moles per mole of the compound represented by the general formula [3].

5. The method for producing an imide acid or an imide salt according to claim 1 or 2, wherein the reaction temperature in the reaction step is -20 to 200°C.

6. The method for producing an imide acid or an imide salt according to claim 1 or 2, wherein the reaction step is carried out in a reaction solvent.

7. The method for producing an imidic acid or an imidic acid salt according to claim 6, wherein the reaction solvent is at least one solvent selected from the group consisting of nitriles, chain ethers, cyclic ethers, chain esters, cyclic esters, chain carbonates, cyclic carbonates, and sulfur-containing solvents.

8. Said M ｍ＋ 3. The method for producing an imide acid or an imide salt according to claim 1 or 2, wherein is a proton, a lithium ion, a sodium ion, a potassium ion, a trialkylammonium ion, or a tetraalkylammonium ion.

9. The above X １ , X ２ and each independently represent a group selected from a chlorine atom, a fluorine atom, a methyl group, a trifluoromethyl group, a phenyl group, a fluorophenyl group, a vinyl group, a thienyl group, and a pyridinyl group.

10. The method for producing an imide acid or an imide salt according to claim 1 or 2, wherein the reaction liquid after the reaction step is degassed and concentrated.

11. A method for producing an imidic acid or imidic acid salt represented by the following general formula [4], comprising a reaction step of reacting a sulfonyl isocyanate represented by the following general formula [5] with a compound represented by the following general formula [6], wherein a basic compound is present during and / or after the reaction step. [In general formula [4], X １ , X ２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may contain at least one selected from a fluorine atom, an oxygen atom, a nitrogen atom, and an unsaturated bond. １ is an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and at least one type selected from a fluorine atom, an oxygen atom, and an unsaturated bond may be present in the organic group. ｍ＋ represents a proton, an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation. [In general formula [5], R １ is an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may also contain at least one type selected from a fluorine atom, an oxygen atom, and an unsaturated bond.] [In general formula [6], X １ , X ２ are each independently an organic group selected from a chlorine atom, a fluorine atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkynyloxy group having 2 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, a cycloalkenyloxy group having 3 to 10 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms, and the organic group may contain at least one selected from a fluorine atom, an oxygen atom, a nitrogen atom, and an unsaturated bond. ｍ＋ represents a proton, an alkali metal cation, an alkaline earth metal cation, or an onium cation, and m represents an integer equal to the valence of the corresponding cation.

12. The method for producing an imide acid or an imide salt according to claim 11, wherein the basic compound comprises one or more compounds selected from the group consisting of amine compounds, nitrogen-containing heterocyclic compounds, carbodiimide group-containing compounds, phosphite ester compounds, alkali metal compounds, and alkaline earth metal compounds.

13. The method for producing an imidic acid or an imidic acid salt according to claim 11 or 12, wherein the basic compound is present in an amount of 0.01 to 30 mol % relative to the compound represented by general formula [6] during the reaction step and / or after the reaction step.

14. The method for producing an imidic acid or imidic acid salt according to claim 11 or 12, wherein the amount of the sulfonyl isocyanate represented by the general formula [5] used is 0.1 to 10 moles per mole of the compound represented by the general formula [6].

15. The method for producing an imide acid or an imide salt according to claim 11 or 12, wherein the reaction temperature in the reaction step is 0 to 150°C.

16. The method for producing an imide acid or an imide salt according to claim 11 or 12, wherein the reaction step is carried out in a reaction solvent.

17. The method for producing an imidic acid or an imidic acid salt according to claim 16, wherein the reaction solvent is at least one solvent selected from the group consisting of nitriles, linear ethers, cyclic ethers, linear esters, cyclic esters, linear carbonates, cyclic carbonates, and sulfur-containing solvents.

18. Said M ｍ＋ 13. The method for producing an imidic acid or an imidic acid salt according to claim 11 or 12, wherein is a proton, a lithium ion, a sodium ion, a potassium ion, a trialkylammonium ion, or a tetraalkylammonium ion.

19. The above X １ , X ２ are each independently selected from a chlorine atom, a fluorine atom, a methyl group, a trifluoromethyl group, a phenyl group, a fluorophenyl group, a vinyl group, a thienyl group, and a pyridinyl group.

20. The method for producing an imide acid or an imide salt according to claim 11 or 12, wherein the reaction liquid after the reaction step is degassed and concentrated.

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