Method for producing fluorine-containing sulfonic acid anhydride

Abstract

To provide a method for producing a fluorinated sulfonic acid anhydride (2) that is useful as pharmaceuticals, catalysts for organic synthesis and the like, or synthetic materials, the method capable of suppressing consolidation in a reaction between a fluorinated sulfonic acid and diphosphorus pentoxide, achieving a high yield.SOLUTION: A method for producing a fluorinated sulfonic acid anhydride (2) causes a fluorinated sulfonic acid (1) to react with diphosphorus pentoxide in coexistence with zirconia.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a fluorine-containing sulfonic acid anhydride. [Background technology]

[0002] Fluorine-containing sulfonic acid anhydrides have conventionally been useful as catalysts for pharmaceuticals and organic synthesis, or as synthetic raw materials. As a method for producing a fluorine-containing sulfonic anhydride, for example, a method is known in which diphosphorus pentoxide is added to trifluoromethanesulfonic acid, a dehydration condensation reaction is carried out to produce trifluoromethanesulfonic anhydride, and the produced trifluoromethanesulfonic anhydride is volatilized and recovered. However, metaphosphoric acid (a reaction product of diphosphorus pentoxide and water) produced as a by-product in the dehydration condensation reaction is glassy and has an extremely high viscosity, and a mixture containing trifluoromethanesulfonic acid and diphosphorus pentoxide becomes unstirable during the reaction (hereinafter, the phenomenon in which a mixture containing trifluoromethanesulfonic acid and diphosphorus pentoxide becomes unstirable during the reaction is referred to as "caking"). As a result, the reaction does not proceed and the produced trifluoromethanesulfonic anhydride cannot be recovered by heating. As a result, it is known that the yield of trifluoromethanesulfonic anhydride is at most 60% or less on a trifluoromethanesulfonic acid basis (Patent Documents 1 to 7). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2-268148 [Patent Document 2] Japanese Patent Application Publication No. 9-227498 [Patent Document 3] Japanese Patent Application Publication No. 10-114734 [Patent Document 4] JP 2007-145815 A [Patent Document 5] JP 2007-297359 A [Patent Document 6] JP 2013-112670 A [Patent Document 7] JP 2016-47861 A Summary of the Invention [Problem to be solved by the invention]

[0004] Patent Document 1 discloses a production method in which water or phosphoric acid is added to a reaction product of solidified trifluoromethanesulfonic acid and diphosphorus pentoxide to dissolve metaphosphoric acid, and the reactor is allowed to be stirred, and then vacuum distillation is performed again to recover unreacted trifluoromethanesulfonic acid, thereby increasing the yield of trifluoromethanesulfonic anhydride based on the reacted trifluoromethanesulfonic acid. However, this method does not prevent the reaction product of trifluoromethanesulfonic acid and diphosphorus pentoxide from solidifying. In addition, this method requires the addition of water or phosphoric acid little by little to prevent a sudden temperature rise due to reaction heat, and stirring cannot be performed until it is dissolved. Therefore, it is necessary to wait a long time until metaphosphoric acid is completely dissolved in the added water or phosphoric acid, and from an industrial point of view, it is not necessarily a productive process.

[0005] Patent Documents 2 and 3 disclose a production method in which the reaction of trifluoromethanesulfonic acid with diphosphorus pentoxide is carried out in a fluorine-based solvent to suppress caking. However, since a large amount of solvent is required to suppress caking, it is not necessarily considered to be a highly productive process from an industrial point of view. From the same point of view, it is desirable to reuse the fluorine solvent used, but an additional step is required for reuse, which may make the process complicated.

[0006] Patent Document 4 discloses a production method in which caking is suppressed in the reaction between trifluoromethanesulfonic acid and diphosphorus pentoxide by using an excess amount of trifluoromethanesulfonic acid relative to diphosphorus pentoxide. However, although it is desirable to reuse the raw material trifluoromethanesulfonic acid from an industrial point of view, an additional step is required for reuse, which is considered to complicate the process.

[0007] Patent Documents 5 to 7 disclose a production method in which the reaction between trifluoromethanesulfonic acid and diphosphorus pentoxide is carried out using a kneader reactor equipped with a twin-shaft blade having a predetermined power per volume of the reaction vessel, thereby forcibly kneading even in a state of solidification caused by metaphosphoric acid. However, it is necessary to use a special device, a kneader reactor equipped with a twin-shaft blade having a predetermined power per volume of the reaction vessel, and a production method capable of suppressing solidification by a simpler method is required. [Means for solving the problem]

[0008] As a result of intensive investigations aimed at solving the above-mentioned problems, the present inventors have found that by reacting a fluorine-containing sulfonic acid (1) (hereinafter also referred to as "compound (1)") with diphosphorus pentoxide in the coexistence of zirconia, caking can be suppressed and a fluorine-containing sulfonic anhydride (2) (hereinafter also referred to as "compound (2)") can be produced, thereby completing the present invention.

[0009] That is, the present invention is as follows. [1] The following general formula (2): (R f SO 2 ) 2 O (2) (In the formula, R f teeth , tired Saturated or unsaturated fats Tribe A hydrocarbon group, but- CH 2 -of If so, -CH 2- may be substituted with a structure having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, Among the hydrogen atoms of the hydrocarbon group, the —CH 2 All but the hydrogen atoms in - are replaced with fluorine atoms. R f The carbon number is 1 to 20, and two R f They may be the same or different) The present invention relates to a method for producing a fluorine-containing sulfonic anhydride (2) represented by the following formula: The following general formula (1): R f SO 3 H (1) (In the formula, R f teeth , tired Saturated or unsaturated fats Tribe A hydrocarbon group, but- CH 2 -of If so, -CH 2 - may be substituted with a structure having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, Among the hydrogen atoms of the hydrocarbon group, the —CH 2 All but the hydrogen atoms in - are replaced with fluorine atoms. R f has 1 to 20 carbon atoms. A fluorine-containing sulfonic acid (1) represented by the formula: Diphosphorus pentaoxide and React in the presence of zirconia, the ratio (ε / (γ+δ)) of the mass (ε) of the zirconia to the total mass (γ+δ) of the mass (γ) of the fluorine-containing sulfonic acid (1) and the mass (δ) of the diphosphorus pentoxide is 0.1 to 100; A manufacturing method comprising: [2] The production method according to [1], wherein a ratio (β / α) of the amount of substance (β) of the diphosphorus pentoxide to the amount of substance (α) of the fluorine-containing sulfonic acid (1) is 0.1 to 100. [3] The production method according to [1] or [2], wherein the reaction temperature is −40 to 300° C. Effect of the Invention

[0010] According to the present invention, solidification in the reaction between a fluorinated sulfonic acid (1) and diphosphorus pentoxide can be suppressed, and a fluorinated sulfonic anhydride (2) can be produced in good yield. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, an embodiment of the present invention (hereinafter, referred to as the present embodiment) will be described in detail. However, the present invention is not limited to the present embodiment, and can be modified in various ways within the scope of the present invention.

[0012] The manufacturing method of this embodiment is as follows: The following general formula (2): (R f SO 2 ) 2 O (2) (In the formula, R f represents a saturated or unsaturated aliphatic or aromatic hydrocarbon group in which at least one hydrogen atom is substituted with a fluorine atom, and the ethylene structure in the hydrocarbon group may be substituted with a structure having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; R f The carbon number is 1 to 20, and two R f They may be the same or different) The present invention relates to a method for producing a fluorine-containing sulfonic acid anhydride (2) represented by the following formula: The following general formula (1): R f SO 3 H (1) (In the formula, R f represents a saturated or unsaturated aliphatic or aromatic hydrocarbon group in which at least one hydrogen atom is substituted with a fluorine atom, and the ethylene structure in the hydrocarbon group may be substituted with a structure having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; R f has 1 to 20 carbon atoms. A fluorine-containing sulfonic acid (1) represented by the formula: Diphosphorus pentaoxide and React in the presence of zirconia It is characterized by:

[0013] The compound (1), diphosphorus pentoxide, and zirconia, as well as the reaction conditions for producing compound (2) from compound (1), will be described in detail below.

[0014] <Fluorine-containing sulfonic acid (1) (compound (1))> The fluorine-containing sulfonic acid (1) is represented by the following general formula (1): R f SO 3 H (1) (In the formula, R f represents a saturated or unsaturated aliphatic or aromatic hydrocarbon group in which at least one hydrogen atom is substituted with a fluorine atom, and the ethylene structure in the hydrocarbon group may be substituted with a structure having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; R f has 1 to 20 carbon atoms. It is expressed as: The fluorine-containing sulfonic acids (1) may be used alone or in combination of two or more kinds.

[0015] R f R is a saturated or unsaturated aliphatic or aromatic hydrocarbon group in which a hydrogen atom is substituted with a fluorine atom, as described below. f may be at least one hydrocarbon group selected from the group consisting of saturated aliphatic, unsaturated aliphatic, and aromatic groups in which a hydrogen atom is substituted with a fluorine atom, as described below. Saturated or unsaturated aliphatic hydrocarbons are preferred because they tend to be easily available or produced and economically advantageous.

[0016] R fThe substituent of the hydrogen atom of the hydrocarbon group is not particularly limited as long as it is a commonly used substituent, but specific examples include halogen atoms such as fluorine atom, chlorine atom, and bromine atom; aliphatic hydrocarbon groups such as nitrile group, methyl group, ethyl group, vinyl group, allyl group, 1-methylvinyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and fluoromethyl group; aromatic hydrocarbon groups such as benzyl group, phenyl group, nitrile-substituted phenyl group, and fluorinated phenyl group; groups having a structure in which the aliphatic hydrocarbon group and aromatic hydrocarbon group are fluorinated; amino group; nitro group; sulfo group; hydroxyl group; silyl group; phosphoric acid group; and thiol group. These substituents may be used alone or in combination of two or more types.

[0017] R f When the hydrocarbon group has an aliphatic portion, the ethylene structure (-CH 2 -) may be substituted with a structure having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom, or may be substituted with a structure having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. R f The ethylene structure of the hydrocarbon group (-CH 2 The structure in which the - is substituted is not particularly limited as long as it is a commonly used structure, but may be a divalent structure. Specific examples include an ether group (-O-), a carbonate group (-OCO 2 -), ester group (-CO 2 -), carbonyl group (-CO-), sulfide group (-S-), sulfoxide group (-SO-), sulfone group (-SO 2 -), urethane group (-NHCO 2 These structures may be used alone or in combination of two or more.

[0018] R fThe number of carbon atoms is 1 to 20, preferably 1 to 10, more preferably 1 to 7, and particularly preferably 1 to 5, since these tend to be easily available or produced and are economically advantageous.

[0019] R f The number of fluorine atoms resulting from the substitution of hydrogen atoms in the aliphatic or aromatic hydrocarbon group (the number of hydrogen atoms in the hydrocarbon group substituted with fluorine atoms) is not particularly limited as long as it is 1 or more, but is preferably 3 or more. Depending on the type of compound (1), it is more preferably 5 or more, and even more preferably 7 or more. When high durability of compound (1) and / or compound (2) is required, it is particularly preferable that all of the hydrogen atoms in the aliphatic or aromatic hydrocarbon group are fluorine atoms.

[0020] R f The number of substituted ethylene structures (the number of ethylene structures substituted with structures having oxygen atoms or the like) may be 0 to 10, more preferably 0 to 7, and further preferably 0 to 5.

[0021] In this embodiment, the compound (1) is represented by the following general formula (3): [ka] (In the formula, m is an integer of 0 to 3, and n is an integer of 1 to 6). Particularly preferred is a fluorine-containing vinyl sulfonic acid (3) represented by the following formula:

[0022] As m, an integer of 0 to 1 is preferable, and 0 is more preferable, since it is easily available or produced and tends to be economical. As n, 1 to 4 is preferable, 2 to 4 is more preferable, and 2 is even more preferable, because n is easily available or produced and tends to be economical. As a combination of m and n, m=0 and n=2 are particularly preferable.

[0023] The structure of the compound (2) produced from the above-mentioned fluorine-containing vinyl sulfonic acid (3) is represented by the following general formula (4): [ka] (In the formula, m is an integer of 0 to 3, and n is an integer of 1 to 6). It is expressed as:

[0024] m and n are the same as in compound (3), and m is preferably 0 to 1, and more preferably 0, since it is easily available or produced and tends to be economical. As n, 1 to 4 is preferable, 2 to 4 is more preferable, and 2 is even more preferable, because n is easily available or produced and tends to be economical. As a combination of m and n, m=0 and n=2 are particularly preferable.

[0025] The fluorine-containing sulfonic acid (1) can be produced by a conventional method or can be purchased commercially.

[0026] <Diphosphorus pentoxide> Diphosphorus pentoxide has the formula "P 2 O 5 " However, the actual structure is "P 4 O 10 It has the chemical formula: tetraphosphorus decaoxide. It is also known as phosphorus oxide, phosphorus pentoxide, and phosphoric anhydride.

[0027] The purity of diphosphorus pentoxide is not particularly limited as long as it is a generally available purity, but since side reactions can be suppressed and the yield of compound (2) tends to be improved, the purity is preferably 90% by mass or more, more preferably 95% by mass or more, even more preferably 97% by mass or more, and particularly preferably 98% by mass or more.

[0028] Diphosphorus pentoxide having the desired purity can be purchased from Fujifilm Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., Aldrich, Nacalai Tesque, Inc., Kanto Chemical Co., Ltd., Nippon Chemical Industry Co., Ltd., Rasa Kogyo Co., Ltd., and the like.

[0029] <Zirconia> In this embodiment, zirconia refers to zirconium dioxide (ZrO 2 ) is 50% by mass or more. The content of zirconium dioxide contained in zirconia is preferably 80% by mass or more, and more preferably 90% by mass or more, since side reactions can be suppressed and the yield of compound (2) tends to be improved. In the reaction between compound (1) and diphosphorus pentoxide, when the coexisting zirconia is unlikely to be crushed and the effect on fluidity is small, the content of zirconium dioxide is more preferably 97% by mass or more, and particularly preferably 99% by mass or more. In the reaction between compound (1) and diphosphorus pentoxide, when the coexisting zirconia is likely to be crushed and the fluidity is likely to change, it is preferable to use yttria-stabilized zirconia. Yttrium oxide (Y 2 O 3 The content of ) is preferably more than 0 mass % and 20 mass % or less, more preferably 1 to 10 mass %, and further preferably 3 to 8 mass %. The content of zirconium dioxide in zirconia can be known from information provided by the manufacturer selling the zirconia, or by common analytical methods such as fluorescent X-ray analysis, X-ray diffraction analysis, ICP emission spectrometry, and ICP mass spectrometry. Zirconium dioxide (ZrO 2 ) contains hafnium dioxide (HfO 2 ) is generally contained in trace amounts. Therefore, zirconium dioxide (ZrO 2 The content of hafnium dioxide (HfO 2 ) is generally also included.

[0030] The shape of zirconia is not particularly limited as long as it is a generally available shape, and may be any of spherical, spindle-shaped, rod-shaped, needle-shaped, cylindrical, columnar, scaly, thin, plate-shaped, and crushed. The mixture of compound (1), diphosphorus pentoxide, and zirconia, and the mixture during the reaction, tend to have improved fluidity, and tend to have high stability of shape in a fluid state. Therefore, if this viewpoint is emphasized, spherical zirconia is preferable. When it is desired to use zirconia having a small particle size, if it is important that it is easy to obtain and tends to be economically excellent, zirconia having various shapes is preferable.

[0031] In this embodiment, the particle size refers to the cumulative average diameter measured by a particle size distribution measuring device (the particle size at the point where the cumulative curve is 50% when the total volume of the powder population to be analyzed is taken as 100%). The particle size of the zirconia is not particularly limited as long as it is a generally available particle size, but it is preferably 0.01 to 1000 μm. Since there is a tendency for caking to be suppressed, the particle size of zirconia is preferably 1000 μm or less, more preferably 150 μm or less, further preferably 60 μm or less, and particularly preferably 40 μm or less. The particle size of zirconia is preferably 0.01 μm or more, more preferably 0.1 μm or more, because it is easily available or produced and tends to be economical. The particle size of zirconia is further preferably 0.3 μm or more, particularly preferably 0.5 μm or more, because the bulk density of zirconia increases, the capacity of the apparatus used for producing compound (2) tends to be small, and the cost of the apparatus tends to be low.

[0032] The zirconia is not particularly limited as long as it is generally available or can be produced. Specific examples include YTZ (registered trademark) balls and YTZ (registered trademark)-S balls manufactured by Nikkato Corporation (for each ball, for example, spherical shapes with diameters of 0.03 mm, 0.05 mm, 0.1 mm, 0.2 mm, 0.3 mm, 0.4 mm, 0.5 mm, 0.65 mm, 0.8 mm, 1.0 mm, 1.25 mm, 1.5 mm, 1.75 mm, 2.0 mm, 2.3 mm, 3 mm, 4 mm, 5 mm, 10 mm, 15 mm, 20 mm, and 25 mm can be exemplified), zirconia microbeads TZ-B series and zirconia powder TZ series manufactured by Tosoh Corporation, and high-purity zirconia KZ series (fully stabilized zirconia, partially stabilized zirconia, unstabilized zirconia, etc.) manufactured by Kyoritsu Material Co., Ltd. zirconia), zirconia beads manufactured by Hira Ceramics Co., Ltd., zirconia balls manufactured by DSC Corporation, NZ series micro zirconia beads manufactured by Niimi Sangyo Co., Ltd., EP zirconium oxide, SPZ zirconium oxide, DK-3CH zirconium oxide, UEP zirconium oxide, RC-100 zirconium oxide, TMZ zirconium oxide, MIZ zirconium oxide, ASR-1 zirconium oxide, ASR-2 zirconium oxide, ASF-1S zirconium oxide, ASF-2S zirconium oxide, BR-QZ zirconium oxide, BR-3QZ zirconium oxide, BR-12QZ zirconium oxide, BR-90G zirconium oxide, SRP-2 zirconium oxide, and UEP-100 zirconium oxide manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.

[0033] Zirconia having a desired particle size can be produced by crushing available zirconia. The crushing method is not particularly limited as long as it is a commonly used method, and may be wet or dry, and examples of the crushing device include a jaw crusher, a gyration crusher, a cone crusher, an impact crusher, a rod mill, a hammer crusher, a roll crusher, a cutter mill, an autogenous crusher, a stamp mill, a stone mill, a crushing machine, a ring mill, a roller mill, a jet mill, a pin mill, a rotary mill, a vibration mill, a planetary mill, an attritor, a bead mill, etc. These devices may be used alone or in combination of two or more types. More specific examples of grinding equipment include Nibbler, Feather Mill, Farma Mill, Hammer Mill, Hammer Blade, Disintegrator, Rubber Chopper, Rotoplex, Compact Line, ACM Pulverizer, Glacis, Fine Impact Mill, Victory Mill, Contraplex, Linrex Mill, Micro Pulverizer, Counter Jet Mill, Micron Jet, Super Micron Mill, Innomizer, Pulvis, Spiral Jet Mill, Disper Mill, and Hydro Mill manufactured by Hosokawa Micron Corporation, and Automatic Pulverizer manufactured by Nara Machinery Co., Ltd. Manufactured by Kurimoto Iron Works Co., Ltd.: New Cosmomizer, Micros, Super Clean Mill, Sample Mill, Super Free Mill, Mill Box, Cosmo Box, Hammer Mill, Goblin, Baryonyx, Briodon, Polvogene, and Gina; Kurimoto Iron Works Co., Ltd.: Cross Jet Mill, Pocket Jet, Gadget, Hi-G, Agitator Mill, VX Mill, Roller Mill, Ball Mill, Rod Mill, K-VIX Mill, and Granulator; Sugiyama Heavy Industries Co., Ltd.: Jaw Crusher, Ratchet Roll Crusher, Corrugated Roll Crusher, Roll Crusher, Tan Dem roll crusher, Oniha roll crusher, S-shaped crusher, 4-axis crusher, fiber mill, bevel impactor, radical impactor, ball mill, attrition mill, and cube rotor mill, Super Powder Mill, Fairy Powder Mill, Stamp Mill, High-speed Crusher, Hammer Crusher, Sloot Mill, Seryuner, Shredder, and Cutter Mill manufactured by Nishimura Machinery Works, Inc., Vertical Roller Mill, Kryptron Zepros, Kryptron Venti, Kryptron, Kryptron Eddy, Kryptron Prime, Jedi, Converge Mill, Oshlobit, Conibit, and Hammer Mill, Super Jet Mill, Super Rotor, and Blade Mill manufactured by Nisshin Engineering Inc., Dry Star, Sigma Dry, Lab Star, Nano Getter, Mugen Flow, and Delta Vita manufactured by Ashizawa Finetech Co., Ltd., Single Track Jet Mill, Sk Jet O Mill, Cojet System α-mkV, Sanitary JOM Series, AO Jet Mill, Impeller Mill, Planetary Mill, Orient Crusher,Atomizers, pin mills, and spiral mills, solution frame machines manufactured by Makino Sangyo Co., Ltd., ghost tooth crushers, tear crushers, hammer crushers, Makino type crushers, Ixeed mills, disk type crushers, coloplex type crushers, controplex type crushers, and ultra plex type crushers, Paukutter, Paukrasher, line mills, wave mills, and Paujets manufactured by Tsukasa Kogyo Co., Ltd., Easy Nano, Lady Mill, Neo-alpha mill, low temperature / freeze-crushing bead mills, viscomills, and sand grinders manufactured by Aimax Co., Ltd., Apex mills, Ultra Apex mills, Wide Separator Apex mills, Dual Apex mills, Ultra Apex mill Advance, Apex Disperser ZERO, and Apex LABO manufactured by Hiroshima Metal & Machinery Co., Ltd., MSC mills, SC mills, SC mill long, MY mills, attritors, trigonals, fine mills, dynamic mills, alchemies, stream mills, and centricutters manufactured by Nippon Coke Industry Co., Ltd., Mighty Mill Mark II, spike mills, key mills, MP mills, MF mills, Mighty Mill, nanosonic mills, three-roll mill ceramic rolls, and three-roll mill chilled rolls, etc. manufactured by Inoue Seisakusho Co., Ltd.

[0034] The zirconia may be surface-modified as necessary. The surface-modified zirconia may be a generally available one, or may be subjected to a surface modification treatment. The compound used for the surface modification is not particularly limited as long as it is a generally used compound, but examples thereof include organic acids such as organic sulfonic acids, organic phosphoric acids, organic phosphoric acid esters, and carboxylic acids, and alkoxysilane compounds (compounds also called silane coupling agents) because they tend to have excellent adsorption ability to zirconia.More specific examples of organic acids include methanesulfonic acid, ethanesulfonic acid, octane sulfonic acid, dodecanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, dimethylbenzenesulfonic acid, biphenylsulfonic acid, styrenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tridecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, naphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, naphthalenedisulfonic acid, anthracenesulfonic acid, phenanthrenesulfonic acid, tributyl phosphate, diethyl phosphate, methyl phosphate, butoxyethyl phosphate, bis(butoxyethyl)phosphate, dibutyl phosphate, dihexyl phosphate, triphenyl phosphate, phenyl phosphate, dimethylphenyl phosphate, naphthyl phosphate, dimethylphosphonate ... dibutyl phosphate, dihexyl phosphate, triphenyl phosphate, phenyl phosphate, dimethylphenyl phosphate, naphthyl phosphate, dimethylphosphonate, tributyl phosphate, diethyl phosphate, methyl phosphate, butoxyethyl phosphate, dibutyl phosphate, dihexyl phosphate, triphenyl phosphate, phenyl phosphate, dimethylphenyl phosphate, naphthyl phosphate, dimethylphosphonate, tributyl phosphate, diethyl phosphate, methyl phosphate, diethyl Examples of the phosphonic acids include tributyl phosphite, triphenyl phosphite, triphenylphosphine oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, methyl phosphonic acid, ethyl phosphonic acid, octyl phosphonic acid, dodecyl phosphonic acid, phenyl phosphonic acid, octyl phenyl phosphonic acid, dodecyl phenyl phosphonic acid, naphthalene phosphonic acid, anthracene phosphonic acid, and phenanthrene phosphonic acid; methyl phosphinic acid, ethyl phosphinic acid, phenyl phosphinic acid, diphenyl phosphinic acid, acetic acid, caproic acid, caprylic acid, capric acid, lauric acid, and stearic acid; benzoic acid, toluic acid, dodecyl benzoic acid, methoxybenzoic acid, phenoxybenzoic acid, naphthalene carboxylic acid, phthalic acid, salicylic acid, dodecyl benzoic acid, anthracene carboxylic acid, phenanthrene carboxylic acid, lactic acid, malic acid, and adipic acid.Examples of alkoxysilane compounds include alkylalkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, and octyltrimethoxysilane, epoxyalkoxysilanes such as γ-glycidoxypropyltriethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, aminoalkoxysilanes such as aminopropyltriethoxysilane and N-phenylaminopropyltrimethoxysilane, vinylalkoxysilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, and acrylicalkoxysilanes such as acryloxytrimethoxysilane and acrylomethoxytriethoxysilane. The compounds used for surface modification may be used alone or in combination.

[0035] Zirconia may be used alone or in combination of two or more types.

[0036] When compound (1) is reacted with diphosphorus pentoxide in the presence of zirconia, additives such as ether compounds, nitrile compounds, amide compounds, sulfo compounds, saturated hydrocarbon compounds, aromatic hydrocarbon compounds, halogenated hydrocarbon compounds, ketone compounds, ester compounds, and fluorine compounds can be used as needed. The additives may be used alone or in combination.

[0037] The additive is not particularly limited as long as it is a commonly used compound. Specific examples of the additive include tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 4-methyltetrahydropyran, cyclopentyl methyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, methyl tert-butyl ether, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethylene glycol dibutyl ether, 1,2-dimethoxypropane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol diisopropyl ether. ether compounds such as diethyl glycol isopropyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether; nitrile compounds such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, 2-methylbutyronitrile, cyclohexanecarbonitrile, benzonitrile, and adiponitrile; N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpyrrolidone, tetramethylurea, and 1,Amide compounds such as 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, dibutyl sulfoxide, ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, and sulfocompounds such as 3-methyl sulfolane, n-pentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, cyclopentane, cyclohexane, cycloheptane, and saturated hydrocarbon compounds such as cyclooctane, aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, naphthalene, tetralin, and biphenyl, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichloroethane, tetrachloroethane, pentachloroethane, hexachloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene, dichloropropane, trichloropropane, isopropyl chloride, butyl chloride, hexyl chloride, chlorobenzene, dichlorobenzene, trichlorobenzene, chlorotoluene, and halogenated hydrocarbon compounds such as chloronaphthalene, acetone, methyl acetone, ethyl methyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, methyl hexyl ketone, diethyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, and ketone compounds such as cyclohexanone, and ester compounds such as ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, hexyl acetate, octyl acetate, cyclohexyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, and benzyl benzoate, fluoroalkylsulfonic anhydride (C, m F 2m+1 SO 2 ) 2 O (m = 1 to 10), fluoroalkylsulfonic ester C m F 2m+1 SO 2 OC n F 2n+1 (m = 1 to 10, n = 1 to 10), perfluoroalkane C m F 2m+2 (m = 4 to 20), perfluoroalkylamine (C mF 2m+1 ) 3 Examples of the fluorine compound include fluorine compounds such as N (m = 2 to 10) perfluoropolyether.

[0038] If necessary, the additive with reduced water content can also be used. Additives with low water content can be purchased, or methods for reducing the water content of the additive can also be utilized. The method for reducing the water content of the additive is not particularly limited as long as it is a generally available method. Examples include methods using a dehydrating agent and distillation. The dehydrating agent is not particularly limited as long as it is a generally used dehydrating agent. Examples include sodium hydride, magnesium sulfate, sodium sulfate, calcium sulfate, calcium chloride, zinc chloride, calcium oxide, magnesium oxide, diphosphorus pentoxide, activated alumina, silica gel, and molecular sieves. When using a dehydrating agent, an additive containing the dehydrating agent may be used as long as it does not affect the reaction between compound (1) and diphosphorus pentoxide, or an additive not containing the dehydrating agent may be used by filtration or the like. The dehydrating agent may be used alone or in combination of multiple types.

[0039] <Ratio (β / α) of the amount of substance of diphosphorus pentoxide (β) to the amount of substance of compound (1) (α)> In this embodiment, the amount of substance of diphosphorus pentoxide is 141.94 g / mol. The ratio (β / α) of the amount of substance of diphosphorus pentoxide (β) to the amount of substance of compound (1) (α) is preferably 0.1 or more, more preferably 0.5 or more, because it tends to suppress the remaining of unreacted compound (1). Depending on the type of compound (1), it is more preferably 1 or more, and particularly preferably 2 or more. The upper limit of the ratio (β / α) of the amount of substance (β) of diphosphorus pentoxide to the amount of substance (α) of compound (1) is not particularly limited, but since the amount of diphosphorus pentoxide used is reduced and the process for producing compound (2) tends to be more economical, β / α is preferably 100 or less, and more preferably 20 or less. Since the yield of compound (2) tends to increase and the process for producing compound (2) tends to be more economical, β / α is further preferably 10 or less, and particularly preferably 5 or less.

[0040] <The ratio (ε / (γ+δ)) of the mass of zirconia to the total mass (γ+δ) of the mass (γ) of compound (1) and the mass (δ) of diphosphorus pentoxide> The ratio (ε / (γ+δ)) of the mass (ε) of zirconia to the total mass (γ+δ) of the mass (γ) of compound (1) and the mass (δ) of diphosphorus pentoxide tends to suppress caking in the reaction between compound (1) and diphosphorus pentoxide, and is therefore preferably 0.1 or more, more preferably 2.0 or more, even more preferably 2.5 or more, and particularly preferably 3.0 or more. The upper limit of the ratio (ε / (γ+δ)) of the mass (ε) of zirconia to the total mass (γ+δ) of the mass (γ) of compound (1) and the mass (δ) of diphosphorus pentoxide is not particularly limited, but since the amount of zirconia used is reduced and the method for producing compound (2) tends to be more economical, (ε / (γ+δ)) is preferably 100 or less, and more preferably 50 or less. Since the yield of compound (2) tends to increase and the method for producing compound (2) tends to be more economical, (ε / (γ+δ)) is further preferably 30 or less, and particularly preferably 20 or less.

[0041] <Reaction of compound (1) with diphosphorus pentoxide> The reaction temperature of compound (1) with diphosphorus pentoxide is not particularly limited as long as it is a reaction temperature that is generally used, but since the reactivity of compound (1) with diphosphorus pentoxide tends to be high, the reaction temperature is preferably −40° C. or higher, and more preferably −20° C. or higher. From the same viewpoint and because the reaction temperature tends to be economical when adjusting the temperature industrially, the reaction temperature is further preferably 0° C. or higher, and particularly preferably 10° C. or higher. The upper limit of the reaction temperature between compound (1) and diphosphorus pentoxide is not particularly limited, but since volatilization of compound (1) can be suppressed and the yield of compound (2) tends to be more stable, the upper limit is preferably 300° C. or lower, and more preferably 250° C. or lower. Since deterioration of compound (2) can be suppressed and the method for producing compound (2) tends to be more economical, the upper limit is further preferably 200° C. or lower, and particularly preferably 180° C. or lower. The reaction temperature of compound (1) and diphosphorus pentoxide does not have to be constant so long as it is within the above range, and may be changed during the reaction.

[0042] When compound (2) is produced by the reaction of compound (1) with diphosphorus pentoxide, it is presumed that compound (1) reacts with diphosphorus pentoxide to form a reactant, and then compound (2) is produced from the reactant. Therefore, the reaction temperature for forming the reactant and the reaction temperature for producing compound (2) from the reactant may be the same or different. The reaction temperature when forming the reactant is preferably −40° C. or higher, more preferably −20° C. or higher, since the reactivity of compound (1) with diphosphorus pentoxide tends to be high. From the same viewpoint and because it tends to be economically advantageous when adjusting the temperature industrially, it is more preferably 0° C. or higher, particularly preferably 10° C. or higher. Since suppressing the reaction between compound (1) and diphosphorus pentoxide tends to suppress deterioration of compound (1) due to reaction heat, the reaction temperature is preferably 180° C. or lower, more preferably 150° C. or lower, and even more preferably 120° C. or lower. The reaction temperature for producing compound (2) from the reactant is preferably 80° C. or higher, more preferably 100° C. or higher, and even more preferably 120° C. or higher, since the production of compound (2) tends to be promoted. The reaction temperature is preferably 300° C. or lower, and more preferably 250° C. or lower, since the yield of compound (2) tends to be stable. The reaction temperature is more preferably 200° C. or lower, and particularly preferably 180° C. or lower, since deterioration of compound (2) can be suppressed and the economic efficiency of the method for producing compound (2) tends to be improved.

[0043] The reaction time of compound (1) with diphosphorus pentoxide is not particularly limited as long as it is within a range generally used, but since the stability of the yield of compound (2) is further increased, it is preferably 0.5 hours or more, and more preferably 1 hour or more. Since an excessive reaction time tends to result in a more economical production method, it is preferably 100 hours or less, and from the same viewpoint, it is more preferably 50 hours or less, and even more preferably 20 hours or less.

[0044] The reaction pressure between compound (1) and diphosphorus pentoxide is not particularly limited as long as it is within a range that is usually used, and may be any of pressurized, normal, and reduced pressure. Depending on the type of compound (1), the vapor pressure at the reaction temperature is high, so that reaction under pressurized pressure may be preferable since volatilization of compound (1) can be suppressed. Depending on the type of compound (1), the vapor pressure at the reaction temperature is low, so that reaction under normal pressure may be preferable since it tends to be more economical. Depending on the type of compound (2), the vapor pressure at the reaction temperature is low, so that when compound (2) is volatilized and recovered, reduced pressure may be preferable. Depending on the type of compound (2), the vapor pressure at the reaction temperature is low, so that reaction under normal pressure may be preferable since it tends to be more economical. The upper limit of the pressure when applying pressure is not particularly limited as long as it is within a range that is commonly used, but since this tends to reduce the complexity of the pressurizing device, the pressure is preferably 100 MPaG or less, more preferably 1 MPaG or less, even more preferably 0.4 MPaG or less, and particularly preferably 0.2 MPaG or less. The lower limit of the pressure when reducing the pressure is not particularly limited as long as it is within a range that is commonly used. However, since this tends to reduce the complexity of the device for reducing the pressure, the lower limit is preferably 0.01 PaA or more, more preferably 1 PaA or more, even more preferably 100 PaA or more, and particularly preferably 500 PaA or more. The pressure in the reaction of compound (1) with diphosphorus pentoxide does not need to be constant so long as it is within the above range, and may be changed during the reaction.

[0045] The atmosphere for the reaction of compound (1) with diphosphorus pentoxide is not particularly limited as long as it is a commonly used atmosphere, and typically includes air, nitrogen, and argon atmospheres. Among these, nitrogen and argon atmospheres are preferred because they tend to produce compound (2) more safely. In addition, nitrogen atmosphere is more preferred because it tends to be a more economical production method. The atmospheric dew point of the reaction atmosphere is preferably -10°C or lower, more preferably -30°C or lower, and even more preferably -50°C or lower, since this tends to suppress deterioration of diphosphorus pentoxide. The reaction atmosphere may be used alone or in combination of a plurality of reaction atmospheres.

[0046] As described above, in the reaction between compound (1) and diphosphorus pentoxide, compound (1) and diphosphorus pentoxide react to form a reactant, and then compound (2) is produced from the reactant. As a result of detailed observation of this reaction, the present inventors found that the reactant solidifies when it becomes a reactant, and even if the solidified reactant is pulverized, it solidifies again when compound (2) is produced from the reactant. Therefore, by reacting compound (1) with diphosphorus pentoxide to produce a reactant using an apparatus capable of suppressing solidification when it becomes a reactant, and then adding zirconia, it is also possible to suppress solidification when compound (2) is produced from the reactant. That is, zirconia may be added when compound (1) is reacted with diphosphorus pentoxide to form a reactant, or zirconia may be added after compound (1) is reacted with diphosphorus pentoxide to form a reactant, or zirconia may be added when compound (1) is reacted with diphosphorus pentoxide to form a reactant, and zirconia may be further added after the reactant is formed. Among these, the method of adding zirconia when compound (1) is reacted with diphosphorus pentoxide to form a reactant is preferred because it tends to always suppress solidification in the reaction in which compound (1) reacts with diphosphorus pentoxide to produce compound (2) and tends to reduce the complexity of operations during the reaction. In the method of adding zirconia when reacting compound (1) with diphosphorus pentoxide to form a reactant, the order in which compound (1), diphosphorus pentoxide, and zirconia are added is not particularly limited. However, because there is a tendency to further suppress caking due to the reaction between compound (1) and diphosphorus pentoxide, preferred examples of the method include a method of adding a mixture of compound (1) and zirconia to diphosphorus pentoxide, a method of adding diphosphorus pentoxide to a mixture of compound (1) and zirconia, a method of adding a mixture of diphosphorus pentoxide and zirconia to compound (1), and a method of adding compound (1) to a mixture of diphosphorus pentoxide and zirconia.

[0047] The method for mixing compound (1), diphosphorus pentoxide, and zirconia is not particularly limited as long as it is a commonly used method, and examples of such methods include a mixing tank type (horizontal or vertical), the number of stirring shafts (two shafts, three shafts, or four shafts), the shape of agitating blades (for example, fan, propeller, cross, butterfly, dragonfly, turbine, disc turbine, disperse, paddle, inclined paddle, helical, double helical, ribbon, straight blade, 45° twist blade, 90° twist blade, etc.), and the installation of a baffle in a mixing tank. More specifically, examples of mixing equipment include the pressure kneader, Wonder Kneader, Mix Lab, kneading test equipment, small-volume pressure kneader, MS-type small pressure kneader, twin-arm kneader, valve kneader, kneader ruder, special pressure kneader, reduced pressure kneader, twin-screw taper extruder, twin-screw single-screw extruder, and feeder ruder manufactured by Nihon Spindle Mfg. Co., Ltd., the KRC kneader, batch kneader, pressure kneader, extruder, CD dryer, SC processor, and CD dryer manufactured by Kurimoto Iron Works, Ltd., and the I BDM twin-shaft mixer, butterfly mixer, CDM concentric twin-shaft mixer, pony mixer, trimix, planetary mixer, PD mixer, kneader, flushing kneader, salt milling kneader, pressure kneader, and KX kneader manufactured by Kamiseisakusho Co., Ltd.; Pam Apex mixer, super double mixer manufactured by Pacific Machinery Co., Ltd.; vertical mixer, ribbon mixer, high-speed paddle mixer, and paddle mixer manufactured by Nishimura Machinery Co., Ltd.; Byte mix, Nauta mixer, solid air, micron thermo processor, and torus disk manufactured by Hosokawa Micron Co., Ltd.; paddle dryer, single paddle dryer, Buno cooler, multi-fin processor, extruder, and high-speed mixing and granulating machine manufactured by Nara Machinery Co., Ltd.; PV mixer and SV mixer manufactured by Kobelco Eco-Solutions Co., Ltd.; Ribocone and flow jet granulator manufactured by Okawara Manufacturing Co., Ltd.; twin-shaft kneading extruder manufactured by The Japan Steel Works, Ltd.; Hivismix, Hivisdispermix, and Combimix manufactured by Primix Corporation. , the ACM series manufactured by Aikosha Seisakusho Co., Ltd., the mixer, twin servo mixer, S kneader, spherical kneader, spherical beveled axis kneader, and high-speed kneading granulator manufactured by Shinagawa Kogyosho Co., Ltd., the intensive mixer and Evactherm manufactured by Nippon Eirich Co., Ltd., the axial mixer and Hemisphere mixer manufactured by Sugiyama Heavy Industries Co., Ltd., the vacuum mixer dryer manufactured by Katsuragi Kogyo Co., Ltd., the vacuum mixer dryer manufactured by Yasujima Co., Ltd., the mixer, semi-pressure kneader, kneader ruder, and vacuum extruder manufactured by MIG Co., Ltd., etc. In the case where a large amount of zirconia is used or where zirconia is added to the pulverized reaction product to produce compound (2), in addition to the above-mentioned apparatuses, examples of the apparatuses that can be used include the KID dryer, Rotlouba dryer, rotary dryer, and rotary kiln manufactured by Kurimoto Iron Works, Ltd., the conical dryer manufactured by Kobelco Eco-Solutions Co., Ltd., the electrically heated rotary kiln, gas heated rotary kiln, batch type rotary kiln, desktop rotary kiln, vacuum desktop rotary kiln, and special atmosphere + vacuum rotary kiln manufactured by Takasago Industrial Co., Ltd., the super rotary dryer and eco dryer manufactured by Okawara Manufacturing Co., Ltd., the rotary kiln and double cone mixer manufactured by Sugiyama Heavy Industries Co., Ltd., the double cone dryer manufactured by Katsuragi Kogyo Co., Ltd., and the rotary kiln manufactured by Yasujima Corporation. The above mixing device may be used alone or in combination of a plurality of mixing devices.

[0048] In the case where compound (1), diphosphorus pentoxide, and zirconia are not mixed at the same time, but any one of the combinations of compound (1) and diphosphorus pentoxide, the combination of compound (1) and zirconia, and the combination of diphosphorus pentoxide and zirconia is mixed before being supplied to an apparatus for mixing compound (1), diphosphorus pentoxide, and zirconia, in addition to the above-mentioned apparatus, a nibbler, feather mill, farmer mill, hammer mill, hammer blade, disintegrator, rubber chopper, Rotoplex, compact line, ACM permeabilizer, grating mill, etc., manufactured by Hosokawa Micron Corporation, may be used. Lasis, Fine Impact Mill, Victory Mill, Contraplex, Linrex Mill, Micro Pulverizer, Counter Jet Mill, Micron Jet, Super Micron Mill, Innomizer, Pulvis, Spiral Jet Mill, Disper Mill, and Hydro Mill, Jiyuu Grinding Mill, New Cosmomizer, Micros, Super Clean Mill, Sample Mill, Super Jiyuu Mill, Mill Box, Cosmo Box, Hammer Mill, Goblin, Baryonyx, Briodon, Polvogene, and Gina manufactured by Nara Machinery Works, Ltd., and Kuro Mill, ... Jet mill, Pocket jet, Gadget, Hi-G, Agitator mill, VX mill, Roller mill, Ball mill, Rod mill, K-VIX mill, and Granulator, Jaw crusher, Ratchet roll crusher, Corrugated roll crusher, Roll crusher, Tandem roll crusher, Oniha roll crusher, S-shaped crusher, 4-axis crusher, Fiber mill, Bevel impactor, Radical impactor, Ball mill, Attrition mill, and Cube rotor mill manufactured by Sugiyama Heavy Industries Co., Ltd., Super powder mill manufactured by Nishimura Machinery Co., Ltd. Centrifugal crushers, Fairy Powder Mills, Stamp Mills, High Speed ​​Crushers, Hammer Crushers, Sloot Mills, Seryuners, Shredders, and Cutter Mills; Vertical Roller Mills, Kryptron Zepros, Kryptron Venti, Kryptron, Kryptron Eddy, Kryptron Prime, Jedi, Converge Mill, Oshlobit, Conibit, and Hammer Mills manufactured by EarthTechnica Corporation; Super Jet Mills, Super Rotors, and Blade Mills manufactured by Nisshin Engineering Inc.; Drystar and Sigma Dry manufactured by Ashizawa Finetech Co., Ltd.Labstar, Nano Getter, Mugen Flow, and Delta Vita, Seishin Enterprise Co., Ltd.'s Single Track Jet Mill, Sk Jet O Mill, Cojet System α-mkV, Sanitary JOM Series, AO Jet Mill, Impeller Mill, Planetary Mill, Orient Crusher, Atomizer, Pin Mill, and Spiral Mill, Makino Sangyo Co., Ltd.'s Frame Dismantler, Oniha Crusher, Tear Crusher, Hammer Crusher, Makino Crusher, Exceed Mill, Disc Type Crusher, Coroplex Crusher, Contraplex Crusher, and Ultraplex Crusher, Tsukasa Industrial Co., Ltd.'s Pow Cutter, Pow Crusher, Line Mill, Wave Mill, and Pow Jet, Imex Co., Ltd.'s Easy Nano, Ready Mill, Ne Other examples include o-Alpha Mill, low-temperature / freeze grinding bead mill, Visco Mill, and sand grinder, Apex Mill, Ultra Apex Mill, Wide Separator Apex Mill, Dual Apex Mill, Ultra Apex Mill Advance, Apex Disperser ZERO, and Apex LABO manufactured by Hiroshima Metal & Machinery Co., Ltd., MSC Mill, SC Mill, SC Mill Long, MY Mill, Attritor, Trigonal, Fine Mill, Dynamic Mill, Alchemy, Stream Mill, and Centri Cutter manufactured by Nippon Coke & Engineering Co., Ltd., Mighty Mill Mark II, Spike Mill, Key Mill, MP Mill, MF Mill, Mighty Mill, Nano Sonic Mill, Three-roll Mill Ceramic Roll, and Three-roll Mill Chilled Roll manufactured by Inoue Seisakusho Co., Ltd., and the like. The above mixing device may be used alone or in combination of a plurality of mixing devices.

[0049] Examples of methods for adding compound (1) to an apparatus for mixing compound (1), diphosphorus pentoxide, and zirconia include a method of adding compound (1) by utilizing its own weight, a method of adding compound (1) under pressure, a method of adding compound (1) by using a liquid delivery pump (e.g., a smooth flow pump, a motor-driven metering pump, a solenoid-driven metering pump, an air-driven pump, a dynamic vacuum pump, a tube pump, a slurry pump, a magnet pump, an air-driven bellows pump, an electromagnetically-driven metering pump, a rotary volumetric pump, etc.), etc. The method of using a liquid delivery pump is preferred because it tends to have excellent controllability over the rate at which compound (1) is added.

[0050] Examples of the method of adding diphosphorus pentoxide and / or zirconia to an apparatus for mixing compound (1), diphosphorus pentoxide, and zirconia include a method of adding by utilizing its own weight, a method of adding by passing an air current (e.g., suction-type pneumatic transport, low-pressure pressure-fed pneumatic transport, high-pressure pressure-fed pneumatic transport, etc., and the pneumatic transport may be transport in a different atmosphere such as dry air transport, nitrogen transport, argon transport, etc.), and a method of adding by using a powder feeder (e.g., a screw feeder, a vibration feeder, a circle feeder, a conveyor-type feeder, an auger-type powder filling machine, a weighing-type powder feeder, a volumetric-type powder feeder, etc.). The method of using a powder feeder is preferred because it tends to have excellent controllability of the rate at which diphosphorus pentoxide and / or zirconia is added.

[0051] Regarding the above-mentioned respective devices, adding means, containers, etc. (for example, a device used when reacting compound (1) with diphosphorus pentoxide, a container containing compound (1), diphosphorus pentoxide, and zirconia, a liquid delivery pump used when adding compound (1), a powder feeder used when adding compound (2) and / or zirconia, etc.), and piping etc. connecting each of them, materials used in the places where compound (1), compound (2), and zirconia come into contact with each other are not particularly limited as long as they are generally used materials, and examples thereof include metals, metal alloys, resins, composite materials of metals and resins, ceramics, etc. More specific examples include titanium, nickel, zirconia, platinum, carbon steel, alloy steel, cast iron, stainless steel (SUS304, SUS304L, SUS430, SUS410, SUS316, SUS316L, SUS329J1, SUS329J4L, etc.), nickel-titanium alloys, nickel-chromium-molybdenum alloys (Inconel (registered trademark) 600, 625, 718, X750, etc., Hastelloy (registered trademark) C-22, C276, etc.), nickel-copper alloys (Monel (registered trademark) 400, K, S, H, Nickelvac (registered trademark) 400, Nikoros (registered trademark) 400, etc.), nickel-cobalt-chromium-molybdenum alloys, nickel-molybdenum alloys (Hastelloy (registered trademark) ALLOY B2, B, etc.), nickel-cobalt alloys, nickel-iron alloys, nickel-tungsten alloys, cobalt-chromium alloys, cobalt-chromium-molybdenum alloys (ELGILOY, PHYNOX (registered trademark), etc.), platinum-enriched stainless steel, fluorine-based resins (Teflon (registered trademark), copolymers of tetrafluoroethylene and perfluoroalkoxyethylene, perfluoroethylene propene copolymers, ethylene tetrafluoroethylene copolymers, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene chlorotrifluoroethylene copolymers, etc.), polyether ether ketone, polypropylene, polyphenylene ether, polyamide 6, polyamide 66, aromatic polyamide, polyphenylene sulfide, polysulfone, polyether sulfone, polyether imide, polyamide imide, etc. The above materials may be used alone or in combination of two or more.

[0052] <Fluorine-containing sulfonic acid anhydride (2) (compound (2))> The following general formula (2): (R f SO 2 ) 2 O (2) (In the formula, R f represents a saturated or unsaturated aliphatic or aromatic hydrocarbon group in which at least one hydrogen atom is substituted with a fluorine atom, and the ethylene structure in the hydrocarbon group may be substituted with a structure having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom; R f The carbon number is 1 to 20, and two R f They may be the same or different) It is expressed as: The fluorine-containing sulfonic acid anhydride (2) may be one type alone or a combination of two or more types.

[0053] In the formula, R f The details of R in the general formula (1) representing the fluorine-containing sulfonic acid (1) are as follows: f may be considered the same as

[0054] INDUSTRIAL APPLICABILITY As described above, the present invention can suppress caking in the reaction of a fluorinated sulfonic acid (1) with diphosphorus pentoxide, and can produce a fluorinated sulfonic anhydride (2) useful as a catalyst for medicines, organic synthesis, etc., or as a synthetic raw material with good yield. EXAMPLES

[0055] The present invention is not limited to the following examples, so long as they do not depart from the gist of the present invention.

[0056] The analytical methods used in the examples and comparative examples are as follows.

[0057] <Nuclear magnetic resonance analysis (NMR): 19 Molecular structure analysis using F-NMR> Regarding the products obtained in the examples and comparative examples, 19Molecular structure analysis was carried out using F-NMR under the following measurement conditions. [Measurement conditions] Measurement equipment: JNM-ECZ400S nuclear magnetic resonance equipment (manufactured by JEOL Ltd.) Observation kernel: 19 F Solvent: deuterated chloroform Reference substance: tetramethylsilane (0.00 ppm) Observation frequency: 400MHz ( 1 H) Pulse width: 6.5μsec Wait time: 2 seconds Number of times: 16

[0058] <Nuclear magnetic resonance analysis (NMR): 1 Molecular structure analysis using H-NMR> Regarding the products obtained in the examples and comparative examples, 1 Molecular structure analysis was carried out using H-NMR under the following measurement conditions. [Measurement conditions] Measurement equipment: JNM-ECZ400S nuclear magnetic resonance equipment (manufactured by JEOL Ltd.) Observation kernel: 1 H Solvent: deuterated chloroform Reference substance: tetramethylsilane (0.00 ppm) Observation frequency: 400MHz ( 1 H) Pulse width: 7.3 μsec Wait time: 5 seconds Number of times: 8

[0059] The raw materials used in the examples and comparative examples are shown below.

[0060] [Production Example 1] (Fluorine-containing sulfonic acid (1) (compound (1)) According to JP 2019-156782 A, compound (5) represented by the following formula (5) was produced. CF 2 =CFOCF 2 CF 2 SO 3 Na (5) Using the obtained compound of formula (5) above, a fluorine-containing sulfonic acid (6) (compound (6)) was produced by the following method with reference to WO 2020 / 012913. Compound (5) (800 g, 2.67 mol), 23 mass% sulfuric acid (prepared from sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) and distilled water (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)) (1.71 kg, the amount of sulfuric acid contained is 4.00 mol) was added to a 6 L separable flask, stirred, and then cyclopentyl methyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade reagent) (1.20 kg) was added, stirred for 1 hour, and then allowed to stand for 2 hours. The upper cyclopentyl methyl ether phase was collected in a flask, placed in an evaporator set at 45 ° C., and rotated at 120 rpm. The pressure was gradually reduced, and finally reduced to 3.0 kPaA, and then volatile components were distilled off for 4 hours. Distilled water (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (600 g) was added to the flask, placed in an evaporator set at 45 ° C., and rotated at 120 rpm. The pressure was gradually reduced, and finally reduced to 3.0 kPaA, after which the volatile components were distilled off for 2 hours. Furthermore, distilled water (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (600 g) was added to the flask, which was then placed in an evaporator set at 45°C and rotated at 120 rpm. The pressure was gradually reduced, and finally reduced to 3.0 kPaA, after which the volatile components were distilled off for 1 hour. 0.30 g of the resulting concentrate was taken out, 1As a result of the H-NMR analysis, no peak of cyclopentyl methyl ether was detected. 391.2 g of the concentrate obtained was transferred to a flask equipped with a stirrer and a Liebig condenser with a receiver, and the atmosphere was replaced with nitrogen three times. Cooling water set at -5°C was passed through the Liebig condenser, the flask was placed in an oil bath set at 90°C, stirred, and the pressure was reduced to 0.7 kPaA. After confirming the distillation of the volatile components, the oil bath was gradually heated to 130°C, and one hour after confirming the distillation, the pressure was returned to normal pressure with nitrogen, and the flask was removed from the oil bath. After the flask reached room temperature, the mass of the contents was measured and found to be 320.9 g. To the resulting content (0.30 g), 1,2-dimethoxyethane (Fujifilm Wako Pure Chemical Industries, Ltd., Wako special grade, dried molecular sieve 4A 1 / 16 (Fujifilm Wako Pure Chemical Industries, Ltd.) was added, dehydrated, and the water content was adjusted by removing the molecular sieve 4A 1 / 16) (1.0 g) and benzotrifluoride (Tokyo Chemical Industry Co., Ltd.) (0.10 g) were added for analysis, and the mixture was stirred. 19 F-NMR analysis revealed that 301.5 g (1.08 mol) of fluorine-containing sulfonic acid (6) represented by the following formula (6) was obtained. CF 2 =CFOCF 2 CF 2 SO 3 H (6) For analysis, 1,2-dimethoxyethane (Fujifilm Wako Pure Chemical Industries, Ltd., Wako special grade, dried molecular sieve 4A 1 / 16 (Fujifilm Wako Pure Chemical Industries, Ltd.) was added, dehydrated, and the molecular sieve 4A 1 / 16 was removed to adjust the moisture content) (2.0 g) was added to the content (0.20 g) and stirred, and the moisture content was analyzed using a Karl Fischer moisture meter (Kyoto Electronics Manufacturing Co., Ltd., MKC-710D). As a result, it was found that the content contained 17.8 g of water. The moisture content of the 1,2-dimethoxyethane used was also measured, and the moisture content of the content was calculated excluding the moisture content contained in the 1,2-dimethoxyethane used. The product obtained as described above will be referred to as "fluorine-containing compound (6) obtained in Production Example 1" or "compound (6) obtained in Production Example 1" in the following examples, comparative examples, etc.

[0061] (Diphosphorus pentoxide) Phosphorus(V) oxide (Wako Pure Chemical Industries, Fujifilm, Wako special grade)

[0062] (Zirconia) Zirconia A (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., EP zirconium oxide, particle size 2.0 μm, zirconium dioxide content 99.9% by mass) Zirconia B (manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd., UEP zirconium oxide, particle size 0.6 μm, zirconium dioxide content 99.9% by mass) Zirconia C (Nikkato Corporation, YTZ (registered trademark) ball 0.03, particle size 30 μm, zirconium dioxide content 95 mass%, yttrium oxide content 4.9 mass%) Zirconia D (Nikkato Corporation, YTZ (registered trademark) ball 0.05, particle size 50 μm, zirconium dioxide content 95 mass%, yttrium oxide content 4.9 mass%) Zirconia E (Nikkato Corporation, YTZ (registered trademark) ball 0.1, particle size 100 μm, zirconium dioxide content 95 mass%, yttrium oxide content 4.9 mass%)

[0063] (others) Benzotrifluoride (Tokyo Chemical Industry Co., Ltd.) Hexafluorobenzene (Tokyo Chemical Industry Co., Ltd.)

[0064] [Example 1] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (30.8 g, 217 mmol) and zirconia A (224 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 20.1 g (containing 18.9 g (67.9 mmol) of fluorine-containing sulfonic acid (6)). The oil bath was set to 90° C. and the mixture was stirred for 1 hour, and then stirred for 20 minutes at 140° C. and 10 kPaA. When the oil bath was set to 160° C., the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that the distillation had ceased, the stirring was stopped. After the flask was purged with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 15.0 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed. 19 The product was analyzed by F-NMR. As a result of the analysis, it was found that 14.6 g (27.1 mmol, yield 79.7%) of fluorine-containing sulfonic anhydride (7) represented by the following general formula (7) was obtained. It was also found that 0.36 g (1.3 mmol) of fluorine-containing sulfonic acid (6) was contained. In the analysis, the mass of benzotrifluoride, the CF 3, fluorine-containing sulfonic anhydride (7), and fluorine-containing sulfonic acid (6) CF 2 From the integral value of the above, the masses of the fluorine-containing sulfonic anhydride (7) and the fluorine-containing sulfonic acid (6) were calculated. (CF 2 =CFOCF 2 CF 2 SO 2 ) 2 O (7) 19 F-NMR: δ(ppm) -85.3(4F), -112.0(4F), -116.4(2F), -123.6(2F), -139.0(2F) The yield of the fluorine-containing sulfonic acid anhydride (7) was calculated according to the following formula (1). Yield (%) of fluorine-containing sulfonic anhydride (7) = amount of fluorine-containing sulfonic anhydride (7) / (amount of fluorine-containing sulfonic acid (6) used as raw material × 0.5) × 100 (1) For example, the yield (%) of the fluorine-containing sulfonic acid anhydride (7) in this example is 27.1 (mmol) / (67.9 (mmol)×0.5)×100=79.7. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, β / α was 3.2 and ε / (γ+δ) was 4.5.

[0065] [Example 2] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (23.7 g, 167 mmol) and zirconia A (203 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 19.8 g (containing 18.6 g (66.9 mmol) of fluorine-containing sulfonic acid (6)). The oil bath was set to 90° C. and the mixture was stirred for 1 hour, and then stirred for 20 minutes at 140° C. and 10 kPaA. When the oil bath was set to 160° C., the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that the distillation had ceased, the stirring was stopped. After the flask was purged with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 13.1 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed. 19 The product was analyzed by F-NMR. As a result of the analysis, it was found that 12.1 g (22.5 mmol, 67.4% yield) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.86 g (3.1 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, β / α was 2.5 and ε / (γ + δ) was 4.8.

[0066] [Example 3] In a nitrogen atmosphere space dried in a dry column (manufactured by Nippon Kayaku Co., Ltd., DC-A4), phosphorus pentoxide (42.3 g, 298 mmol) and zirconia A (279 g) were placed in a flask, and a semi-circular stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached and removed from the nitrogen atmosphere space. Dry nitrogen was introduced through the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled by dry ice. The flask was placed in an oil bath (manufactured by Tokyo Rikakikai Co., Ltd., OHB-3100S) set at 40°C, and while stirring, the fluorine-containing compound (6) was gradually added dropwise. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 19.6 g (containing 18.4 g (66.2 mmol) of fluorine-containing sulfonic acid (6)). After stirring for 1 hour with the oil bath set at 90°C, it was stirred at 140°C and 10 kPaA for 20 minutes. When the oil bath was set at 160°C, distillate was gradually recovered in the receiver. The pressure was gradually reduced from the time when the distillation slowed down to 2 kPaA. When it was confirmed that the distillation had stopped, stirring was stopped. After replacing the flask with nitrogen, it was removed from the oil bath, the circulation of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled by dry ice, and the temperature was returned to room temperature. After removing the Liebig condenser from the flask and plugging the flask with a glass stopper, the flask was transferred to a dry nitrogen atmosphere space. As a result of measuring the mass of the contents of the receiver, it was 13.3 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed, 19 and analyzed by 19F-NMR. As a result of the analysis, it was found that 13.0 g (24.1 mmol, yield 72.9%) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.18 g (0.7 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, β / α was 4.5 and ε / (γ+δ) was 4.6.

[0067] [Example 4] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (28.7 g, 202 mmol) and zirconia A (145 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 19.3 g (containing 18.1 g (65.2 mmol) of fluorine-containing sulfonic acid (6)). The oil bath was set to 90° C. and the mixture was stirred for 1 hour, and then stirred for 20 minutes at 140° C. and 10 kPaA. When the oil bath was set to 160° C., the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that the distillation had ceased, the stirring was stopped. After the flask was purged with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 14.2 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed. 19The product was analyzed by F-NMR. As a result of the analysis, it was found that 13.9 g (25.8 mmol, 79.2% yield) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.24 g (0.8 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings. As a result, 14.3 g remained on the sieve and 164 g of material passed through the sieve. In this example, β / α was 3.1 and ε / (γ+δ) was 3.1.

[0068] [Example 5] In a nitrogen atmosphere space dried in a dry column (manufactured by Nikkak Seiko Co., Ltd., DC-A4), phosphorus pentoxide (15.3 g, 108 mmol) and zirconia A (359 g) were placed in a flask, and a semi-circular stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached and removed from the nitrogen atmosphere space. Dry nitrogen was introduced through the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled by dry ice. The flask was placed in an oil bath (manufactured by Tokyo Rika Kikai Co., Ltd., OHB-3100S) set at 40°C, and while stirring, the fluorine-containing compound (6) was gradually added dropwise. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 10.0 g (containing 9.40 g (33.8 mmol) of fluorine-containing sulfonic acid (6)). After stirring for 1 hour with the oil bath set at 90°C, it was stirred at 140°C·10 kPaA for 20 minutes. When the oil bath was set at 160°C, distillates were gradually recovered in the receiver. The pressure was gradually reduced from the time when the distillation slowed down to 2 kPaA. After confirming that the distillation had stopped, stirring was stopped. After replacing the flask with nitrogen, it was removed from the oil bath, the circulation of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled by dry ice, and the temperature was returned to room temperature. After removing the Liebig condenser from the flask and plugging the flask with a glass stopper, the flask was transferred to a dry nitrogen atmosphere space. As a result of measuring the mass of the contents of the receiver, it was 6.98 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed, 19 and analyzed by 19F-NMR. As a result of the analysis, it was found that 6.57 g (12.2 mmol, yield 72.3%) of the fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.35 g (1.3 mmol) of the fluorine-containing sulfonic acid (6) was contained. The contents of the flask transferred to a dry nitrogen atmosphere were sieved through a sieve with a mesh size of 11.2 mm. As a result, there was no substance remaining on the sieve. In this example, β / α was 3.2 and ε / (γ+δ) was 15.

[0069] [Example 6] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (31.7 g, 223 mmol) and zirconia A (227 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 20.0 g (containing 18.8 g (67.6 mmol) of fluorine-containing sulfonic acid (6)). The oil bath was set to 90° C. and the mixture was stirred for 1 hour, and then stirred for 20 minutes at 140° C. and 10 kPaA. When 140° C. and 10 kPaA were maintained, the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that the distillation had ceased, the stirring was stopped. After the flask was purged with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 14.7 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed. 19 The product was analyzed by F-NMR. The analysis showed that 14.2 g (26.4 mmol, 78.1% yield) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.39 g (1.4 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, β / α was 3.3 and ε / (γ+δ) was 4.5.

[0070] [Example 7] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (30.2 g, 213 mmol) and zirconia B (224 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 19.7 g (containing 18.5 g (66.6 mmol) of fluorine-containing sulfonic acid (6)). The oil bath was set to 90° C. and the mixture was stirred for 1 hour, and then stirred for 20 minutes at 140° C. and 10 kPaA. When the oil bath was set to 160° C., the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that the distillation had ceased, the stirring was stopped. After the flask was purged with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 15.2 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed. 19The product was analyzed by F-NMR. As a result of the analysis, it was found that 14.7 g (27.3 mmol, yield 82.1%) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.37 g (1.3 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, β / α was 3.2 and ε / (γ+δ) was 4.6.

[0071] [Example 8] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (30.9 g, 217 mmol) and zirconia C (226 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 19.5 g (containing 18.3 g (65.9 mmol) of fluorine-containing sulfonic acid (6)). The oil bath was set to 90° C. and the mixture was stirred for 1 hour, and then stirred for 20 minutes at 140° C. and 10 kPaA. When the oil bath was set to 160° C., the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that the distillation had ceased, the stirring was stopped. After the flask was purged with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 14.6 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed. 19 The product was analyzed by F-NMR. As a result of the analysis, it was found that 14.0 g (26.0 mmol, 79.0% yield) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.40 g (1.4 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, β / α was 3.3 and ε / (γ+δ) was 4.6.

[0072] [Example 9] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (29.7 g, 209 mmol) and zirconia D (218 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 20.0 g (containing 18.8 g (67.6 mmol) of fluorine-containing sulfonic acid (6)). The oil bath was set to 90° C. and the mixture was stirred for 1 hour, and then stirred for 20 minutes at 140° C. and 10 kPaA. When the oil bath was set to 160° C., the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that the distillation had ceased, the stirring was stopped. After the flask was purged with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 14.5 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed. 19 The product was analyzed by F-NMR. As a result of the analysis, it was found that 14.0 g (26.0 mmol, 77.0% yield) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.36 g (1.3 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, leaving 35.5 g on the sieve and 218 g of material passing through the sieve. In this example, β / α was 3.1 and ε / (γ+δ) was 4.5.

[0073] [Example 10] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (31.3 g, 221 mmol) and zirconia E (227 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 20.4 g (containing 19.2 g (68.9 mmol) of fluorine-containing sulfonic acid (6)). The oil bath was set to 90° C. and the mixture was stirred for 1 hour, and then stirred for 20 minutes at 140° C. and 10 kPaA. When the oil bath was set to 160° C., the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that the distillation had ceased, the stirring was stopped. After the flask was purged with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 15.0 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed. 19The product was analyzed by F-NMR. The analysis results showed that 14.4 g (26.8 mmol, 77.7% yield) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.44 g (1.6 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings. As a result, 84.3 g remained on the sieve and 179 g of material passed through the sieve. In this example, β / α was 3.2 and ε / (γ+δ) was 4.5.

[0074] [Example 11] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (30.1 g, 212 mmol) and zirconia A (145 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 19.6 g (containing 18.4 g (66.2 mmol) of fluorine-containing sulfonic acid (6)). After stirring for 1 hour with the oil bath set to 90°C, the flask was removed from the oil bath and cooled to room temperature. Stirring in the flask was stopped, and zirconia A (73.0 g) measured in the space under a nitrogen atmosphere was added to the flask. Stirring was resumed, the flask was placed in an oil bath, the oil bath was set to 90°C, and stirring was continued for 10 minutes, and then the mixture was stirred at 140°C and 10 kPaA for 20 minutes. When the oil bath was set to 160°C, the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. After confirming that distillation had ceased, stirring was stopped. After replacing the air in the flask with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, and the receiver was removed from the ethanol cooled with dry ice and returned to room temperature. The Liebig condenser was removed from the flask, and the flask was then sealed with a glass stopper and moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 14.6 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed, and 19The product was analyzed by F-NMR. As a result of the analysis, it was found that 14.1 g (26.2 mmol, 79.2% yield) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.37 g (1.3 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, β / α was 3.2 and ε / (γ+δ) was 4.5.

[0075] [Comparative Example 1] In a space with a nitrogen atmosphere dried by a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (31.2 g, 219 mmol) was placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 20.3 g (containing 19.1 g (68.6 mmol) of fluorine-containing sulfonic acid (6)). When the oil bath was set to 90° C. and stirring was performed for 1 hour, it was confirmed that the contents of the flask were attached to the stirring rod and the inner surface of the flask, and stirring was not possible. From this, it was determined that solidification occurred in this comparative example. In this comparative example, β / α was 3.2.

[0076] [Comparative Example 2] In a space with a nitrogen atmosphere dried by a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (28.2 g, 199 mmol) was placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing the fluorine-containing compound (6) obtained in Production Example 1 were attached, and the flask was taken out of the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and the fluorine-containing compound (6) was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of the fluorine-containing compound (6) obtained in Production Example 1 introduced into the flask was 12.0 g (containing 11.3 g (40.5 mmol) of fluorine-containing sulfonic acid (6)). When the oil bath was set to 90° C. and stirring was performed for 1 hour, it was confirmed that the contents of the flask were attached to the stirring rod and the inner surface of the flask, and stirring was not possible. From this, it was determined that solidification occurred in this comparative example. In this comparative example, β / α was 4.9.

[0077] [Reference example 1] In a space with an air atmosphere dried by a membrane dryer (IDG100SAV4-03, manufactured by SMC Corporation) and a dry column (DC-L4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (307 g, 2.16 mol) was placed in a semi-pressurized kneader (ND-025, manufactured by MIG Co., Ltd.) at room temperature, and two shafts were rotated in the same direction (one shaft was set at 90 rpm, the other shaft was set at 60 rpm). Fluorine-containing sulfonic acid (6) (200 g) (containing 188 g (676 mmol) of fluorine-containing sulfonic acid (6)) produced by the same method as in Production Example 1 was gradually added, and kneaded for 2 hours. When the rotation of the apparatus was stopped and the contents were taken out, a kneaded product of fluorine-containing sulfonic acid (6) and diphosphorus pentoxide was obtained as a powder. In this reference example, β / α was 3.2.

[0078] [Reference example 2] In a space of an air atmosphere dried with a membrane dryer (IDG100SAV4-03, manufactured by SMC Corporation) and a dry column (DC-L4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (161 g, 1.14 mol) and fluorine-containing sulfonic acid (6) (102 g) (containing 95.8 g (345 mmol) of fluorine-containing sulfonic acid (6)) produced by the same method as in Production Example 1 were put into a kneader (2P-03, manufactured by Primix Corporation) at room temperature, and kneaded for 10 minutes at a revolution setting of 50 rpm, and then kneaded for 50 minutes at a revolution setting of 100 rpm. When the rotation of the apparatus was stopped and the contents were removed, a kneaded product of fluorine-containing sulfonic acid (6) and diphosphorus pentoxide was obtained as a powder. In this reference example, β / α was 3.3.

[0079] [Reference example 3] In a space of an air atmosphere dried by a membrane dryer (IDG100SAV4-03, manufactured by SMC Corporation) and a dry column (DC-L4, manufactured by Nikka Seiko Co., Ltd.), a continuous twin-screw kneader (S1KRC, manufactured by Kurimoto Iron Works Co., Ltd.) was operated at a rotation speed of 200 rpm, diphosphorus pentoxide (360 g / h, 2.54 mol / h) was supplied using a powder micro-quantitative supplying device (FeedCommu M-030F, manufactured by Nisshin Engineering Inc.), and fluorine-containing sulfonic acid (6) (221 g / h) (fluorine-containing sulfonic acid (6) was 208 g / h (747 mmol / h)) produced by the same method as in Production Example 1 was supplied using a macro tube pump (MP-1000, manufactured by Tokyo Rikakikai Co., Ltd.) and kneaded. As a result, a kneaded product of fluorine-containing sulfonic acid (6) and diphosphorus pentoxide was obtained as a powder. In this reference example, β / α was 3.4.

[0080] [Example 12] In a space with a nitrogen atmosphere dried with a dry column (manufactured by Nikka Seiko Co., Ltd., DC-A4), the kneaded product (40.0 g) produced in Reference Example 1 (containing 14.9 g (53.4 mmol) of fluorine-containing sulfonic acid (6) and 24.3 g (171 mmol) of diphosphorus pentoxide) and zirconia A (88.0 g) were placed in a flask, a half-moon-shaped stirring rod with a stirring seal and a Liebig condenser with a receiver were attached, and the flask was taken out of the space with a nitrogen atmosphere. A refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (manufactured by Tokyo Rikakikai Co., Ltd., OHB-3100S) set at 40°C, stirred, the oil bath was set to 90°C and stirred for 1 hour, and then stirred at 140°C·10 kPaA for 20 minutes. When the oil bath was set to 160°C, the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that distillation had ceased, the stirring was stopped. After replacing the atmosphere in the flask with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 12.2 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed, and 19 The product was analyzed by F-NMR. As a result of the analysis, it was found that 11.8 g (22.0 mmol, yield 82.4%) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.24 g (0.9 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, ε / (γ+δ) was 2.3.

[0081] [Example 13] In a space with a nitrogen atmosphere dried with a dry column (manufactured by Nikka Seiko Co., Ltd., DC-A4), the kneaded product (39.9 g) produced in Reference Example 2 (containing 14.5 g (52.3 mmol) of fluorine-containing sulfonic acid (6) and 24.5 g (173 mmol) of diphosphorus pentoxide) and zirconia A (85.9 g) were placed in a flask, a half-moon-shaped stirring rod with a stirring seal and a Liebig condenser with a receiver were attached, and the flask was taken out of the space with a nitrogen atmosphere. A refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (manufactured by Tokyo Rikakikai Co., Ltd., OHB-3100S) set at 40°C, stirred, the oil bath was set to 90°C and stirred for 1 hour, and then stirred at 140°C·10 kPaA for 20 minutes. When the oil bath was set to 160°C, the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that distillation had ceased, the stirring was stopped. After replacing the atmosphere with nitrogen, the flask was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, and the flask was then sealed with a glass stopper and moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 11.7 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed, and 19 The product was analyzed by F-NMR. As a result of the analysis, it was found that 11.3 g (21.1 mmol, yield 80.5%) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.31 g (1.1 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, ε / (γ+δ) was 2.2.

[0082] [Example 14] In a space with a nitrogen atmosphere dried with a dry column (manufactured by Nikka Seiko Co., Ltd., DC-A4), the kneaded product (40.1 g) produced in Reference Example 3 (containing 14.4 g (51.6 mmol) of fluorine-containing sulfonic acid (6) and 24.9 g (175 mmol) of diphosphorus pentoxide) and zirconia A (90.3 g) were placed in a flask, a half-moon-shaped stirring rod with a stirring seal and a Liebig condenser with a receiver were attached, and the flask was taken out of the space with a nitrogen atmosphere. A refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (manufactured by Tokyo Rikakikai Co., Ltd., OHB-3100S) set at 40°C, stirred, the oil bath was set to 90°C and stirred for 1 hour, and then stirred at 140°C·10 kPaA for 20 minutes. When the oil bath was set to 160°C, the distillate was gradually collected in the receiver. Once the distillation slowed down, the pressure was gradually reduced to 2 kPaA. Once it was confirmed that distillation had ceased, the stirring was stopped. After replacing the atmosphere with nitrogen, the flask was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was then moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 11.6 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed, and 19 The product was analyzed by F-NMR. As a result of the analysis, it was found that 11.2 g (20.7 mmol, yield 80.4%) of fluorine-containing sulfonic anhydride (7) was obtained. It was also found that 0.27 g (1.0 mmol) of fluorine-containing sulfonic acid (6) was contained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, ε / (γ+δ) was 2.3.

[0083] [Comparative Example 3] In a nitrogen atmosphere space dried by a dry column (manufactured by Nippon Kasei Kogyo Co., Ltd., DC-A4), the kneaded product (39.2 g) produced in Reference Example 1 was placed in a flask, a semi-circular stirring rod with a stirring seal and a Liebig condenser with a receiver were attached, and it was taken out from the nitrogen atmosphere space. A refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled by dry ice. The flask was placed in an oil bath (manufactured by Tokyo Rika Kikai Co., Ltd., OHB-3100S) set at 40°C and stirred. When the setting of the oil bath was changed to 90°C and stirred for 1 hour, it was confirmed that the contents of the flask adhered to the stirring rod and the inner surface of the flask and could not be stirred. From this, it was determined that solidification occurred in this comparative example.

[0084] [Comparative Example 4] In a nitrogen atmosphere space dried by a dry column (manufactured by Nippon Kasei Kogyo Co., Ltd., DC-A4), the kneaded product (40.5 g) produced in Reference Example 2 was placed in a flask, a semi-circular stirring rod with a stirring seal and a Liebig condenser with a receiver were attached, and it was taken out from the nitrogen atmosphere space. A refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled by dry ice. The flask was placed in an oil bath (manufactured by Tokyo Rika Kikai Co., Ltd., OHB-3100S) set at 40°C and stirred. When the setting of the oil bath was changed to 90°C and stirred for 1 hour, it was confirmed that the contents of the flask adhered to the stirring rod and the inner surface of the flask and could not be stirred. From this, it was determined that solidification occurred in this comparative example.

[0085] [Comparative Example 5] In a space with a nitrogen atmosphere dried by a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), the kneaded product (39.7 g) produced in Reference Example 3 was placed in a flask, a half-moon-shaped stirring rod with a stirring seal and a Liebig condenser with a receiver were attached, and the flask was taken out of the space with a nitrogen atmosphere. A refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, stirred, and the oil bath was set to 90°C and stirred for 1 hour, and it was confirmed that the contents of the flask were attached to the stirring rod and the inner surface of the flask, and stirring was not possible. From this, it was determined that solidification occurred in this comparative example.

[0086] [Example 15] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (12.9 g, 90.7 mmol) and zirconia A (171 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing trifluoromethanesulfonic acid (Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were attached, and the flask was removed from the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and trifluoromethanesulfonic acid was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of trifluoromethanesulfonic acid introduced into the flask was 25.2 g (168 mmol). The oil bath was set to 90°C, and the mixture was stirred at 90 kPaA, during which the distillate was gradually collected in the receiver. After confirming that no more distillate was being removed, the stirring was stopped. After the flask was purged with nitrogen, it was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, and the receiver was removed from the ethanol cooled with dry ice and allowed to return to room temperature. The Liebig condenser was removed from the flask, and the flask was then sealed with a glass stopper, after which it was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 19.9 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed, 19 F-NMR analysis revealed that 19.1 g (67.8 mmol, yield 80.7%) of fluorine-containing sulfonic acid anhydride (2) was obtained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, β / α was 0.54 and ε / (γ+δ) was 4.5.

[0087] [Example 16] In a space with a nitrogen atmosphere dried with a dry column (DC-A4, manufactured by Nikka Seiko Co., Ltd.), diphosphorus pentoxide (14.7 g, 104 mmol) and zirconia A (206 g) were placed in a flask, and a crescent-shaped stirring rod with a stirring seal, a Liebig condenser with a receiver, a three-way cock, and a dropping funnel containing nonafluoro-1-butanesulfonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were attached, and the flask was removed from the space with a nitrogen atmosphere. Dry nitrogen was introduced from the three-way cock, a refrigerant at -5°C was circulated through the Liebig condenser, and the receiver attached to the Liebig condenser was cooled with ethanol cooled with dry ice. The flask was placed in an oil bath (OHB-3100S, manufactured by Tokyo Rikakikai Co., Ltd.) set at 40°C, and nonafluoro-1-butanesulfonic acid was gradually dropped while stirring. After the dropping was completed, the dropping funnel and the three-way cock were removed, and a glass stopper was attached. At this time, the amount of nonafluoro-1-butanesulfonic acid introduced into the flask was 30.2 g (101 mmol). The oil bath was set to 90°C and the mixture was stirred for 1 hour, then the mixture was stirred for 20 minutes at 140°C and 10 kPaA. When the oil bath was set to 160°C, the distillate was gradually collected in the receiver. When the distillation slowed down, the pressure was gradually reduced to 2 kPaA. When it was confirmed that the distillation had stopped, the stirring was stopped. After replacing the flask with nitrogen, the flask was removed from the oil bath, the flow of the refrigerant in the Liebig condenser was stopped, the receiver was removed from the ethanol cooled with dry ice, and the temperature was returned to room temperature. The Liebig condenser was removed from the flask, the flask was sealed with a glass stopper, and the flask was moved to a space with a dry nitrogen atmosphere. The mass of the contents of the receiver was measured and found to be 24.4 g. The contents of the receiver (0.30 g), hexafluorobenzene (1.30 g), and benzotrifluoride (0.10 g) were mixed. 19 F-NMR analysis revealed that 23.3 g (40.0 mmol, yield 79.4%) of fluorine-containing sulfonic acid anhydride (2) was obtained. The contents of the flask were transferred to a dry nitrogen atmosphere and passed through a sieve with 11.2 mm openings, resulting in no material remaining on the sieve. In this example, β / α was 1.0 and ε / (γ+δ) was 4.6. [Industrial Applicability]

[0088] According to the production process of the present invention, solidification in the reaction of fluorinated sulfonic acid (1) with diphosphorus pentoxide can be suppressed and fluorinated sulfonic anhydride (2) can be produced in good yield, and therefore the process can be suitably used in the production of raw materials that are useful as catalysts for medicines, organic synthesis, etc., or synthetic raw materials.

Claims

1. The following general formula (2): (R ｆ SO ２ ) ２ O (2) (In the formula, R ｆ is a saturated or unsaturated aliphatic hydrocarbon group, the hydrocarbon group being -CH ２ When the -CH 2 - has a structure, the -CH 2 - may be substituted with a structure having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom, and all of the hydrogen atoms of the hydrocarbon group other than the hydrogen atoms of the -CH 2 - that has been substituted are substituted with fluorine atoms, and R ｆ has 1 to 20 carbon atoms, and two R ｆ They may be the same or different) The present invention relates to a method for producing a fluorine-containing sulfonic acid anhydride (2) represented by the following formula: The following general formula (1): R ｆ SO ３ H (1) (In the formula, R ｆ is a saturated or unsaturated aliphatic hydrocarbon group, the hydrocarbon group being -CH ２ When the -CH 2 - has a structure, the -CH 2 - may be substituted with a structure having an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom, and all of the hydrogen atoms of the hydrocarbon group other than the hydrogen atoms of the -CH 2 - that has been substituted are substituted with fluorine atoms, and R ｆ has 1 to 20 carbon atoms. A fluorine-containing sulfonic acid (1) represented by the formula: Diphosphorus pentaoxide and React in the presence of zirconia, the ratio (ε / (γ+δ)) of the mass (ε) of the zirconia to the total mass (γ+δ) of the mass (γ) of the fluorine-containing sulfonic acid (1) and the mass (δ) of the diphosphorus pentoxide is 0.1 to 100; A manufacturing method comprising:

2. 2. The process according to claim 1, wherein a ratio (β / α) of the amount of substance (β) of said diphosphorus pentoxide to the amount of substance (α) of said fluorine-containing sulfonic acid (1) is 0.1 to 100.

3. The method according to claim 1 or 2, wherein the reaction temperature is from -40 to 300°C.

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